JP7183565B2 - Method for producing a resin composition, and method for producing a molded article using the resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a resin composition and a method for producing a molded article using the resin composition.

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

However, since cellulose fibers are hydrophilic, it is known that they are difficult to disperse in hydrophobic thermoplastic resins and the like. Therefore, various methods of dispersing cellulose fibers in thermoplastic resins and the like have been investigated.

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 fraction of the cellulose I-type crystal component of the cellulose crystals and the cellulose The sum of the fraction of the type II crystalline component and the fraction of the amorphous cellulose component is 1, the fraction of the cellulose type I crystalline component is 0.4 or more, and the fraction of the cellulose type II crystalline component is 0 .1 or more. Patent Document 1 describes that the cellulose/resin composite can uniformly disperse cellulose 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 dissolving the ionic liquid in which the cellulose is dissolved in a polar solvent in which fine resin particles are dispersed is disclosed. a step of adding and reprecipitating cellulose; a step of filtering and washing the solution in which the fine resin particles are dispersed and the cellulose is reprecipitating to form a cellulose/resin powder; heating the cellulose/resin powder; applying pressure to melt the resin and form a cellulose/resin composite.

Further, in Patent Document 1, it is known that cellulose is soluble in ionic liquids, and cellulose solubilized in ionic liquids is added to polar liquids capable of dissolving ionic liquids such as alcohol and water. It is known that the ionic liquid dissolves in a polar solvent and reprecipitates cellulose that is insoluble in liquids such as alcohol and water.

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 cellulose fibers in the ionic liquid, the cost is high and it is not suitable for industrial production.

Accordingly, an object of the present invention is to provide a method for producing a resin composition that is excellent in production cost.

The present inventors have made intensive studies in order to solve the above problems. As a result, the present inventors have found that the above-described problems can be solved by using a predetermined amount of ionic liquid in combination when melt-kneading cellulose fibers in a thermoplastic resin, and have completed the present invention.

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 amount of the ionic liquid added is 100 parts by mass of the cellulose fibers. On the other hand, it relates to the production method, which is less than 20 parts by mass.

ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the resin composition which is excellent in manufacturing cost is provided.

DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below.

<Method for producing resin composition>
A method for producing a resin composition according to the present embodiment includes melt-kneading a mixture containing a thermoplastic resin and cellulose fibers in the presence of an ionic liquid. At this time, the amount of the ionic liquid added is less than 20 parts by mass with respect to 100 parts by mass of the cellulose fibers.

The production method disperses the cellulose fibers and/or the defibrated product in the thermoplastic resin while defibrating at least a portion of the cellulose fibers in the process of melt-kneading (that is, in the process of melt-kneading , defibration and dispersion of cellulose fibers can occur simultaneously). In this case, when a predetermined amount of ionic liquid is used together, defibration and dispersion of cellulose fibers surprisingly proceed favorably. As a result, it is possible to obtain a resin composition in which the cellulose fibers are suitably defibrated and dispersed in the thermoplastic resin.

Although the reason why the above effect is obtained is not necessarily clear, it is believed to be due to, for example, the following mechanism. That is, the ionic liquid swells at least a portion of the cellulose fibers by interacting with the cellulose fibers in the thermoplastic resin. Then, the swollen cellulose fibers can easily undergo fibrillation and dispersion due to force applied during melt-kneading. As a result, the cellulose fibers can be suitably defibrated and dispersed in the thermoplastic resin. It should be noted that the mechanism by which the above effect is obtained is merely a guess, and even if the above effect is obtained by a mechanism other than the above mechanism, it is included in the technical scope of the present invention.

According to the above-described production method, fibrillation and dispersion are performed in the process of melt-kneading, so steps such as dissolution and reprecipitation of cellulose are not required, and the production cost is excellent. Moreover, since the amount of the ionic liquid added is small, the manufacturing cost is excellent.

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

(Thermoplastic resin)
By thermoplastic resin is meant a resin that softens at its glass transition temperature (Tg) or melting point.

The thermoplastic resin is not particularly limited, but polyethylene (PE) resins (high density polyethylene (HDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), ultra 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 (nylon, 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, polyetherimide (PEI) resin, polyketone resin, and the like. 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 preferred.

The thermoplastic resin content is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, based on the total mass of the thermoplastic resin and cellulose fibers. When the content of the thermoplastic resin is 50% by mass or more, the obtained resin composition can be suitably molded into various shapes by heating and melting, which is preferable. On the other hand, if the content of the thermoplastic resin is 99% by mass or less, it is preferable because the resulting resin composition can be reinforced to impart high mechanical properties.

(cellulose fiber)
A cellulose fiber is a material in which cellulose has a fibrous shape. In this specification, "cellulose fiber" means a fibrous cellulose fiber having a width of 100 µm or less.

As described above, the width of the cellulose fibers is 100 μm or less, preferably 75 μm or less, more preferably 4 nm to 50 μm, still more preferably 4 nm to 25 μm. It is preferable that the width of the cellulose fibers is 100 μm or less, because a composite effect appears and the reinforcing effect can be enhanced. In addition, in this specification, the value measured by the following method shall be employ|adopted for "the width of a cellulose fiber." That is, cellulose fibers are observed with a scanning electron microscope (SEM), and straight lines intersecting 20 or more cellulose fibers are provided in one field of view. Then, for all the cellulose fibers crossed on the straight line, the distance between the two points with the smallest numerical value in the observation screen is measured, and the average value is taken as the width of the cellulose fiber.

Also, the fiber length of the cellulose fibers is preferably 100 nm or more, more preferably 500 nm to 10000 μm, even more preferably 1 to 1000 μm. 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 addition, in this specification, the value measured by the following method shall be employ|adopted for "the fiber length of a cellulose fiber." That is, cellulose fibers are observed with a scanning electron microscope (SEM), 25 fields of view are synthesized, 20 cellulose fibers are selected from which the starting point and the end point are observed, and the distance between the two points with the largest numerical value is selected. are measured, and the average value is taken as the fiber length of the cellulose fiber.

The aspect ratio of the cellulose fibers is preferably 30 or more, more preferably 50 or more, even more preferably 50 to 20,000, and particularly preferably 100 to 2,000. A cellulose fiber having an aspect ratio of 30 or more is preferable because high mechanical properties can be obtained. In the present specification, the term "aspect ratio" means the fiber length of cellulose fiber to the width of cellulose fiber (fiber length of cellulose fiber/width of cellulose fiber).

The cellulose fiber is not particularly limited, and known ones are used.

In one embodiment, cellulose fibers include pulp and synthetic fibers, and fibrillated products thereof (fibrillated products). The "width of cellulose fibers" of pulp and synthetic fibers is usually 10 µm or more, preferably 10 to 50 µm, more preferably 20 to 30 µm. In addition, the "width of cellulose fibers" of the defibrated product is usually less than 10 µm, preferably 50 nm to 5 µm.

The pulp is wood pulp such as softwood pulp using fir, pine, etc., hardwood pulp using eucalyptus, poplar, etc.; non-wood pulp such as straw pulp, kenaf pulp, bagasse pulp, bamboo pulp, reed pulp, mulberry pulp, cotton linter pulp; Waste paper pulp and the like obtained by deinking waste paper and the like can be mentioned.

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

In this case, the pulp and the synthetic fiber may be bleached (bleached pulp, etc.) or may not be bleached (unbleached pulp, etc.).

Among the above-mentioned pulps and synthetic fibers, pulp is preferable, and wood pulp is more preferable. More preferably, hardwood bleached kraft pulp (LBKP), hardwood unbleached kraft pulp (LUKP), hardwood oxygen bleached kraft pulp (LOKP), softwood unbleached kraft pulp (NUKP), softwood oxygen bleached kraft pulp (NOKP), Softwood bleached kraft pulp (NBKP) is particularly preferred.

The fibrillated material is not particularly limited, and includes cellulose microfibrils, cellulose nanofibers (CNF), cellulose nanocrystals (CNC), and the like.

Note that the defibrated material contained in the mixture is usually prepared by performing a separate fibrillation treatment in advance. At this time, the defibration treatment may be performed by mechanical treatment, chemical treatment, or a combination thereof. Examples of the method for obtaining a fibrillated product by mechanical treatment include a high-pressure homogenizer method, an underwater facing collision method, a grinder method, a ball mill method, and the like. Moreover, the TEMPO catalytic oxidation method etc. are mentioned as a method of obtaining a fibrillated material by chemical treatment. Further, defibration may be performed by utilizing the force applied during production of the resin composition (for example, during melt-kneading).

These fibrillated products may be applied singly or in combination of two or more.

Cellulose fibers may also contain hemicellulose, lignin, and the like.

The hemicellulose content is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the cellulose fibers. In addition, in this specification, the "content rate of hemicellulose" shall be calculated using the value measured by the detergent analysis method.

The lignin content is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 5% by mass or less, relative to the total mass of the cellulose fibers. In addition, in this specification, "the content rate of lignin" shall be calculated using the value measured by the Klason method.

The above cellulose fibers may be unmodified, or may be modified.

"Cellulose fibers are modified" means that at least one of the hydroxy groups (-OH) at the C2, C3, and C6 positions of the β-glucose molecule constituting cellulose is modified with an acyl group (-COR). , means an ester bond (--OCOR). In this case, the acyl groups may be evenly substituted at the C2, C3 and C6 positions of the β-glucose unit, or may be substituted with a distribution.

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, 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.

The alkenyl group having 2 to 20 carbon atoms is not particularly limited, but vinyl group, allyl group, propenyl group, 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.

Examples of alkynyl groups having 2 to 20 carbon atoms include, but are not limited to, ethynyl, 2-propynyl, and 2-butynyl groups.

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 such substituents include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxy groups, carboxy groups, amino groups, alkylamino groups (--NHR' ₂ ), dialkylamino groups (--NR' ₂ ), a trialkylammonium group (--NR' ₃ ⁺ ), a nitro group, a thiol group and the like. In this case, R' includes 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 present alone or may be present in two or more.

The aromatic group having 6 to 20 carbon atoms is not particularly limited, but includes phenyl group, naphthyl group, anthracenyl group, pentalenyl 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, isobenzofuranyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, carbazolyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenothiazinyl group , phenoxazinyl group, antilysinyl group and the like.

The substituent of the aromatic group having 6 to 20 carbon atoms is not particularly limited, but an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 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 present alone or may be present in 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-tridekenyl group, 2- A carboxy-4-tetradekenyl group, a 1-carboxymethyl-2-heptadekenyl group and a 2-carboxy-3-octadekenyl group are preferred.

When the cellulose fiber is modified and the cellulose fiber contains hemicellulose and lignin, at least one of the hydroxyl groups of the hemicellulose and lignin may be modified.

In addition, when the cellulose fiber has a plurality of Rs described above, each R may be the same or different.

Modification of the above-mentioned cellulose fibers can be carried out using known compounds. For example, when R is a methyl group (when the hydroxy group of the cellulose fiber is modified with an acetyl group to form a methylcarbonyloxy group (--OCOCH ₃ )), acetic acid, acetic anhydride, etc. are used to convert the cellulose fiber into Denaturation can be performed. Moreover, when R is an alkenyl group, the cellulose fiber can be modified by using an alkenylcarboxylic acid. Furthermore, when R is an alkenyl group having a carboxy group as a substituent, cellulose fibers can be modified by using alkenylsuccinic anhydride, alkenyldicarboxylic acid, or the like.

The degree of substitution when the cellulose fiber is modified is preferably 0.05 to 2.0, more preferably 0.1 to 1.0, and 0.1 to 0.8. is more preferred. A degree of substitution of 0.05 or more is preferable because the cellulose fibers can be suitably dispersed in the resin. On the other hand, when the degree of substitution is 2.0 or less, the strength of the cellulose fibers can be maintained and high mechanical properties can be achieved, which is preferable. As used herein, the term "degree of substitution" means the average number of degrees of substitution of hydroxyl groups per β-glucose unit, and is calculated by the following formula.

degree of substitution = 3-DS

In this case, "DS" means the number of hydroxyl groups per β-glucose unit, which can be measured by the following formula.

DS = 0.0113X - 0.0122

In the above formula, X is ^the carbonyl (C =O) is the absorption peak area. The DS can be used to track the reaction because it can be measured sequentially during the cellulose modification 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, the cellulose fiber is preferably pulp, synthetic fiber, more preferably pulp.

In one embodiment, the cellulose fibers are preferably unmodified cellulose, partially modified cellulose (having a degree of substitution of 2 or less, preferably 0.1 to 1).

In addition, the above-mentioned cellulose fibers may be used alone or in combination of two or more.

The content of cellulose fibers is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, more preferably 0.1 to 30% by mass, based on the total mass of the thermoplastic resin and cellulose fibers. More preferably, it is 5 to 25% by 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 cellulose fiber content 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 dispersing agent. The dispersing agent has a function of favorably dispersing the cellulose fibers in the thermoplastic resin.

Dispersants include, but are not particularly limited to, at least one hydrophilic group selected from the group consisting of a hydroxy group, a carboxyl group, a quaternary ammonium group, a phosphate group, a sulfonic acid group, and salts thereof. A hydrophilic group-containing compound, a glycol ether compound, a homopolymer of the hydrophilic group-containing compound or the glycol ether compound, at least one of the hydrophilic group-containing compound and the glycol ether compound, and / or a hydrophobic compound. 1, a (meth)acrylic acid alkyl ester monomer having an alkyl group of 6 to 18 carbon atoms and an acrylic monomer having an amide group, and/or a second copolymer of other monomers, a choline compound, etc. mentioned.

The hydrophilic group-containing compound is not particularly limited, but 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 - hydroxy group-containing compounds such as hydroxybutyl (meth) acrylate, 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-acylglutamic acid; ) Quaternary ammonium group-containing compounds such as acryloyloxy}ethyl]trimethylammonium; Group-containing compounds; sulfonic acid group-containing compounds such as dodecylsulfuric acid, dodecylbenzenesulfonic acid, styrenesulfonic acid, and dimethylsulfosuccinic acid.

At this time, when the hydrophilic group-containing compound is a salt, the counter ion of the salt is not particularly limited. ions) 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.

Glycol ether compounds are not particularly limited as long as they are other than the hydrophilic group-containing compounds described above, and are methoxyethylene glycol (meth)acrylate, ethylethyleneglycol (meth)acrylate, methoxypropyleneglycol (meth)acrylate, and phenoxyethylene. Glycol methacrylate and the like can be mentioned.

The homopolymer is not particularly limited, but poly(meth)acrylic acid, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyphosphoric acid, polystyrenesulfonic acid, methoxypolyethylene glycol (meth)acrylate. , ethyl polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and the like.

The hydrophilic group-containing compound and the glycol ether compound that can be used in the first copolymer are those described above. At this time, the hydrophilic group-containing compound and the glycol ether compound may be used alone, or two or more of them may be used in combination.

Hydrophobic compounds that can be used in the first copolymer are not particularly limited, but 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 , linolel (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate (meth)acrylic monomers such as oxyethyl and benzyl (meth)acrylate; styrene monomers such as styrene, methylstyrene, ethylstyrene and dimethylstyrene; 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, a quaternary A copolymer of an ammonium group-containing compound and a (meth)acrylic monomer, and the like are included. 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)acrylate 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, copolymer of (meth)acrylic acid and methyl (meth)acrylate, copolymer of (meth)acrylic acid and lauryl (meth)acrylate, (meth)acrylic acid and cyclohexyl (meth)acrylate, copolymer of (meth)acrylic acid and t-butylcyclohexyl (meth)acrylate, copolymer of (meth)acrylic acid and isobornyl (meth)acrylate Copolymer of (meth)acrylic acid and (meth)acrylic acid, copolymer of (meth)acrylic acid and dicyclopentenyloxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate Copolymer of benzylated product and methyl (meth)acrylate, copolymer of benzylated product of dimethylaminoethyl (meth)acrylate and lauryl (meth)acrylate, benzylated product of dimethylaminoethyl (meth)acrylate and cyclohexyl (meth)acrylate, copolymer of benzylated dimethylaminoethyl (meth)acrylate and t-butylcyclohexyl (meth)acrylate, benzyl of dimethylaminoethyl (meth)acrylate ( Copolymer of dicyclopentenyloxyethyl meth)acrylate, copolymer of [2-{(meth)acryloyloxy}ethyl]trimethylammonium and methyl (meth)acrylate, [2-{(meth)acryloyl Copolymer of oxy}ethyl]trimethylammonium and lauryl (meth)acrylate, [2-{( Copolymer of meth)acryloyloxy}ethyl]trimethylammonium and cyclohexyl (meth)acrylate, copolymer of [2-{(meth)acryloyloxy}ethyl]trimethylammonium and t-butylcyclohexyl (meth)acrylate Copolymer of [2-{(meth)acryloyloxy}ethyl]trimethylammonium and isobornyl (meth)acrylate, [2-{(meth)acryloyloxy}ethyl]trimethylammonium and (meth)acrylic acid and copolymers 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. preferable. By incorporating the hydrophobic compound into the dispersant by copolymerization, the hydrophobicity of the dispersant can be increased, and the affinity with the thermoplastic resin can be further improved.

The (meth)acrylic acid alkyl ester monomer having an alkyl group having 6 to 18 carbon atoms that can be used in the second copolymer is not particularly limited, but cyclohexyl (meth)acrylate, hexyl (meth)acrylate, 2 - ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and the like. These (meth)acrylic acid alkyl ester monomers having an alkyl group of 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 Methylacrylamide, 6-(meth)acrylamidohexanoic 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 and the like. These amido group-containing acrylic monomers 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 the hydrophilic group-containing compound, the glycol ether compound, 2-methylaminoethyl (meth)acrylate, (meth)acrylic acid Tetrahydrofurfuryl, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, glycidyl (meth)glycidyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate 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 copolymers of hexyl (meth) acrylate and (meth) acrylamide, copolymers of hexyl (meth) acrylate and N-methyl (meth) acrylamide, 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 with acrylamide, copolymer of 2-ethylhexyl (meth)acrylate and N,N-dimethyl (meth)acrylamide, copolymer of lauryl (meth)acrylate and (meth)acrylamide, lauryl (meth) Copolymer of acrylate and N-methyl(meth)acrylamide, copolymer of lauryl(meth)acrylate and N,N-dimethyl(meth)acrylamide, lauryl(meth)acrylate, (meth)acrylamide and (meth) A copolymer with acrylic acid, a copolymer of lauryl (meth)acrylate, (meth)acrylamide, and methyl (meth)acrylate, and the like can be mentioned. The second copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer, provided that it is a random copolymer or a block copolymer. is preferred.

The choline compound is not particularly limited, but 2-(meth)acryloyloxymethylphosphorylcholine, 2-(meth)acryloyloxyethylphosphorylcholine, 2-(meth)acryloyloxymethylphosphorylcholine-methyl(meth)acrylate copolymer. , 2-(meth)acryloyloxymethylphosphorylcholine-ethyl (meth)acrylate copolymer, 2-(meth)acryloyloxymethylphosphorylcholine-(meth)propylacrylate copolymer, 2-(meth)acryloyloxymethylphosphorylcholine -(meth)butyl acrylate copolymer, 2-(meth)acryloyloxymethylphosphorylcholine-(meth)capryl acrylate copolymer, 2-(meth)acryloyloxymethylphosphorylcholine-(meth)lauryl acrylate copolymer , 2-(meth)acryloyloxymethylphosphorylcholine-(meth)myristyl acrylate copolymer, 2-(meth)acryloyloxymethylphosphorylcholine-(meth)stearyl acrylate copolymer, 2-(meth)acryloyloxymethylphosphorylcholine -(meth)oleyl acrylate copolymer, 2-(meth)acryloyloxyethylphosphorylcholine-(meth)methylacrylate copolymer, 2-(meth)acryloyloxyethylphosphorylcholine-(meth)ethyl acrylate copolymer , 2-(meth)acryloyloxyethylphosphorylcholine-propyl(meth)acrylate copolymer, 2-(meth)acryloyloxyethylphosphorylcholine-butyl(meth)acrylate copolymer, 2-(meth)acryloyloxyethylphosphorylcholine -(meth)capryl acrylate copolymer, 2-(meth)acryloyloxyethylphosphorylcholine-(meth)lauryl acrylate copolymer, 2-(meth)acryloyloxyethylphosphorylcholine-(meth)myristyl acrylate copolymer , 2-(meth)acryloyloxyethylphosphorylcholine-(meth)acrylate stearylcholine copolymer, 2-(meth)acryloyloxyethylphosphorylcholine-(meth)acrylate oleylcopolymer and the like.

Among the above, the dispersant is preferably the first copolymer, the second copolymer, the choline compound, more preferably the second copolymer, 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 (meth) ) acrylamide, N,N-diethyl(meth)acrylamide, and N,N-dipropyl(meth)acrylamide are more preferably copolymers containing lauryl (meth)acrylate, stearyl (meth)acrylate, and (meth)acrylamide. ) copolymers containing acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl(meth)acrylamide are particularly preferred.

The amount of the dispersant added 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 amount of the dispersant added is 1 part by mass or more because the cellulose fibers can be more finely dispersed. On the other hand, when the amount of the dispersant added is 200 parts by mass or less, it is preferable because deterioration in the performance of the resin composition due to heat deterioration and bleeding out can be suppressed.

(solvent)
In one embodiment, the mixture may contain a solvent.

Examples of the solvent include, but are not limited to, water and organic solvents.

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 and 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; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like are included. Among these, alcohols and ketones are preferably used as the organic solvent, 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 types.

The content of the solvent is preferably 1000 parts or less, more preferably 200 parts or less, per 100 parts of the solid mass of the mixture. In addition, in this specification, the "solid content of the mixture" means the total mass of the components excluding the solvent in the mixture. Thus, if the mixture does not contain solvent, the total weight of the composition will be solids.

(Additive)
In one embodiment, the mixture may contain additives.

Examples of the additive include, but are not limited to, defibration aids such as urea, urea derivatives, sugars, sugar alcohols, organic acids, and organic acid salts; decomposition products of the fibrillation aids; talc, mica, suumetite, and graphite. , Fillers such as graphene; Flame retardants such as phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants; plasticizers; antioxidants; UV absorbers; light stabilizers agent; antistatic agent; conductivity imparting agent; stress relaxation agent; release agent; crystallization accelerator; Fluid control agent; Dye; Sensitizer; Pigment for coloring; Rubber polymer; Thickener; Anti-settling agent; 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 defibration and dispersion of the cellulose fibers in the thermoplastic resin. As used herein, the term "ionic liquid" means a salt that exists in the form of a liquid at 100° C. or lower and has cations and anions as basic constituents.

The cation of the ionic liquid is not particularly limited, but includes aromatic cations and aliphatic cations. That is, in one embodiment, the ionic liquid includes an ionic liquid having cations selected from the group consisting of aromatic cations and aliphatic cations.

Examples of aromatic cations include, but are not limited to, pyridinium cations, imidazolium cations, aromatic ammonium cations, aromatic sulfonium cations, and the like.

The pyridinium cations include 1-methylpyridinium cation, 1-ethylpyridinium cation, 1-propylpyridinium cation, 3-methyl-1-propylpyridinium cation, 1-butylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-(3-cyanopropyl)pyridinium cation and the like.

Examples of the imidazolium cation include 1-methylimidazolium cation, 1,3-dimethylimidazolium cation, 1,2,3-trimethylimidazolium cation, 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-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-methylimidazolium cation, 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.

Moreover, the aliphatic cation is not particularly limited, but includes aliphatic ammonium cation, pyrrolidinium cation, piperidinium cation, morpholinium cation, phosphonium cation, aliphatic sulfonium cation, choline cation and the like.

Examples of the aliphatic ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, trimethylpropylammonium cation, ethyldimethylpropylammonium cation, diethylmethylpropylammonium cation, tetrabutylammonium cation, butyltrimethylammonium cation, tributyl methylammonium cation, tetrapentylammonium cation, triethylpentylammonium cation, tetrahexylammonium cation, tetraoctylammonium cation, methyltrioctylammonium cation, tetradecylammonium cation, tetradodecylammonium cation, cyclohexyltrimethylammonium cation, dimethyl(2-methoxy ethyl)methylammonium cation, ethyl(2-methoxyethyl)dimethylammonium cation, ethyl(3-methoxypropyl)dimethylammonium cation, tris(2-hydroxyethyl)methylammonium cation, 2-hydroxyethyltrimethylammonium cation, etc. .

The pyrrolidinium cations include 1-butyl-1-methylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-allyl-1-methylpyrrolidinium cation, 1-methyl-1- propylpyrrolidinium cation, 1-(2-methoxyethyl)-1-methylpyrrolidinium cation, and the like.

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 triethylmethylphosphonium cation, tetrabutylphosphonium cation, tributylmethylphosphonium cation, and trihexyltetradecylphosphonium cation.

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

The choline cations include choline cations, acetylcholine cations, fluorocholine cations, chlorocholine cations, and the like.

Among the above, the cation of the ionic liquid is preferably an aromatic cation, more preferably a pyridinium cation, an imidazolium cation, more preferably an imidazolium cation, 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-dimethylimidazolium cation Lithium cations and 1-allyl-3-methylimidazolium cations are particularly preferred.

The anions of the ionic liquid are not particularly limited, but are halide ions, borate anions, carboxylate anions, sulfonate anions, sulfate anions, sulfonimide anions, phosphate anions, phosphate anions, phosphonate anions, di cyanamide anion ((NC) ₂ N ⁻ ), thiocyanate anion (SCN ⁻ ), tricyanometanide anion (C(CN) ₃ ⁻ ), nitrate anion (NO ₃ ⁻ ), and the like. Thus, in one embodiment, the ionic liquid is a halide ion, borate anion, carboxylate anion, sulfonate anion, sulfate anion, sulfonimide anion, phosphate anion, phosphate anion, phosphonate anion, dicyanamide anion, thio Including ionic liquids having anions selected from the group consisting of cyanate anions, tricyanometanide anions, and nitrate anions.

Examples of the halide ion include chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), tribromide ion (Br ₃ ⁻ ), triiodide ion (I ₃ ⁻ ), and the like. 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 include 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 ⁻ ) and ethyl sulfate anion (C ₂ H ₅ SO ₄ ⁻ ).

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

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 methylphosphonate anion (HP(=O)(- _OCH3 ) ^-O- ) _, ethylphosphonate anion (HP(=O)(- _OC2H5 )-O ⁻ ), butylphosphonate anion (HP(=O)(—OC ₄ H ₉ )—O ⁻ ), and the like.

Among the above, the anion of the ionic liquid is preferably a halide ion, a borate anion, a sulfonate anion, a sulfate anion, a sulfonimide anion, a phosphate anion, a phosphate anion, or a phosphonate anion. , borate anions, and phosphonate anions are more preferred, halide ions are even more preferred, and chloride ions are particularly preferred.

The ionic liquid may contain neutral molecules for the purpose of lowering the melting point. Examples of the neutral molecule include, but are not limited to, 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, 2-trifluoroacetamide, imidazole and the like. Among these, ethylene glycol, glycerin, benzoic acid, and urea are preferred as neutral molecules.

The ionic liquid is a combination of the above-described cations and anions, and is not particularly limited. Specific ionic liquids include, for example, 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 methylsulfate, 1,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dimethylimidazolium dimethylphosphate, 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 ethylsulfate, 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(trifluoromethanesulfonyl)imide, benzylethyldimethylammonium bis(trifluoromethanesulfonyl)imide, ethyldimethyl(2-phenylethyl)ammonium bis(trifluoromethanesulfonyl)imide, cyclopropyldiphenylsulfonium tetrafluoroborate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium tetrafluoroborate, tetrapentylammonium chloride, tetrapentylammonium bromide, trahexylammonium chloride, tetrahexylammonium 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, tetrabutylphosphonium chloride, tetra Butylphosphonium bromide, trihexyltetradecylphosphonium chloride, trimethylsulfonium iodide, tributylsulfonium iodide, choline chloride, acetylcholine chloride, chlorocholine chloride, fluorocholine bromide, cholineacetic acid, choline formate, choline propionate and the like.

The ionic liquid may also be a mixture of cations and anions and neutral molecules. Examples of the ionic liquid include 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. Ammonium and urea mixtures, tetrabutylammonium chloride and ethylene glycol mixtures, tetrabutylammonium chloride and glycerin mixtures, tetrabutylammonium chloride and urea mixtures, and the like.

Among these, ionic liquids include 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 methylsulfate, 1,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dimethylimidazolium dimethylphosphate, 1-ethyl-3-methyl imidazolium 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 ethylsulfate, 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(trifluoromethanesulfonyl)imide 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-butyl-3-methylpyridinium bromide, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl -4-methylpyridinium chloride, 1-butyl-4-methylpyridinium bromide, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium bromide, 1-ethyl-3-methylimidazo Lithium chloride, 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 -methylpyridinium bromide, 1,3-dimethylimidazolium 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, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide are more preferred, and 1,3-dimethyl imidazolium 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, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide are particularly preferred, and 1,3-dimethylimidazolium chloride, 1-ethyl-3- Most preferred are methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride.

In addition, the above-mentioned ionic liquids may be used alone or in combination of two or more.

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 100 to 200. is highly preferred, and 130-200 is most preferred. When the molecular weight of the ionic liquid is 400 or less, it is preferable because the tensile modulus of the resulting molded article can be increased.

The amount of the ionic liquid added is less than 20 parts by mass, preferably 0.01 parts by mass or more and less than 20 parts by mass, and more preferably 0.3 to 18 parts by mass with respect to 100 parts by mass of cellulose fibers. , more preferably 3 to 15 parts by mass, and particularly preferably 4 to 12 parts by mass. When the amount of the ionic liquid to be added is less than 20 parts by mass, it is preferable because the tensile modulus of the resulting molded article can be increased while being excellent in production cost.

In another embodiment, the amount of ionic liquid added is preferably 0.3 to 18 parts by mass, more preferably 0.75 to 15 parts by mass, with respect to 100 parts by mass of cellulose fibers. It is preferably from 1 to 12.5 parts by mass, and particularly preferably from 2 to 7.5 parts by mass. When the amount of the ionic liquid to be added is within the above range, it is preferable because the tensile strength of the molded article obtained is high while the production cost is excellent.

[Melt kneading]
A resin composition can be obtained by melt-kneading the above 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, dispersant, ionic liquid, etc. during melt-kneading, if necessary.

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

The melt-kneading time varies depending on the thermoplastic resin used, but is preferably 1 to 30 minutes, more preferably 3 to 20 minutes.

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

The resin composition contains a thermoplastic resin, cellulose fibers and/or fibrillated products thereof, and an ionic liquid. At this time, 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 were not defibrated in the process of melt-kneading, those that were defibrated but whose degree of fibrillation was low, 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 portion of the cellulose fibers may be defibrated during the melt-kneading process. That is, the cellulose fibers in the mixture and the cellulose fibers in the resin composition may differ in cellulose fiber width, fiber length, aspect ratio, and the like.

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

For measuring the width and length of the cellulose fibers present in the resin composition, cellulose fibers for measurement prepared by the following method are used. That is, first, a composition sample of 1 cm×1 cm×0.1 mm is prepared. The sample is then immersed in an extraction solvent to extract the thermoplastic resin of the sample. At that time, it may be heated and boiled. Then, the cellulose fibers for measurement can be obtained by drying the remaining cellulose fibers. The extraction solvent for extracting the thermoplastic resin differs depending on the thermoplastic resin 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.

The ionic liquid, dispersant, solvent, additive, etc. in the resin composition are basically the same as described above. These particles may also differ in shape, average particle diameter, etc. between those in the mixture before melt-kneading and those in the resulting resin composition.

<Method for manufacturing molded body>
According to one aspect of the present invention, a method for manufacturing a compact is provided. A method for producing a molded article includes molding the resin composition produced by the method described above.

A method for molding the composition is not particularly limited, and a known method can be appropriately employed. Specific types include compression molding, injection molding, extrusion molding, blow molding, foam molding, and the like. 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 fibers and/or fibrillated materials, a dispersant, etc. to the resin composition before or during molding.

Molded bodies obtained in this manner have excellent mechanical properties, and are therefore used as interior materials, exterior materials, structural materials, etc. for automobiles, trains, ships, airplanes, etc.; It can be suitably applied to housings, structural materials, internal parts, etc. of reproducing equipment, video reproducing equipment, printing equipment, copying equipment, sporting goods, building materials, office equipment such as stationery, containers, containers, and the like.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. In the examples, "parts" or "%" are used, but "mass parts" or "mass%" are indicated unless otherwise specified.

[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. Acrylamide 135.3 parts by mass, lauryl methacrylate 108.2 parts by mass, methyl acrylate 2.5 parts by mass, IPA 246 parts by mass, a polymerization initiator (azo initiator, manufactured by Wako Pure Chemical Industries, Ltd.) 4 parts by mass, and a dissolved mixture of 10 parts by mass of methyl ethyl ketone (MEK) was added dropwise over 2 hours, and the reaction was carried out at 73 to 77°C. Then, the reaction vessel was maintained at 73 to 77° C. for 2 hours to complete the polymerization reaction. After removing the solvent from the obtained resin solution using a vacuum pump under conditions of 0.08 to 0.095 MPa and 60 ° C., it is dried by heating at 80 ° C. for 30 minutes using a dryer to remove the solid. 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 high-speed GPC HLC-8220 (manufactured by Tosoh Corporation), column (TSK-GELGMHXL × 2), 200 mL of a solution of 5 mg of sample dissolved in 10 g of tetrahydrofuran (THF) was injected into the apparatus, flow rate: Measurement was performed at 1 mL/min (THF), constant temperature bath temperature: 40° C., and a differential refraction (RI) detector.

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 cellulose fiber (width: 50 μm, fiber length: 2 mm, manufactured by Howe Sound Pulp and Paper), 30 parts of dispersant , and 0.05 part of ionic liquid 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) were mixed. The resulting mixture was melt-kneaded for 10 minutes at 140° C. and 200 rpm in a small kneader (manufactured by Leo Labo Co., Ltd.) 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 prepared in the same manner as in Example 1, except that the amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) added was changed to 0.25 parts.

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

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

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

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

[Example 7] (However, Example 7 is a comparative example)
A resin composition was prepared in the same manner as in Example 5, except that no dispersant was 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 prepared in the same manner as in Example 1, except that the amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) added was changed to 20 parts.

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

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

(Manufacturing method of compact)
Using a small injection molding machine (manufactured by Leo Labo Co., Ltd.), the resin composition is injection molded under the conditions of a mold temperature of 50 ° C. and a cylinder temperature of 150 ° C., and a tensile test specimen ( length 74 mm, width 5 mm, thickness 2 mm).

(tensile modulus)
The test piece for the tensile test produced above is used with a tensile tester "AUTOGRAPH AGS-X" (manufactured by Shimadzu Corporation), tensile speed: 50 mm / min, distance between chucks: 50 mm, temperature: 23 degrees, humidity: Tensile modulus was measured under the condition of 50%. The results obtained are shown in Table 1 below.

(tensile strength)
The test piece for the tensile test produced above is used with a tensile tester "AUTOGRAPH AGS-X" (manufactured by Shimadzu Corporation), tensile speed: 50 mm / min, distance between chucks: 50 mm, temperature: 23 degrees, humidity: Tensile strength was measured under the condition of 50%. The results obtained are shown in Table 1 below.

From the results in Table 1, according to the production method of the example, fibrillation 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, it is excellent in manufacturing cost.

It is also found that the molded article obtained from the resin composition produced by the above method has excellent mechanical properties such as high tensile modulus and tensile strength.

Claims (3)

A method for producing a resin composition, comprising melt-kneading a mixture containing a thermoplastic resin , cellulose fibers and a dispersant in the presence of an ionic liquid,
The amount of the ionic liquid added is less than 20 parts by mass with respect to 100 parts by mass of cellulose fibers ;
The ionic liquid contains an ionic liquid having a cation selected from the group consisting of aromatic cations and aliphatic cations;
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 comprising an ionic liquid having an anion selected from the group consisting of a methanide anion and a nitrate anion;
The production method, wherein the dispersant is a copolymer obtained by using a (meth)acrylic acid alkyl ester monomer having an alkyl group of 6 to 18 carbon atoms and an acrylic monomer having an amide group. The production method according to claim 1, wherein the ionic liquid has a molecular weight of 400 or less. A method for producing a molded article, comprising molding the resin composition produced by the method according to claim 1 or 2 .