JP2019065137A - bumper - Google Patents

Abstract

To provide a bumper having a resin part that is formed using a thermoplastic resin composition in which fine cellulose is uniformly dispersed in a thermoplastic resin.SOLUTION: A bumper has a resin part which is formed of a thermoplastic resin composition that contains a thermoplastic synthetic resin, cellulose and an ionic compound, where a content of the cellulose is 1-100 pts.mass based on 100 pts.mass of the thermoplastic resin, and a content of the ionic compound is 0.001 time or more and less than 1.000 time the cellulose.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a bumper, in particular to a bumper for a vehicle. More specifically, the present invention relates to a bumper provided with a resin portion formed of a thermoplastic resin composition containing cellulose, particularly fibrous cellulose of plant origin and an ionic compound.

  The bumper, which is one of the exterior parts of a vehicle such as a car, protects the vehicle body and protects the passenger's body, and at the same time the object or person who collided, when the vehicle collides with an obstacle or the like and receives an impact. It acts as a shock absorbing member that minimizes the damage to the people as much as possible. As materials for such vehicle bumpers, thermoplastic resins such as polyethylene and polypropylene are often used from the viewpoint of appropriate flexibility. Further, the exterior member for a vehicle is required to have high rigidity and impact resistance in order to improve safety and quality. Therefore, reinforcing fibers such as glass fibers and carbon fibers have been used as a reinforcing material in thermoplastic resins.

However, molded articles of fiber-reinforced thermoplastic resin (hereinafter also referred to as "FRTP") of reinforcing fibers such as glass fibers and carbon fibers and a thermoplastic resin have surface smoothness due to the floating of these fibers on the surface. It may be damaged, resulting in poor appearance. Therefore, development of FRTP excellent in surface smoothness is desired. In recent years, reinforcing materials for thermoplastic resins are also required to have high recyclability with less concern about resource exhaustion in order to reduce environmental impact. Furthermore, in vehicles such as automobiles, further weight reduction is also being considered in order to improve fuel consumption from the viewpoint of regulation of CO ₂ emissions.

  In order to meet the above-mentioned requirements, cellulose is considered promising as a reinforcing material for thermoplastic resins. Cellulose is a natural resource that is abundant and renewable on earth, and thus is suitable as a highly recyclable material. Cellulose is also known to be lightweight, and its mechanical properties are increased by refining it to a minute size, and when it is refined to nano size, it becomes a material with extremely high elastic modulus and high strength. There is. Furthermore, finely divided cellulose has better surface smoothness than glass fibers and carbon fibers. The research which utilizes the cellulose which has such a characteristic as a reinforcing material of a thermoplastic resin is also done, and the possibility is noted.

  As a method for producing a composite resin comprising such cellulose fine fibers and a thermoplastic resin, first, plant fibers are fibrillated (microfibrillated), and the microfibrillated plant fibers (cellulose fine fibers) are obtained. There is known a method of mixing and kneading with a thermoplastic resin such as polypropylene, using a compatibilizer and an interfacial reinforcing material, in order to control the dispersibility and the interface between the fiber and the resin (for example, Patent Document 1). However, in such a method, at least the step of disaggregating (microfibrillating) plant fibers and the step of mixing and combining the microfibrillated plant fibers (cellulose-based fine fibers) with a thermoplastic resin including. For this reason, in addition to the procedure becoming complicated and manufacturing cost becoming high, it is easy to re-aggregate when knead | mixing to a thermoplastic resin, and it is the fact that the control is difficult.

  Recently, a method has been proposed in which vegetable fibers are chemically treated to modify the surface, and then the modified vegetable fibers and the thermoplastic resin are kneaded with a processing machine (see, for example, Patent Document 2). This method is a method of promoting refinement of plant fibers while kneading denatured plant fibers together with a thermoplastic resin in a processing machine. However, although such a method is also improved as compared with the above-mentioned method, since the plant fiber is once swollen, treated with the chemical substance, dried and then introduced into the processing machine in the step of chemical treatment. However, the procedure is complicated and there is a limit in cost reduction.

  In addition, when damage due to a collision or the like occurs on the surface of the bumper, it is usually repaired by painting or the like. However, most of the bumpers are formed of polyethylene, polypropylene or the like having a low surface free energy, and therefore have a drawback in that they have poor adhesion (adhesion) to the paint. Therefore, there was a possibility that a painted surface exfoliated and a repair part was exposed.

U.S. Patent Application Publication No. 2008/0146701 International Publication No. 2013/133093

  In view of the problems with bumpers using conventional materials, the present invention enables the micronization of cellulose and is formed using a thermoplastic resin composition in which the micronized cellulose is uniformly dispersed in a thermoplastic resin. It is an object of the present invention to provide a bumper provided with a resin portion.

  As a result of intensive studies to solve the above problems, the present inventors uniformly dispersed finely divided cellulose in a thermoplastic resin by causing an ionic substance to be present in addition to the cellulose and the thermoplastic resin. It has been found that a cellulose reinforced thermoplastic resin which is a composite resin is obtained, and a bumper provided with a resin portion formed of the cellulose reinforced thermoplastic resin is obtained.

As a result of further studies based on the above findings, it was found that the above problems can be achieved by the following configurations.
[1] A thermoplastic synthetic resin, cellulose and an ionic compound are contained, and the content of the cellulose is 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic synthetic resin, and the content of the ionic compound is the A bumper provided with a resin portion formed of a thermoplastic resin composition that is 0.001 times or more and less than 1.000 times that of cellulose.
[2] The bumper according to [1], wherein the ionic compound is represented by the following general formula (1) or (2).

In the general formulas (1) and (2), Z ¹ represents = C (Ra)-or = N-. Here, Ra represents a hydrogen atom or a substituent. L ¹ represents a divalent linking group. Each of R ^{1 to} R ⁵ independently represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of R ^{2 to} R ⁵ may bond to each other to form a ring. X < ^- > shows an anion.
[3] The compound represented by the general formula (1) or (2) is described in [2] represented by any of the following general formulas (1a), (1b), (2a) to (2c) Bumper.

Formula (1a), in (1b), (2a) ~ (2c), R 1, R 2 and X ^- is, ^R 1 in the general formula (1) or (2), ^{R 2} and X ^- synonymous It is. R ¹¹ and R ¹² each independently represent a substituent. n ¹¹ is an integer of 0 to 3, and n ¹² is an integer of 0 to 5. Here, when R ¹¹ is 2 or more, plural R ^{11 s} may be the same as or different from each other. In addition, at least two R ¹¹ may be bonded to each other to form a ring.
R ¹³ to R ¹⁵ each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. However, at least two of R ² and R ^{13 to} R ¹⁵ are not bonded to each other to form a ring. R ²¹ has the same meaning as R ² . Z ² is a single bond, a methylene group, -C (= O)-, -O-, -S-, -S (= O)-, -SO _2- , -N (Rα1)-or -N ⁺ (Rα1 ) (Rα2)-, Rα1 represents a hydrogen atom or a substituent, and Rα2 represents a substituent. Here, Rα1 and Rα2 may be bonded to each other to form a ring.
[4] The compound according to [2] or [3], wherein X ^- is a halogen ion, a carboxylate anion, a sulfonate anion, a phosphate anion, a phosphonate anion, a dicyanamide ion or a bis (trifluoromethanesulfonyl) imide ion bumper.
[5] The bumper according to any one of [1] to [4], wherein the cellulose is fibrous cellulose of plant origin.
[6] The bumper according to any one of [1] to [5], wherein 15% or more of the cellulose has a short side length of 2 μm or less.
[7] The bumper according to any one of [1] to [6], wherein the area of the cellulose aggregate of the thermoplastic resin composition is less than 20000 μm ² .

In the present invention, it has become possible to provide a bumper provided with a resin portion in which finely divided cellulose is uniformly dispersed and contained in a thermoplastic resin without aggregation or reaggregation.
That is, by simply kneading the fibrous cellulose (pulp) of plant origin containing an ionic compound with the thermoplastic resin, it is possible to advance the refining of the pulp in the process.
For this reason, the process which refine | miniaturizes fibrous cellulose derived from a plant beforehand becomes unnecessary, and significant reduction of manufacturing cost can be anticipated. In addition, since the elastic modulus is increased by the finely divided cellulose, the reinforcement efficiency of the bumper provided with the resin portion can be enhanced.
As described above, according to the present invention, it is possible to provide a bumper provided with a resin part of finely divided cellulose fibers, and a significant reduction in manufacturing cost can be expected.
Further, in the present invention, since a cellulose reinforced thermoplastic resin obtained by heat-kneading a thermoplastic resin composition is used, weight reduction and high strength can be achieved, as well as recyclability, surface smoothness, and the like. It becomes possible to realize a bumper provided with a resin part excellent in adhesion performance.

FIG. 1 is a perspective view showing a vehicle bumper having a resin portion according to an embodiment of the present invention. FIG. 2 is a partially cutaway perspective view showing the back side of the vehicle bumper of FIG.

  The bumper provided with the resin portion of the present invention, particularly the resin portion of the bumper contains a thermoplastic synthetic resin, cellulose and an ionic compound, and the content of the cellulose is 1 to 100 mass with respect to 100 mass parts of the thermoplastic synthetic resin. The thermoplastic resin composition is a part, and the content of the ionic compound is 0.001 times or more and less than 1.000 times that of the cellulose.

<< Thermoplastic resin composition >>
The thermoplastic resin composition for forming the resin portion of the bumper according to the present invention contains at least a thermoplastic synthetic resin, cellulose and an ionic compound.
First, the thermoplastic synthetic resin will be described in order.

<Thermoplastic synthetic resin>
The thermoplastic synthetic resin used in the present invention is not particularly limited, and any synthetic resin generally used as a thermoplastic synthetic resin may be used.
This is due to the reason described below.

In the present invention, as described below, the cellulose is made finer by kneading the cellulose and the ionic compound in the thermoplastic synthetic resin.
For this reason, the viscosity of the thermoplastic synthetic resin at the time of mixing with cellulose becomes an important characteristic.
That is, the stress (Fh) which a dispersion of cellulose (including an ionic compound) present in the thermoplastic synthetic resin feels in a shear field is simply expressed by the following formula (1.1).

なお、上記式（１．１）において・付きγを、以下では、単にγとして説明する。
上記分散体がせん断場で感じる応力（Ｆｈ）は、γのせん断速度を持つ粘度ηの熱可塑性合成樹脂内で、半径Ｒの球形フィラーが感じる力を表している。
ただし、熱可塑性合成樹脂中に存在するセルロースは球状ではなく繊維状であるため、このままの式を適用できないが、原理的には同じことであり、上記分散体がせん断場で感じる応力（Ｆｈ）に影響するパラメーター（η、γ、Ｒ）も同じであると考えられる。
従って、セルロースを微細化するためには、熱可塑性合成樹脂内のせん断場で、いかに大きな力をかけられるかが重要であるため、ηもしくはγが大きいほど有利になると考えられる。

In the above equation (1.1), the appended γ will be described simply as γ below.
The stress (Fh) felt by the dispersion in the shear field represents the force felt by the spherical filler of radius R within the thermoplastic synthetic resin of viscosity η having a shear rate of γ.
However, since the cellulose present in the thermoplastic synthetic resin is not spherical but in the form of fibers, the formula as it is can not be applied, but the principle is basically the same, and the stress felt by the dispersion in a shear field (Fh) The parameters affecting (, γ, R) are also considered to be the same.
Therefore, in order to refine cellulose, it is important how large force can be applied in the shear field in the thermoplastic synthetic resin, so it is considered that the larger η or γ, the more advantageous.

Here, to increase the shear rate (γ) means to increase the shear rate applied mechanically to the thermoplastic synthetic resin.
Therefore, when the shear rate (γ) is increased, the force felt by the cellulose in the thermoplastic synthetic resin is increased, but the friction force due to the kneading is simultaneously increased, and the temperature of the thermoplastic synthetic resin is increased.
However, since cellulose generally discolors when it exceeds 200 ° C. and it is thermally decomposed from near 300 ° C., a method of exposing to a shear field that extremely raises the temperature is characteristic of the material. It is not appropriate from the viewpoint of maintaining.

From this, it is important to increase the viscosity (η) of the thermoplastic synthetic resin in order to make the cellulose finer.
Generally, the viscosity (η) of a thermoplastic synthetic resin satisfies the following relationship (Andredo's equation).

Here, A is a constant of proportionality, Ev is a fluid activation energy, R is a gas constant, and T is a temperature (K). The flow activation energy corresponds to the activation energy in Arrhenius's chemical reaction, and is understood by regarding flow as a velocity process.
Thus, an important parameter to control viscosity (η) is temperature.
The temperature can be manipulated and adjusted as the processing temperature regardless of the type of thermoplastic synthetic resin.
Therefore, thermoplastic synthetic resin as a medium which gives the force necessary to refine cellulose is widely applicable without any particular limitation.

Examples of the thermoplastic synthetic resin include polyolefin resin, polyester resin, polycarbonate resin, polyamide resin, polyimide resin, polyurethane resin, polyphenylene sulfide resin, polyphenylene oxide resin, cellulose acylate resin, phenoxy resin and the like.
Among these, in the present invention, a polyolefin resin is preferred.

<Polyolefin resin>
The polyolefin resin is a polyolefin resin formed by polymerizing at least one olefin, and may be a homopolymer or a copolymer.
As such an olefin, for example, ethylene, propylene, isobutylene, α-olefin having 4 to 12 carbon atoms including isobutene (1-butene), butadiene, isoprene, (meth) acrylic acid ester, (meth) acrylic acid And (meth) acrylamide, vinyl alcohol, vinyl acetate, vinyl chloride, styrene, acrylonitrile and the like.

  Examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, and the like. -Ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene 1-heptene, methyl 1-hexene, dimethyl 1-pentene, ethyl 1-pentene, trimethyl 1-butene, methyl ethyl 1-butene, 1-octene, methyl 1-pentene, ethyl 1- Hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-none , 1-decene, 1-undecene, and 1-dodecene, and the like.

  Examples of polyolefin resins include polyethylene resins, polypropylene resins, polyisobutylene resins, polyisobutene resins, polyisoprene resins, polybutadiene resins, (meth) acrylic resins (so-called allyl resins), vinyl resins such as polyvinyl chloride resins, and poly (meth) resins. 2.) Acrylamide resin, polystyrene resin, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), ethylene / (meth) acrylate copolymer, ethylene / vinyl acetate copolymer, etc. may be mentioned.

  Among these resins, polyethylene resin, polypropylene resin, acrylonitrile / butadiene / styrene copolymer resin (ABS resin) are preferable, and polyethylene resin and polypropylene resin are particularly preferable.

  As a polyethylene resin, an ethylene homopolymer, an ethylene-alpha-olefin copolymer, etc. are mentioned. As the α-olefin, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  Examples of the ethylene-α-olefin copolymer include ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer and the like. It can be mentioned.

  When classified by density or shape, high density polyethylene (HDPE), low density polyethylene (LDPE), ultra low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMW-PE) Any of) may be used.

  As a polypropylene resin, a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer, a propylene-ethylene-α-olefin copolymer, a propylene block copolymer (propylene homopolymer component Or a copolymer component obtained by copolymerizing propylene and a copolymer component mainly composed of propylene, and at least one of monomers selected from ethylene and α-olefin, and the like. These polypropylene resins may be used alone or in combination of two or more.

  The α-olefin used for the polypropylene resin is preferably 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-butene, 1-hexene, 1- Octene is more preferred.

  Examples of the propylene-α-olefin random copolymer include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, and a propylene-1-octene random copolymer.

  Examples of the propylene-ethylene-α-olefin copolymer include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. Be

  As a propylene block copolymer, for example, (propylene)-(propylene-ethylene) copolymer, (propylene)-(propylene-ethylene-1-butene) copolymer, (propylene)-(propylene-ethylene-1) -Hexene) copolymer, (propylene)-(propylene-1-butene) copolymer, (propylene)-(propylene-1-hexene) copolymer, (propylene-ethylene)-(propylene-ethylene) copolymer Combined, (propylene-ethylene)-(propylene-ethylene-1-butene) copolymer, (propylene-ethylene)-(propylene-ethylene-1-hexene) copolymer, (propylene-ethylene)-(propylene-1) -Butene) copolymer, (propylene-ethylene)-(propylene 1 -hexene) copolymer, (prop -1-butene)-(propylene-ethylene) copolymer, (propylene-1-butene)-(propylene-ethylene-1-butene) copolymer, (propylene-1-butene)-(propylene-ethylene) 1-hexene) copolymer, (propylene-1-butene)-(propylene-1-butene) copolymer, (propylene-1-butene)-(propylene-1-hexene) copolymer, etc. may be mentioned.

  Among these polypropylene resins, a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, a propylene-ethylene-1-butene copolymer, and a propylene block copolymer are preferable.

The crystallinity of the polypropylene resin is determined by the melting temperature (melting point) or stereoregularity, and is adjusted according to the quality required of the polyolefin resin composition and the quality required of a molded product obtained by molding it.
The stereoregularity is referred to as isotactic index or syndiotactic index.

The isotactic index is determined by the ¹³ C-NMR method described in Macromolecules, Vol. 8, p. 687 (1975). Specifically, the isotactic index of the polypropylene resin is determined as the area fraction of the mmmm peak in the entire absorption peak of the carbon region of the methyl group in the ¹³ C-NMR spectrum.
The compound having high isotactic index is high in crystallinity, preferably 0.96 or more, more preferably 0.97 or more, and still more preferably 0.98 or more.

  On the other hand, syndiotactic indexes are described in J.A. Am. Chem. Soc. , 110, 6255 (1988) and Angew. Chem. Int. Ed. Engl. , 1955, 34, 1143-1170, and having a high syndiotactic index has high crystallinity.

The polyolefin resin may be a modified polyolefin resin, or may include a polyolefin resin modified to a non-modified polyolefin resin.
Kraft modification by unsaturated carboxylic acid or its derivative is mentioned, As unsaturated carboxylic acid, for example, maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid etc. are mentioned, As unsaturated carboxylic acid derivative, For example, maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid Diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester and the like can be mentioned. Among these unsaturated carboxylic acids and / or their derivatives, preferred are acrylic acid, glycidyl ester of methacrylic acid, and maleic anhydride.

As an acrylic resin, for example, homopolymers or copolymers of acrylic monomers such as (meth) acrylic acid, (meth) acrylic acid esters, acrylonitrile and the like, and copolymer of acrylic monomers and other monomers A combination etc. are mentioned.
Among these, (meth) acrylic acid ester is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. (Meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms, hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, glycidyl ester of (meth) acrylic acid, and the like.

  As a specific example of the homopolymer or copolymer of an acryl monomer, poly (meth) acrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, polyacrylonitrile etc. are mentioned, for example. Specific examples of the copolymer of an acrylic monomer and another monomer include, for example, (meth) acrylic acid ester-styrene copolymer, (meth) acrylic acid-styrene copolymer, acrylonitrile-butadiene- A styrene copolymer, an acrylonitrile-styrene copolymer, an acrylonitrile-styrene- (meth) acrylic acid ester copolymer, etc. are mentioned.

  As the vinyl resin, for example, vinyl chloride resin [homopolymer of vinyl chloride monomer (polyvinyl chloride resin etc.), copolymer of vinyl chloride monomer and other monomer (vinyl chloride-vinyl acetate copolymer] Coalesced, vinyl chloride- (meth) acrylic acid ester copolymer etc), vinyl alcohol resin (homopolymer such as polyvinyl alcohol, copolymer such as ethylene-vinyl alcohol copolymer), polyvinyl formal etc. Polyvinyl acetal resin etc. are mentioned. These vinyl resins can be used alone or in combination of two or more.

The melt flow rate (MFR) of the polyolefin resin is usually 0.01 to 400 g / 10 min, preferably 0.1 to 400 g / 10 min from the viewpoint of enhancing mechanical strength and production stability. More preferably, it is 0.5 to 200 g / 10 minutes.
In addition, MFR is mass (g / 10 minutes) of the polymer which flows out out per 10 minutes under 190 degreeC and a 2.16-kg load based on JISK7210 unless there is particular notice.

<Cellulose>
The cellulose used in the present invention is preferably a fibrous cellulose of plant origin, and particularly preferably a fibrous cellulose of fine plant origin (powdery pulp). The bumper provided with the resin portion of the present invention uses cellulose as the compounding material of the resin portion, so that weight reduction and high strength can be achieved, and the recyclability and surface smoothness of the bumper can be improved. . Moreover, since cellulose is a polar molecule which has -OH group, the affinity between molecules is high. Therefore, the interfacial adhesion of the resin portion is improved, and a bumper excellent in adhesion performance can be obtained.
Pulp is also a raw material of paper and is mainly composed of a tracheid extracted from plants. Chemically, the main component is polysaccharides, and the main component is cellulose.
The fibrous cellulose of plant origin is not particularly limited, but for example, wood, bamboo, hemp, jute, kenaf, agricultural waste (eg, straw of wheat or rice, stem of corn, cotton etc., Although those derived from plants such as sugar cane), cloth, recycled pulp, waste paper, wood flour and the like can be mentioned, in the present invention, those derived from wood or wood are preferable, wood flour is more preferable, and kraft pulp is particularly preferable.
Kraft pulp is a general term for pulp from which lignin and hemicellulose are removed from wood or plant material by chemical treatment with caustic soda or the like, and almost pure cellulose is taken out.

  In the present invention, an ionic compound is blended to such a cellulose, and kneading in a thermoplastic synthetic resin is performed to realize refinement of the cellulose.

  Plant-derived fibrous cellulose forms a bundle of 30 to 40 molecules and forms ultrafine-thin, highly crystalline microfibrils with a diameter of about 3 nm and a length of several hundred nm to several tens of μm, and these are soft. A bunched structure is formed through the non-crystal part. The powdered cellulose (powdered pulp) used as the raw material of the present invention is this bundle-like aggregate. The microfibrils are said to have an extremely high elastic modulus, and ideally have an elastic modulus of about 140 GPa, because the cellulose molecular chains that constitute them are extended chain crystals. In addition, it is known that the elastic modulus of cellulose increases as the wire diameter decreases. Therefore, in order to improve the performance as a reinforced resin, it is more effective as the diameter of the cellulose dispersed in the thermoplastic synthetic resin is reduced and finer.

In the present invention, the finely divided cellulose is preferably a rod-like fiber cellulose. The form of rod-like fibers is not particularly limited, and straight fibers and bent fibers can be mentioned.
The short side length (diameter) is preferably 2 μm or less, more preferably 3 nm to 2 μm, more preferably 3 nm to 1 μm, still more preferably 3 nm to 0.5 μm, and particularly preferably 4 to 300 nm. On the other hand, 0.03-500 micrometers is preferable and, as for long side length (length), 0.05-200 micrometers is more preferable. The aspect ratio is preferably 5 or more, and more preferably 10 to 1,000. The aspect ratio is a value obtained by dividing the average length by the average fiber diameter.

  Further, in the present invention, it is preferable that in the finely divided cellulose, 15% or more of the contained cellulose has a short side length of 2 μm or less. 20% or more is more preferable, and, as for content of the cellulose fiber of short side length 2 micrometers or less, 25% or more is further more preferable.

In the present invention, it is further preferable that the finely divided cellulose is uniformly dispersed in the thermoplastic resin composition without aggregation or reaggregation.
Therefore, even if cellulose aggregates are present, the area of the cellulose aggregates present is preferably less than 20000 μm ² . That is, even if the cellulose aggregate is present, it is preferable that the area of the largest aggregate among the existing aggregates is less than 20000 μm ² .
The short side length and the area of the cellulose aggregate can be measured by an electron microscope or an industrial microscope.
Specifically, it is as described in the examples.

In the present invention, the content of cellulose is 1 to 100 parts by mass, preferably 5 to 70 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic synthetic resin.
If the content of cellulose is less than 1 part by mass, transmission of force to cellulose does not effectively occur during kneading, and it is difficult to obtain substantially refined cellulose. On the other hand, if it exceeds 100 parts by mass, good dispersion of cellulose in the thermoplastic synthetic resin becomes difficult, and good characteristics for use as a material can not be obtained.

<Ionic compound>
The thermoplastic resin composition used in the present invention contains an ionic compound together with cellulose.
The ionic compound used in the present invention is preferably one generally referred to as an ionic liquid.
An ionic liquid is a salt which exists as a liquid in a wide temperature range, and is a liquid consisting only of ions. In general, a salt having a melting point of 100 ° C. or less is defined as an ionic liquid (IL), and an ionic liquid having a melting point near room temperature is referred to as “RTIL (room temperature IL)”.

The ionic compound used in the present invention is generally preferably referred to as an ionic liquid, but the melting point may be over 100 ° C., for example, 150 ° C. or more.
That is, in the present invention, at the stage of extruding cellulose reinforced resin or cellulose reinforced resin composition, and processing and molding by injection etc, in order to refine cellulose by kneading in processing machine, temperature in processing process and processing machine Can be set to the melting point or more of the ionic compound. Therefore, for example, even if the melting point of the ionic compound is 180 ° C., the same action as a so-called ionic liquid can be expected by processing at a temperature higher than 180 ° C., for example, 190 ° C.

  In the present invention, the ionic compound is preferably an organic ionic compound, and is preferably an onium salt such as quaternary phosphonium salt or quaternary ammonium salt, and among these, it is represented by the following general formula (1) or (2) Compounds are preferred.

In the general formulas (1) and (2), Z ¹ represents = C (Ra)-or = N-. Here, Ra represents a hydrogen atom or a substituent. L ¹ represents a divalent linking group. Each of R ^{1 to} R ⁵ independently represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of R ^{2 to} R ⁵ may bond to each other to form a ring. X < ^- > shows an anion.

Z ¹ is CC (Ra) — or NN—, preferably CC (Ra) —.

  The substituent in Ra is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acyl group, an acylamino group, a sulfonamide group, carbamoyl Groups, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, sulfonyl group, halogen atom, hydroxy group, carboxy group, sulfo group.

1-20 are preferable, as for carbon number of an alkyl group, 1-12 are more preferable, and 1-8 are more preferable.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, t-pentyl, n-hexyl, n-pentyl, n-octyl and 2-ethylhexyl , N-octyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl.
The alkyl group may have a substituent, and the substituent includes the substituents listed for Ra.

2-20 are preferable, as for carbon number of an alkenyl group, 2-12 are more preferable, and 2-8 are more preferable.
Examples of the alkenyl group include vinyl, allyl and oleyl.
The alkenyl group may have a substituent, and the substituent includes the substituents mentioned for Ra.

The cycloalkyl group is preferably a 3- to 7-membered ring cycloalkyl group, more preferably a 3-, 5- or 7-membered ring cycloalkyl group, and still more preferably a 5- or 6-membered ring cycloalkyl group.
3-20 are preferable, as for carbon number of a cycloalkyl group, 3-12 are more preferable, 5-12 are more preferable, and 5-8 are especially preferable.
Examples of the cycloalkyl group include cyclopropyl, cyclopentyl and cyclohexyl.
The cycloalkyl group may have a substituent, and examples of the substituent include the substituents listed for Ra.

6-20 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6-8 are more preferable.
Examples of the aryl group include phenyl and naphthyl.
The aryl group may have a substituent, and the substituent includes the substituents listed for Ra.

The hetero ring constituting the hetero ring of the hetero ring group is selected from an oxygen atom, a sulfur atom and a nitrogen atom, and a 5- or 7-membered hetero ring is preferable. Further, the hetero ring may be an aromatic ring, an unsaturated ring or a saturated ring.
0-20 are preferable, as for carbon number of a heterocyclic group, 1-12 are more preferable, and 1-8 are more preferable.
The heterocycle of the heterocycle group is, for example, furan ring, thiophene ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Triazine ring, indoline ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrolidine ring, mepyrrolidine ring, imidazolidine ring, imidazoline ring, pyrazoline ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, 1,1-dioxothiomorpholine And rings, 1-oxomorpholine ring, quinuclidine ring, 1,4-diazabicyclo [2.2.2] octane ring, cyanuric acid ring and the like.
In addition, as the benzofuran ring, the benzothiophene ring, the benzoimidazole ring, the benzopyrazole ring, the benzotriazole ring, the benzoxazole ring, and the benzothiazole ring, those condensed with a benzene ring or another ring are also included.
The heterocyclic group may have a substituent, and the substituent includes the substituents listed for Ra.

1-20 are preferable, as for carbon number of an alkoxy group, 1-12 are more preferable, and 1-8 are more preferable.
As an alkoxy group, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentyloxy, t-pentyloxy, n-hexyloxy, n-pentyloxy, n- Examples include octyloxy, 2-ethylhexyloxy, n-octyloxy, n-decyloxy, n-dodecyloxy, n-hexadecyloxy and n-octadecyloxy.
The alkoxy group may have a substituent, and examples of the substituent include the substituents listed for Ra.

6-20 are preferable, as for carbon number of an aryloxy group, 6-12 are more preferable, and 6-8 are more preferable.
Examples of the aryloxy group include phenoxy and naphthoxy.
The aryloxy group may have a substituent, and the substituent includes the substituents listed for Ra.

1-20 are preferable, as for carbon number of an alkylthio group, 1-12 are more preferable, and 1-8 are more preferable.
Examples of the alkylthio group include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, n-pentylthio, t-pentylthio, n-hexylthio, n-pentylthio, n-octylthio, 2 -Ethylhexylthio, n-octylthio, n-decylthio, n-dodecylthio, n-hexadecylthio, n-octadecylthio.
The alkylthio group may have a substituent, and examples of the substituent include the substituents listed for Ra.

6-20 are preferable, as for carbon number of an arylthio group, 6-12 are more preferable, and 6-8 are more preferable.
Examples of the arylthio group include phenylthio and naphthylthio.
The arylthio group may have a substituent, and the substituent includes the substituents mentioned for Ra.

The amino group includes an amino group, an alkylamino group, an arylamino group, and a heterocyclic amino group, and the carbon number of the amino group is preferably 0 to 20, more preferably 0 to 12, and still more preferably 1 to 12 To 8 are particularly preferred.
Examples of the amino group include amino, methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, di-n-propylamino, 2-ethylhexylamino, n-octylamino, dodecylamino, phenylamino, diphenylamino, phenylmethyl Amino is mentioned.
The amino group may have a substituent, and the substituent includes the substituents listed for Ra.

The acyl group includes formyl group, alkanoyl group, acycloalkanoyl group, alkenoyl group, aryloyl group and heterocyclic carbonyl group.
1-20 are preferable, as for carbon number of an acyl group, 2-12 are more preferable, and 2-8 are more preferable.
Examples of the acyl group include formyl, acetyl, propionyl, butyryl, valeryl, pivaloyl, lauroyl, palmitoyl, stearoyl, cyclopropylcarbonyl, cyclopentylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, acryloyl, methacryloyl, oleyl, benzoyl, naphthoyl, nicotinoyl and isonicotininoyl. Be
The acyl group may have a substituent, and examples of the substituent include the substituents listed for Ra.

The acylamino group includes an amino group in which the above-mentioned acyl group is substituted to a nitrogen atom. 1-20 are preferable, as for carbon number of an acylamino group, 2-12 are more preferable, and 2-8 are more preferable.
Examples of the acylamino group include formylamino, acetylamino, propionylamino, butyrylamino, valerylamino, pivaloylamino, lauroylamino, palmitoylamino, stearoylamino, cyclopropylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, acryloylamino, methacryloylamino, And oleylamino, benzoylamino, naphthoylamino, nicotinoylamino and isonicotinoylamino.
The acylamino group may have a substituent, and examples of the substituent include the substituents listed for Ra.

The sulfonamide group includes an alkyl sulfonamide group, a cycloalkyl sulfonamide group, an aryl sulfonamide group, and a heterocyclic sulfonamide group.
1-20 are preferable, as for carbon number of a sulfonamide group, 2-12 are more preferable, and 2-8 are more preferable.
Examples of the sulfonamide group include methane sulfonamide, ethane sulfonamide, propane sulfonamide, octane sulfonamide, cyclopentane sulfonamide, cyclohexane sulfonamide, benzene sulfonamide, and naphthalene sulfonamide.
The sulfonamide group may have a substituent, and examples of the substituent include the substituents listed for Ra.

The carbamoyl group includes a carbamoyl group, an alkylcarbamoyl group, a cycloalkylcarbamoyl group, an arylcarbamoyl group and a heterocyclic carbamoyl group.
1-20 are preferable, as for carbon number of a carbamoyl group, 2-12 are more preferable, and 2-8 are more preferable.
Examples of the carbamoyl group include N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl, N-phenyl-N-methylcarbamoyl, N-cyclohexylcarbamoyl, N-imidazolylcarbamoyl, pyrrolidine carbonyl and piperidine carbonyl. Be
The carbamoyl group may have a substituent, and examples of the substituent include the substituents listed for Ra.

The sulfamoyl group includes a sulfamoyl group, an alkylsulfamoyl group, a cycloalkylsulfamoyl group, an arylsulfamoyl group and a heterocyclic sulfamoyl group.
0-20 are preferable, as for carbon number of sulfamoyl group, 1-12 are more preferable, and 1-8 are more preferable.
As the sulfamoyl group, for example, N-methylsulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, N-phenyl-N-methylsulfamoyl, N-cyclohexylsulfamoyl, N- Imidazolyl sulfamoyl, pyrrolidine sulfamoyl, piperidine sulfamoyl is mentioned.
The sulfamoyl group may have a substituent, and examples of the substituent include the substituents listed for Ra.

2-20 are preferable, as for carbon number of the alkoxy carbonyl group, 2-12 are more preferable, and 2-8 are more preferable.
As the alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, n-pentyloxycarbonyl, t-pentyloxycarbonyl, n -Hexyloxycarbonyl, n-pentyloxycarbonyl, n-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, n-octyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, n-hexadecyloxycarbonyl, n- And octadecyloxycarbonyl.
The alkoxycarbonyl group may have a substituent, and examples of the substituent include the substituents listed for Ra.

7-20 are preferable and, as for carbon number of an aryloxy carbonyl group, 7-12 are more preferable.
Examples of the aryloxycarbonyl group include phenoxycarbonyl and naphthoxycarbonyl.
The aryloxycarbonyl group may have a substituent, and examples of the substituent include the substituents mentioned for Ra.

The acyloxy group includes a formyloxy group, an alkanoyloxy group, an acycloalkanoyloxy group, an alkenoyl oxyl group, an aryloyloxy group, and a heterocyclic carbonyloxy group.
1-20 are preferable, as for carbon number of an acyloxy group, 2-12 are more preferable, and 2-8 are more preferable.
As an acyloxy group, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, pivaloyloxy, lauroyloxy, palmitoyloxy, stearoyloxy, cyclopropylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, acryloyloxy, methacryloyloxy, And oleyloxy, benzoyloxy, naphthoyloxy, nicotinoyloxy, isonicotinoyloxy.
The acyloxy group may have a substituent, and examples of the substituent include the substituents listed for Ra.

The sulfonyl group includes an alkylsulfonyl group, a cycloalkyl sulfonyl group, an aryl sulfonyl group, and a heterocyclic sulfonyl group.
1-20 are preferable, as for carbon number of a sulfonyl group, 2-12 are more preferable, and 2-8 are more preferable.
Examples of the sulfonyl group include methanesulfonyl, ethanesulfonyl, propanesulfonyl, octanesulfonyl, cyclopentanesulfonyl, cyclohexanesulfonyl, benzenesulfonyl and naphthalenesulfonyl.
The sulfonyl group may have a substituent, and examples of the substituent include the substituents listed for Ra.

  The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  Ra is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group or an amino group, more preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, a hydrogen atom, An alkyl group is more preferred, and a hydrogen atom is particularly preferred.

L ¹ is a divalent linking group, preferably a linking group which forms a 5- or 6-membered nitrogen-containing heterocycle together with -N ⁺ (R ¹ ) = Z ^1- , and a 5- or 6-membered nitrogen-containing heteroaromatic ring A linking group forming a ring is more preferable, and a 5-membered nitrogen-containing heteroaromatic ring is particularly preferable.
Here, the formed nitrogen-containing heterocycle may be fused with a benzene ring or another ring, or may be substituted with a substituent. As such a substituent, a substituent at Ra can be mentioned.

The divalent linking group in L ¹ is preferably a linking group in which a linking atom is selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom.
The ring formed by the divalent linking group in L ¹ and -N ⁺ (R ¹ ) = Z ¹ -is, for example, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a thiazole ring, a pyridine ring, A pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a 1-pyrrolidine ring, an imidazoline ring, and their benzene condensates can be mentioned.

The alkyl group, the alkenyl group, the cycloalkyl group, the aryl group and the heterocyclic group in R ^{1 to} R ⁵ are the same as the alkyl group, alkenyl group, cycloalkyl group, aryl group and heterocyclic group in Ra, and the preferable range is also It is the same.

A 5- to 7-membered ring is preferable, and a 5- or 6-membered ring is more preferable as a ring formed by bonding at least two of R ^{2 to} R ⁵ to each other. The ring to be formed may be an aromatic ring, an unsaturated ring or a saturated ring, but a saturated ring is preferred.

As a ring which two of R ^{2 to} R ⁵ bond to each other and form, for example, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, a pyrazoline ring, a pyrrole ring, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, 1, Examples include 1-dioxothiomorpholine ring and 1-oxomorpholine ring.

As a ring which three R < ² > -R < ⁵ > mutually couple | bond and form, a quinuclidine ring and a 1, 4- diaza bicyclo [2.2.2] octane ring are mentioned, for example.

Specific examples of the cation (portion other than X ⁻ ) among the compounds represented by the general formula (1) or (2) include the following cations.

  1-alkyl-3-methylimidazolium such as 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-octyl-3-methylimidazolium 1,3-Dimethylimidazolium, 1,3-Diethylimidazolium, 1,2,3-Trimethylimidazolium, 1,2,3,4-Tetramethylimidazolium, 1,3,4-Trimethyl-2- Ethylimidazolium, 1,3-Dimethyl-2,4-diethylimidazolium, 1,2-Dimethyl-3,4-diethylimidazolium, 1-Methyl-2,3,4-triethylimidazolium, 1,2,2-Triethylimidazolium 3,4-tetraethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1-ethyl-2,3-dimethylimi Zolium, 1,2,3-triethylimidazolium 1-ethyl-2,3-dimethylimidazolium, 1-propyl-2,3-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-pentyl -2,3-dimethylimidazolium, 1-hexyl-2,3-dimethylimidazolium, 1-heptyl-2,3-dimethylimidazolium, 1-octyl-2,3-dimethylimidazolium 1-cyanomethyl-3- Methylimidazolium, 1- (2-hydroxyethyl) -3-methylimidazolium, 1-allyl-3-methylimidazolium,

  1-Butylpyridinium, 1-hexylpyridinium, N- (3-hydroxypropyl) pyridinium, N-hexyl-4-dimethylaminopyridinium, N- (methoxyethyl) -N-methylmorpholine, 1- (2-methoxyethyl) ) 1-methylpyrrolidinium, 1- (methoxyethyl) -1-methylpiperidinium, N- (methoxyethyl) -1-methylpyrrolidinium, 1,2-dimethylpyrazolium, N- (methoxy) Ethyl) -2-methyloxazolium, N- (methoxyethyl) -2-methylthiazolium,

  1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2,4- Diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1, 3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3-triethylimidazolinium,

  1,1-dimethyl-2-heptylimidazolinium, 1,1-dimethyl-2- (2-heptyl) imidazolinium, 1,1-dimethyl-2- (3-heptyl) imidazolinium, 1,1 -Dimethyl-2- (4-heptyl) imidazolinium, 1,1-dimethyl-2-dodecylimidazolinium, 1,1-dimethylimidazolinium, 1,1,2-trimethylimidazolinium, 1,1 , 2,4-tetramethylimidazolinium, 1,1,2,5-tetramethylimidazolinium, 1,1,2,4,5-pentamethylimidazolinium,

  Tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium, trimethylpropylammonium, diethylmethyl (2-methoxyethyl) ammonium, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ) Ammonium, N-ethyl-N, N-dimethyl-2-methoxyethylammonium, trimethylbenzylammonium,

  N, N-bis (2-methoxyethyl) pyrrolidinium, N, N-bis (2-hydroxyethyl) pyrrolidinium, N-methyl-N-2-methoxyethylpyrrolidinium, N, N-bis (2-ethylhexyl) Morpholinium, N, N-bis (2-ethylhexyl) thiomorpholinium, N, N-bis (2-hydroxyethyl) piperidinium, N, N, N ′, N′-tetra (2-hydroxyethyl) piperazinium, N , N-bis (2-ethoxyethyl-1,1-dioxothiomorpholinium, N, N-bis (2-ethoxyethyl-1-oxothiomorpholinium,

  1,3-Dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl -1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium,

  1-methyl quinuclidine, 1-ethyl quinuclidine, 1- (2-hydroxyethyl) quinuclidine, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium, 5-methyl-1 5-Diazabicyclo [4.3.0] -5-nonenium, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium, 5-ethyl-1,5-diazabicyclo [4.3] .0] -5-Nonenium.

The anion in X ⁻ may be either an inorganic anion or an organic anion.
As the inorganic anion, a halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a sulfonate anion (HSO ₄ ⁻ , SO ₄ ²⁻ ), a phosphate anion [P (= O) (OH) ₂ (O) ^{-), P (= O)} (OH) (O -) 2, P (= O) (O -) 3 ], phosphonate anion ^{[HP (= O) (OH)} (O -), HP (= O ) (O ⁻ ) ₂ ), tetrafluoroborate (PF ₆ ⁻ ), BF ₄ ⁻ , AsF ₆ ⁻ , SfF ₆ ⁻ , ClO ₄ ⁻ , AlF ₄ ⁻ , AlF ₄ ⁻ , AlCl ₄ ⁻ , TaF ₆ ⁻ , NbF ₆ ⁻ , SiF ₆ ^{− _{6 -, CN -, F (}} HF) n - (n is an integer from 1 to 4) can be mentioned.

As an organic anion, an organic carboxylate anion, an organic sulfonate anion, an organic phosphate anion, an organic phosphonate anion, a dicyanamide ion [N ⁻ (CN) ₂ ], an organic imide ion, an organic methide anion, an organic And phosphorus anions and organic boron anions.

The organic carboxylic acid or sulfonic acid anion may be any of an aliphatic carboxylic acid or sulfonic acid anion, an aromatic carboxylic acid or sulfonic acid anion, and a heterocyclic carboxylic acid or sulfonic acid anion. Further, it may be an anion (polyvalent anion) of polyvalent carboxylic acid or sulfonic acid such as dicarboxylic acid or disulfonic acid.
A preferred anion of the organic carboxylic acid anion is represented by the following general formula (A1).
Moreover, the preferable anion of the organic sulfonate anion is represented by the following general formula (A2).

  In the general formulas (A1) and (A2), Rb represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Rc represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or Indicates a heterocyclic group.

  The alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group in Rb and Rc are the same as the alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group in Ra. In addition, these alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group may have a substituent, and examples of such a substituent include the substituents mentioned for Ra.

  Examples of the organic carboxylate anion include formate anion, acetate anion, propionate anion, butyrate anion, isobutyrate anion, valerate anion, isovalerate anion, pivalate anion, laurate anion, myristate anion, palmitic acid. Anion, stearate, trifluoroacetate, trichloroacetate, anion of amino acid (eg, glycine, glutamine, glutamic acid, arginine, arginine, arginine, asparagine, aspartic acid, cysteine, proline, serine, tyrosine, valine, leucine, isoleucine , Anions of methionine, phenylalanine, tryptophan, histidine, threonine, and lysine), acrylate anion, methacrylate anion, crotonate anion, isocyanate Tonic acid anion, oleic acid anion, cinnamic acid anion, cyclopropanecarboxylic acid anion, cyclopentanecarboxylic acid anion, cyclohexane carboxylic acid anion, benzoic acid anion, toluic acid anion, naphthalenecarboxylic acid anion, nicotinic acid anion, isonicotinic acid anion Folate anion, tenate anion, oxalate mono- or dianion, malonic acid mono- or dianion, succinic acid mono- or dianion, glutaric acid mono- or dianion, adipic acid mono- or dianion, pimelic acid mono- or dianion, suberic acid mono- or dianion , Azelaic acid mono- or dianion, sebacic acid mono- or dianion, maleic acid mono- or dianion, fumaric acid mono- or dianion Cithraconate mono or dianion, mesaconate mono or dianion, phthalate mono or dianion, terephthalic acid mono or dianion, isophthalic acid mono or dianion, camphoric acid mono or dianion, 1,4-naphthalenedicarboxylic acid mono or dianion, trimellitic acid Mono, di or tri anions, pyromellitic acid mono to tetra anions, and mellitic acid mono to hexa anions can be mentioned.

  As an organic sulfonate anion, for example, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion, octanesulfonate anion, 2-ethylhexanesulfonate anion, cyclohexanesulfonate anion, benzenesulfonate anion, toluene sulfone Examples include acid anions, naphthalene sulfonate anions, 4,6-disulfo-1-naphthalene sulfonate mono-, di- or tri-anions, o-sulfobenzene carboxylic acid mono- or dianions.

  The organic phosphoric acid or phosphonic acid anion is preferably an anion represented by the following general formula (A3).

In the general formula (A3), Rd represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, and Y ¹ represents -O- or -ORe . Here, Re represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group and aryloxy group in Rd are each an alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group and aryl in Ra. It is synonymous with an oxy group, and the alkyl group, cycloalkyl group, an alkenyl group, an aryl group, and a heterocyclic group in Re are synonymous with the alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and a heterocyclic group in Ra.

  Organic phosphoric acid or phosphonic acid anions are methylphosphonic acid mono- or dianion, ethylphosphonic acid mono- or dianion, propylphosphonic acid mono- or dianion, heptylphosphonic acid mono- or dianion, hexylphosphonic acid mono- or dianion, decylphosphonic acid mono- or dianion Octyl phosphonic acid mono- or dianion, vinyl phosphonic acid mono- or dianion, aminomethyl phosphonic acid mono- or dianion, phenyl phosphonic acid mono- or dianion, methylene diphosphonic acid mono to tetra anion, nitrilotris (methylene phosphonic acid mono to hexa anion), 1,4-phenylenediphosphonic acid mono-tetraanion, 4-phosphonobutyric acid mono-, di- or trianion, p-xylene Diphosphonic acid mono- to tetra-anion, monoethyl phosphate mono or dianion, diethyl phosphate anion, dibutyl phosphate anion, didecyl phosphate anion, diphenyl phosphate anions, phenyl phosphate mono or dianion.

  The organic imide ion, the organic methide anion, the organic phosphorus anion and the organic boron anion are preferably anions represented by the following general formulas (A4) to (A7).

In formulas (A4) to (A7), Rf ^{1 to} Rf ^{3 each} represent an alkyl group substituted with a fluorine atom or an aryl group substituted with a fluorine atom, and two Rf ¹ , three Rf ² and three Rf ³ are And each may be the same or different. To Rg ¹ ~Rg ⁴ each independently represents an alkyl group, a cycloalkyl group or an aryl group.

Rf ¹ number of carbon atoms of the alkyl group fluorine atom-substituted in ～Rf ³ is preferably 1 to 20, more preferably 1 to 12, more preferably 1-8, 1 or 2 are particularly preferred.
The alkyl group substituted with a fluorine atom is an alkyl group substituted with at least one fluorine atom, preferably a perfluoroalkyl group.
As the alkyl group substituted with a fluorine atom, for example, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluoro 2-ethylhexyl, difluoromethyl, 2 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, perfluorobenzyl.

Rf ¹ number of carbon atoms of the aryl group which fluorine atom-substituted in ～Rf ³ is 6 to 20, more preferably 6 to 12, more preferably 6 to 10, 6 to 8 is particularly preferred.
The aryl group substituted with a fluorine atom is an aryl group substituted with at least one fluorine atom, preferably a perfluoroaryl group.
Examples of the aryl group substituted with a fluorine atom include perfluorophenyl, perfluorotolyl and 2,6-dichloro-3,4,5-trifluorophenyl.

The alkyl group, cycloalkyl group and aryl group in Rg ^{1 to} Rg ⁴ are the same as the alkyl group, cycloalkyl group and aryl group in Ra.
Each of Rg ^{1 to} Rg ⁴ is preferably an alkyl group or an aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 16 carbon atoms. The aryl group is preferably a phenyl group or a naphthyl group.

  Here, examples of the organic boron anion include the following anions.

X ⁻ is preferably a halide ion, a carboxylate anion, a sulfonate anion, a phosphate anion, a phosphonate anion, a dicyanamide ion, an anion represented by the general formula (A4), and a halogen ion, a carboxylate anion, a sulfonate anion The phosphate anion, the phosphonate anion, the dicyanamide ion or the bis (trifluoromethanesulfonyl) imide ion is more preferable, the halogen ion and the carboxylate anion are more preferable, and the carboxylate anion is particularly preferable.

As the ionic compound, quaternary phosphonium salts can be mentioned in addition to the compounds represented by the above general formula (1) or (2), and the present invention is also preferable.
Examples of quaternary phosphonium of the quaternary phosphonium salt include tetramethyl phosphonium, tetraethyl phosphonium, tetrabutyl phosphonium, triethyl methyl phosphonium, methyl tributyl phosphonium and dimethyl diethyl phosphonium. Anion is the X ^- is preferable.

  The compound represented by general formula (1) or (2) is preferably a compound represented by any one of the following general formulas (1a), (1b) and (2a) to (2c).

Formula (1a), in (1b), (2a) ~ (2c), R 1, R 2 and X ^- is, ^R 1 in the general formula (1) or (2), ^{R 2} and X ^- synonymous And the preferred range is also the same. R ¹¹ and R ¹² each independently represent a substituent. n ¹¹ is an integer of 0 to 3, and n ¹² is an integer of 0 to 5. Here, when R ¹¹ is 2 or more, plural R ^{11 s} may be the same as or different from each other. In addition, at least two R ¹¹ may be bonded to each other to form a ring.
R ¹³ to R ¹⁵ each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. However, at least two of R ² and R ^{13 to} R ¹⁵ are not bonded to each other to form a ring. R ²¹ has the same meaning as R ² , and the preferred range is also the same. Z ² is a single bond, a methylene group, -C (= O)-, -O-, -S-, -S (= O)-, -SO _2- , -N (Rα1)-or -N ⁺ (Rα1 ) (Rα2)-, Rα1 represents a hydrogen atom or a substituent, and Rα2 represents a substituent. Here, Rα1 and Rα2 may be bonded to each other to form a ring.

The substituent in R ¹¹ and R ¹² has the same meaning as Ra. R ¹ has the same meaning as ^{R 1} in the general formula (1), and the preferred range is also the same. R ² has the same meaning as ^{R 2} in the general formula (2), and the preferred range is also the same.
R ^{13 to} R ¹⁵ are the same as R ^{3 to} R ⁵ in General Formula (2) except that two or more of R ^{13 to} R ¹⁵ do not combine with each other to form a ring, and a preferred range is Is also the same.

Examples of the substituent for R α1 include the substituents mentioned for Ra, and an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group and a sulfonyl group are preferable, and an alkyl group, an alkenyl group and a cycloalkyl group are preferable. An aryl group and a heterocyclic group are more preferable, and an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group are more preferable.
The substituent in Rα2 has the same meaning as the substituent in Rα1, and the preferred range is also the same.

The ring formed by bonding of at least two R ¹¹ to each other is preferably a 5- or 6-membered ring, more preferably a benzene ring or a heterocycle, still more preferably a benzene ring or a heteroaromatic ring, and particularly preferably a benzene ring.

  The ring formed by combining Rα1 and Rα2 is preferably a 5- or 6-membered ring, more preferably a nitrogen-containing saturated ring, and still more preferably a pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring or thiomorpholine ring.

R ¹¹ and R ¹² are preferably alkyl groups, and R ^{13 to} R ¹⁵ , R ² and R ²¹ are preferably alkyl groups and aryl groups, and more preferably alkyl groups.
Further, R ¹ and R ¹² are preferably alkyl groups having different carbon numbers from each other.

  In the present invention, among the compounds represented by the general formulas (1a), (1b) and (2a) to (2c), the compounds represented by the general formula (1a), (1b) or (2a) are preferable, The compound represented by General Formula (1a) or (2a) is more preferable, and the compound represented by General Formula (1a) is more preferable.

The following ionic liquids are mentioned as an ionic compound used by this invention.
For example, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium dicyanamide, 1- Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl) Imide, 1-octyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-propyl-2,3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-2,3-dimethylimidazo Lithium bis ( Fluoromethylsulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethylsulfonyl) Methide, 1-butyl-3-methylimidazolium tris (trifluoromethylsulfonyl) methide, 1-hexyl-3-methylimidazolium tris (trifluoromethylsulfonyl) methide, 1-octyl-3-methylimidazolium tris (trimethyl) Fluoromethylsulfonyl) methide, 1-propyl-2,3-dimethylimidazolium tris (trifluoromethylsulfonyl) methide, 1-butyl-2,3-dimethylimidazolium tris (trifluoromethylsulfonyl) methide, N, - Diethyl -N- methyl -N- (2-methoxyethyl) ammonium tris (trifluoromethylsulfonyl) methide,

  1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate 1-butyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate 1-hexyl-3-methylimidazolium tris (penta) Fluoroethyl) trifluorophosphate, 1-octyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate, 1-propyl-2,3-dimethylimidazolium tris (pentafluoroethyl) trifluorophosphate, 1-butyl -2,3-Dimethylimidazolium tris (pentafluoroethyl) trifluorophosphate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tris (pentaful) Loethyl) trifluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-octyl-3 -Methylimidazolium hexafluorophosphate, 1-propyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium hexafluorophosphate,

  1-ethyl-3-methylimidazolium butyl triphenylborate, 1-butyl-3-methylimidazolium butyltris (4-t-butylphenyl) borate, 1-hexyl-3-methylimidazolium butyltris (1-naphthyl) borate 1-Octyl-3-methylimidazolium butyltris (4-methylnaphthalen-1-yl) borate, 1-propyl-2,3-dimethylimidazolium butyltriphenylborate, 1-butyl-2,3-dimethylimidazolium Hexyl tris (4-t-butylphenyl) borate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium 2-ethylhexyl triphenylborate,

  1-Butylpyridinium hexafluorophosphate, 1-hexylpyridinium hexafluorophosphate, 1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate, 1-cyanomethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) ) Imide, N-hexyl-4-dimethylaminopyridinium bis (trifluoromethylsulfonyl) imide, 1- (2-hydroxyethyl) -3-methylimidazolium bis (trifluoromethylsulfonyl) imide, N- (3-hydroxy) Propyl) pyridinium bis (trifluoromethylsulfonyl) imide, N-ethyl-N, N-dimethyl-2-methoxyethyl ammonium tris (pentafluoroethyl) trifluoro 1- (2-hydroxyethyl) -3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate, N- (3-hydroxypropyl) pyridinium tris (pentafluoroethyl) trifluorophosphate, N- (methoxyethyl) sulfate ) -N-Methylmorpholine tris (pentafluoroethyl) trifluorophosphate, 1- (2-methoxyethyl) -1-methyl-pyrrolidinium tris (pentafluoroethyl) trifluorophosphate, 1- (methoxyethyl)- 1-Methylpiperidinium tris (pentafluoroethyl) trifluorophosphate, 1- (methoxyethyl) -1-methylpiperidinium bis (trifluoromethylsulfonyl) imide, N- (methoxyethyl) -1-one Chill pyrrolidinium bis (trifluoromethylsulfonyl) imide, N- (methoxyethyl) -N- methylmorpholine bis (trifluoromethylsulfonyl) imide.

In addition, the ion compound containing an ionic liquid can also use what is marketed.
The following ionic liquids are mentioned as such a compound.

1) Water-immiscible ionic liquid 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-propyl-2,3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl -3-Methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-propyl-2,3-dimethylimidazolium tris (trifluoromethylsulfonyl) methide [all available from Covalent Associates Inc], N, N-diethyl- N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethylsulfonyl) imide, 1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1-octyl-3-methylimidazolium bis (Trifluoromethylsulfonyl) imide, 1-ethyl-2,3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, 1-butyl-2,3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide Commercially available from Kanto Chemical Co., Ltd.].

2) Water-miscible ionic liquid N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate [above, from Kanto Chemical Co., Ltd. Commercially available], 1-methyl-3-propylimidazolium iodide (commercially available from Tokyo Chemical Industry Co., Ltd.), 1-ethyl-3-methylimidazolium trifluoroacetate (commercially available from Merck, Inc.).

The ionic compounds may be used alone or in combination of two or more.
In the present invention, the content of the ionic compound is 0.001 or more and less than 1.000 in mass ratio to cellulose, preferably 0.01 or more and less than 1.000. .8 times is more preferable, 0.01 to 0.8 times is more preferable, and 0.05 to 0.7 times is particularly preferable.

An ionic compound is a salt composed of an anionic component and a cationic component, and because of its high affinity to cellulose molecules, it exhibits a solution property enough to completely dissolve cellulose when the ionic substance is in a liquid state. Exists.
The interaction between ionic compounds and cellulose molecules is described, for example, in Green Chem. As reported in J., 2015, 17, 694-714, an ionic compound acts on the hydroxyl group (hydroxy group) possessed by the cellulose molecule to break the hydrogen bond formed by the hydroxyl groups of the cellulose molecule, thereby intermolecularizing the cellulose It is proposed that dissolution in ionic compounds occurs by

For this reason, when the content of the ionic compound is 1.000 times or more with respect to cellulose, crystals in the cellulose are dissolved, and as a result, the elastic modulus is lowered.
Conversely, if the content of the ionic compound is less than 0.001 times that of cellulose, most of the hydrogen bonds between the strong cellulose molecules will remain, so the elastic modulus does not decrease, but in the processing machine Shear stress alone can not cause the refinement of cellulose.
As described above, it is possible to achieve both the refinement of cellulose in the processing machine and the improvement of the mechanical properties obtained by forming strong hydrogen bonds between cellulose molecules in the refined cellulose. It becomes important.

<Other additives>
In the thermoplastic resin composition of the present invention, in addition to the above, antioxidants, light stabilizers, radical scavengers, UV absorbers, colorants (dyes, organic pigments, inorganic pigments), fillers, lubricants, plasticizers , Processing aids such as acrylic processing aids, foaming agents, lubricants such as paraffin wax, surface treatment agents, crystal nucleating agents, mold release agents, hydrolysis inhibitors, antiblocking agents, antistatic agents, antifogging agents, Other additive components such as a mildew proofing agent, an ion trap agent, a flame retardant, a flame retardant auxiliary and the like can be suitably contained within the range not impairing the object.

  Examples of antioxidants and deterioration inhibitors include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hydroxylamine antioxidants, and amine antioxidants. Hindered phenolic compounds having a t-alkyl group are preferred.

  Examples of phenolic antioxidants include tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-t-). Butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2, 4,8,10-Tetraoxaspiro [5.5] undecane, Triethylene glycol N-bis-3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate], more preferably 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, lauryl-3,5-t-butyl-4-hydroxybenzoate, palmityl-3,5-t- Butyl-4-hydroxybenzoate, stearyl-3,5-t-butyl-4-hydroxybenzoate, behenyl-3,5-t-butyl-4-hydroxybenzoate, 2,4-di-t-butyl-phenyl-3 Examples include 5-di-t-butyl-4-hydroxybenzoate, tocopherols and the like.

  As a phosphorus antioxidant, for example, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-) t-Butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl 2.) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylene diphosphonite, 2, 2'-Methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2 -Ethylidene bis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-triphenyl) -T-Butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2 ', 2'-nitrilo [triethyl-tris (3,3', 5,5'-tetra -T-Butyl-1,1'-biphenyl-2,2'-diyl phosphite, 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-) 5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphepine and the like can be mentioned.

  Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-. Thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, neopentanetetrayl tetrakis (3-lauryl thiopropionate), bis [2-methyl-4- (3-n-alkyl (carbon atom number) 12-14 alkyl) thiopropionyloxy) -5-t-butylphenyl] sulfide etc. are mentioned.

  Examples of light stabilizers include hindered amine light stabilizers having a molecular weight of 1,000 or more (light stabilizers having a 2,2,6,6-tetramethylpiperidine skeleton in the molecule).

  Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and nickel compounds.

  As a coloring agent, carbon black, an inorganic pigment, and an organic pigment are mentioned, for example. For example, as carbon black, furnace black, channel black, acetylene black, lamp black and the like can be mentioned. Examples of the inorganic pigment include iron black, red iron oxide, titanium oxide, cadmium red, cadmium yellow, ultramarine blue, cobalt blue, titanium yellow, red lead, lead yellow, bitumen and the like. Examples of the organic pigment include quinacridone, polyazo yellow, anthraquinone yellow, polyazo red, azo lake yellow, perylene, phthalocyanine green, phthalocyanine blue, isoindolinone yellow and the like. These colorants may be used alone or in combination of two or more.

  Preferred examples of the filler include silica, hydroxyapatite, alumina, titania, boehmite, talc, and metal compounds such as calcium carbonate.

<< Method for producing thermoplastic resin composition >>
First, the cellulose is refined in a thermoplastic synthetic resin containing cellulose and an ionic compound.

When producing a thermoplastic resin composition, a thermoplastic synthetic resin, cellulose and an ionic compound are respectively blended, and the content of cellulose is 1 to 100 parts by mass, containing an ionic compound, relative to 100 parts by mass of the thermoplastic synthetic resin. The amount may be 0.001 times or more and less than 1.000 times that of cellulose.
The method of adding the ionic compound for refining the cellulose is not particularly limited. For example, a method of impregnating the ionic liquid with cellulose in advance, or adding the ionic compound when kneading the thermoplastic synthetic resin and the cellulose Methods are included.
It is preferable to prepare a mixture of cellulose and an ionic compound, that is, a cellulose composition, and blend the cellulose composition with a thermoplastic synthetic resin.
For this reason, the process of preparing the cellulose composition whose content of an ionic compound is 0.1 mass% or more and less than 50 mass% is performed.
The blending amount of the cellulose composition or the total blending amount of the cellulose and the ionic compound is such that the content of the cellulose is 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic synthetic resin.

  Here, in the case of an ionic compound, for example, a halogen anion (in particular, a chlorine anion), depending on storage conditions, it may be hygroscopic to be liquid. In such a case, it is preferable to use water dried by vacuum drying and made solid at normal temperature.

Cellulose is a hydrogen bond due to a hydroxyl group in the molecule, and the intermolecular bonding force is strong.
The ionic compounds are believed to break hydrogen bonds between the cellulose molecules. Moreover, it is believed that the anion component in the constituent of the ionic compound directly acts on the hydrogen atom of the hydroxyl group possessed by the cellulose molecule, so the structure of the anion component exerts a great influence on the solubility of cellulose. It is guessed that.
Cellulose itself, as described above, has strong intermolecular bonding force, and therefore, it is impossible to promote miniaturization only by shear stress in a processing machine. For this reason, it becomes possible to advance refinement | miniaturization because an ionic compound partially weakens the cellulose intermolecular bonding force.

The thermoplastic synthetic resin and the cellulose composition or the cellulose and the ionic compound are respectively blended, and subjected to a kneading and processing step, and the cellulose is refined in this step.
In this kneading and processing step, it is preferable to knead in a processing machine at the stage of processing and molding by extrusion, injection and the like.

The kneading temperature is preferably at least the melting point of the ionic compound, and the upper limit is preferably a temperature at which the thermal decomposition of cellulose is small. Therefore, although the lower limit temperature changes depending on the kind of ionic compound, the upper limit temperature is preferably 300 ° C. or less, more preferably 250 ° C. or less, and still more preferably 230 ° C. or less.
Stirring in kneading is carried out by appropriately arranging a kneading disc in the screw axial direction, etc., to form a screw configuration capable of securing sufficient kneadability, and a screw rotation number capable of obtaining a required production amount (usually It is preferable to knead | mix by about 100-300 rpm.
As an apparatus for carrying out the kneading processing, an apparatus of the same direction twin screw system is preferable, and for example, a twin screw extruder [KZW15TW-45MGNH manufactured by Technobel Co., Ltd.] can be mentioned.
However, the present invention is not limited to the co-directional twin-screw extruder, and may be a single-screw extruder, a counter-rotating twin-screw extruder, a multi-screw extruder having three or more shafts, a batch kneader (kneader, Banbury, etc.), etc. Any system may be used as long as such kneadability can be obtained and the same effect as that of the present invention can be obtained.

<< Bumper and its manufacturing method >>
The resin part of the bumper according to the present invention contains a thermoplastic synthetic resin, cellulose and an ionic compound, and the content of cellulose is 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic synthetic resin. The content is formed of a thermoplastic resin composition that is 0.001 times or more and less than 1.000 times that of the cellulose, and in particular, it is formed using the thermoplastic resin composition manufactured by the above manufacturing method.

  FIG. 1 is a perspective view showing a vehicle bumper having a resin portion according to one embodiment. FIG. 2 is a partially cutaway perspective view showing the back side of the vehicle bumper of FIG. As shown in FIGS. 1 and 2, the bumper 100 is integrally formed in its entirety by the resin portion 10, and includes a bumper main body 1 and a bracket 2 for attaching the bumper main body 1 to the vehicle body of an automobile. doing.

  The bracket 2 is provided on the back surface side of the bumper main body 1 so as not to project the tip. The bracket 2 is provided with a bolt through hole 2a, and the bumper main body 1 is attached to the vehicle body of the automobile via the bolt through hole 2a and a bolt (not shown).

  Here, the resin part 10 which comprises the bumper main body 1 and the bracket 2 is formed using the said thermoplastic resin composition. Thereby, in the bumper 100, it is possible to reduce the weight and increase the strength, as well as improve the recyclability, the surface smoothness, and the adhesion performance.

  Although the manufacturing method of this bumper is not particularly limited, it can be molded by injection molding in which the above-mentioned thermoplastic resin material is injected into a mold. For example, a thermoplastic resin composition to be a material of the resin portion of the bumper is melted in a cylinder using an injection molding machine, and then the molten resin composition is injected into a mold corresponding to the shape of the resin portion. After solidifying the resin composition by holding pressure and cooling inside the mold, it can be carried out by taking out the mold.

  The application of the bumper provided with the resin part of the present invention is not limited to automobiles, for example, materials for vehicles such as motorcycles, structural members of robot arms, amusement robot parts, prosthetic members, household electric appliance materials, OA equipment housings, information Processing equipment, portable terminals, building materials, drainage, toiletry materials, various tanks, containers, sheets, toys, sports goods, etc. may be mentioned.

EXAMPLES The present invention will be described in more detail based on examples given below, but the invention is not meant to be limited by these.
The materials used are shown below.

<Material used>
(1) Thermoplastic synthetic resin / thermoplastic synthetic resin A: high density polyethylene [MFR = 5 g / 10 min (190 ° C./2.16 kg), density = 0.953 g / cm ³ ]
Thermoplastic synthetic resin B: ethylene-propylene copolymer [ethylene content 16 mass%, MFR (190 ° C./2.16 kg) = 1.4 g / 10 min, density = 0.862 g / cm ³ ]
Thermoplastic synthetic resin C: ethylene-octene copolymer [MFR = 1.0 g / 10 min (190 ° C./2.16 kg), density = 0.870 g / cm ³ ]
(2) Cellulose cellulose A: KC floc W-200 (trade name: Nippon Paper Industries Co., Ltd., powdered cellulose having an average particle diameter of about 32 μm)
Cellulose B: LIGNOCEL C-120 (trade name J. Rettenmeyer & Sons, particle size 70 to 150 μm)
(3) Ion compound / ion compound A: 1-butyl-3-methylimidazolium acetate (melting point: -20 ° C or less)
· Ion compound B: 1-butyl-3-methylimidazolium chloride (melting point: -70 ° C)
・ Ionic compound C: 1-butyl-3-methylimidazolium dicyanamide (melting point: −6 ° C.)

Example 1
In the following steps, a cellulose reinforced thermoplastic resin was produced.
1) Preparation step of cellulose composition After 90 parts by mass of cellulose A was dispersed in acetone solvent and 10 parts by mass of ionic compound A were mixed, the mixture was stirred for several hours and left in a covered container for 12 hours or more did.
Thereafter, the lid of the container was opened, and the acetone solvent was dried. After the acetone solvent was almost completely ejected, the container was further stored for 12 hours or more in a thermostat at 80 ° C. for drying water.

2) Kneading step of cellulose composition and thermoplastic synthetic resin (production of cellulose reinforced thermoplastic resin composition)
Prepared above with a second feeder while feeding a thermoplastic synthetic resin B at a rate of 300 g / hour at an outlet temperature of 150 ° C. to a twin-screw extruder [KZW15TW-45MG-NH, manufactured by Technobel Co., Ltd.] The resulting cellulose composition was fed at a rate of 300 g / hour and extruded to produce a cellulose reinforced thermoplastic resin composition. At this time, the screw rotation speed was 100 rpm.
In the process of this extrusion, the thermoplastic synthetic resin B and the cellulose A are kneaded to disperse the cellulose, whereby the cellulose fiber is refined. Moreover, it is thought that the refinement | miniaturization will advance further also in the preparation process of following 3). In addition, temporarily, even if refinement | miniaturization is inadequate at the kneading | mixing process of 2), it can refine | miniaturize by performing the preparation process of following 3).

3) Preparation Step of Cellulose-Reinforced Thermoplastic Resin Composition Containing Thermoplastic Synthetic Resin A Cellulose-Reinforced Thermoplastic Resin Composition Having the Cellulose Fiber Fined by the Above Extrusion Dispersed in Thermoplastic Synthetic Resin B, and Thermoplasticity The synthetic resin A was dry-blended so that the mass ratio of thermoplastic synthetic resin A: thermoplastic synthetic resin B would be 78:22, and a twin-screw extruder [manufactured by Technobell KZW15TW-45MG-NH] was used. A cellulose reinforced thermoplastic resin composition containing two types of thermoplastic synthetic resins was prepared and manufactured. At this time, the outlet temperature of the twin screw extruder was set to 190 ° C., and the cellulose reinforced thermoplastic resin composition was prepared while feeding at a rate of 1000 g / hour. At this time, the screw rotation speed was 100 rpm.
Also in this preparation process, it is considered that the refinement of the cellulose fiber is in progress.

4) Manufacturing process of bumper provided with resin part The injection molding of the cellulose reinforced thermoplastic resin composition prepared in said 3) was carried out, and the bumper provided with the resin part was produced. In addition, injection conditions were implemented on the shaping | molding conditions made generally appropriate.

Example 2
A cellulose reinforced thermoplastic resin composition containing one kind of thermoplastic synthetic resin obtained in 2) was manufactured without performing the step 3) of Example 1. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 3
In the step 1) of Example 1, 0.1 parts by mass of the ionic compound A was blended with 99.9 parts by mass of cellulose A, and in the step 2), instead of the thermoplastic synthetic resin B, thermoplasticity A cellulose-reinforced thermoplastic resin composition containing two types of thermoplastic synthetic resins was prepared in the same manner as in Example 2 except that a resin in which the synthetic resins A and B were mixed in a mass ratio of 499: 1 was used. Prepared and manufactured. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 4
Cellulose containing one kind of thermoplastic synthetic resin in the same manner as in Example 2 except that in the step 1) of Example 1, 49.9 parts by mass of the ionic compound A was blended with 50.1 parts by mass of cellulose A. A reinforced thermoplastic resin composition was produced. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 5
The process of 3) of Example 1 is the same as Example 1 except that the thermoplastic synthetic resin A is dry blended so that the thermoplastic synthetic resin A: the thermoplastic synthetic resin B is 98: 2 by mass ratio. Similarly, a cellulose reinforced thermoplastic resin composition containing two kinds of thermoplastic synthetic resins was produced. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 6
A cellulose reinforced thermoplastic resin composition containing two types of thermoplastic synthetic resins was produced in the same manner as in Example 1 except that the type of ionic compound was changed to ionic compound B in the step 1) of Example 1. . Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 7
A cellulose reinforced thermoplastic resin composition containing two kinds of thermoplastic synthetic resins was produced in the same manner as in Example 1 except that in the step 1) of Example 1, the type of ionic compound was changed to ionic compound C. . Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 8
The process of 2) of Example 1 is the same as Example 1 except that 11 parts by mass of the cellulose composition is blended with 100 parts by mass of the thermoplastic synthetic resin A, and the process of 3) is not performed. Then, a cellulose reinforced thermoplastic resin composition containing one kind of thermoplastic synthetic resin was manufactured. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 9
A cellulose reinforced thermoplastic resin composition containing one kind of thermoplastic synthetic resin was produced in the same manner as in Example 8 except that the type of cellulose was changed to cellulose B in the step 1) of Example 1. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 10
In the step 2) of Example 1, instead of the thermoplastic synthetic resin B, a thermoplastic synthetic resin C was used, and the mass ratio of the thermoplastic synthetic resin C: cellulose composition was 90: 100, and Example In step 3) of 1, the cellulose reinforced thermoplastic resin composition dispersed in the thermoplastic synthetic resin C and the thermoplastic synthetic resin A are dispersed in the thermoplastic synthetic resin A: thermoplastic synthetic resin C in mass ratio A cellulose-reinforced thermoplastic resin composition containing two types of thermoplastic synthetic resins was produced in the same manner as in Example 1 except that the obtained cellulose-reinforced thermoplastic resin composition was dry-blended to be 260: 190. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 11
In the process of 1) of Example 1, 30 parts by mass of the ionic compound A is blended with 70 parts by mass of cellulose A, and in the process of 2) of Example 1, the mass ratio of the thermoplastic synthetic resin C: cellulose composition is 70: 100, and in the step 3) of Example 1, the cellulose reinforced thermoplastic resin composition dispersed in the thermoplastic synthetic resin C and the thermoplastic synthetic resin A in a mass ratio, thermoplasticity Synthetic resin A: Two kinds of thermoplastic synthetic resins are contained in the same manner as in Example 10 except that the cellulose reinforced thermoplastic resin composition dispersed in the thermoplastic synthetic resin C is dry blended so as to be 180: 170. A cellulose reinforced thermoplastic resin composition was produced. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Example 12
In the step 1) of Example 1, 49.9 parts by mass of the ionic compound A was blended with 50.1 parts by mass of cellulose A, and in the step 2) of Example 1, thermoplastic synthetic resin C: cellulose composition Mass ratio of 50: 100, and in the step 3) of Example 1, the mass ratio of the cellulose-reinforced thermoplastic resin composition dispersed in the thermoplastic synthetic resin C and the thermoplastic synthetic resin A In the same manner as in Example 10, except that the thermoplastic synthetic resin A: the cellulose reinforced thermoplastic resin composition dispersed in the thermoplastic synthetic resin C is dry blended to be 100: 150, two kinds of thermoplasticity A cellulose reinforced thermoplastic resin composition containing a synthetic resin was produced. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Comparative Example 1
In the process of 1) of Example 1, 70 parts by mass of the ionic compound A was blended with 30 parts by mass of cellulose A. In this case, the powdered cellulose was dissolved, and partially recrystallization of the cellulose in the acetone solvent, or the dried cellulose liquid which became a liquid of high viscosity after drying was disturbed, and the handling property was impaired, so the process of 2) In place of the twin-screw extruder, Labo Plastomill [Kaboration and extrusion molding evaluation test equipment made by Toyo Seiki Seisakusho Co., Ltd. Labo Plastomill ・ Micro] is used, and the obtained composition is pelletized to obtain a thermoplastic resin composition. Were prepared and manufactured.
In the step 3), the thermoplastic synthetic resin A was dry-blended so that the mass ratio of the thermoplastic synthetic resin A: the thermoplastic synthetic resin B was 50:50, except that A cellulose reinforced thermoplastic resin composition containing two types of thermoplastic synthetic resins was produced in the same manner as in step 3). Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Comparative example 2
In the step 2) of Example 1, the thermoplastic synthetic resin A was used instead of the thermoplastic synthetic resin B, and it was blended in a ratio of 112 parts by mass of the cellulose composition to 100 parts by mass of the thermoplastic synthetic resin A A cellulose reinforced thermoplastic resin composition containing one kind of thermoplastic synthetic resin was prepared and manufactured in the same manner as Example 2 except for the above. Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

Comparative example 3
Cellulose A11.1 is not used in the process of 1) of Example 1, cellulose A itself is used instead of the cellulose composition, and in the process of 2) of Example 1, cellulose A11.1 relative to 100 parts by mass of thermoplastic synthetic resin A A cellulose reinforced thermoplastic resin composition containing one kind of thermoplastic synthetic resin was prepared and manufactured by blending mass parts and extruding with a twin-screw extruder [KZW15TW-45MG-NH manufactured by Technobel Co., Ltd.]. . Next, using this cellulose reinforced thermoplastic resin composition, a bumper provided with a resin portion was produced in the same manner as in Example 1.

  The short side length and the area of the aggregate of the cellulose fibers present in each of the cellulose reinforced thermoplastic resin compositions prepared and manufactured as described above were measured as follows.

(Measurement of short side length of cellulose fiber)
Each of the cellulose reinforced thermoplastic resin compositions was immersed in liquid nitrogen, and an external force was applied thereto in a state below the embrittlement temperature to cause fracture and expose the fractured surface.
The reflection electron image by the electron microscope was observed with respect to this torn surface, and the short side length of the cellulose fiber was measured.
Among 200 cellulose fibers at random, the abundance ratio of 2 μm or less was also determined.
When this ratio is 15% or more, it indicates that the cellulose fiber is miniaturized, which means that the elastic modulus is improved and the reinforcing efficiency of the thermoplastic resin is high.

(Area measurement of cellulose aggregate)
Each cellulose reinforced thermoplastic resin composition was press-molded for 5 minutes at 160 ° C. for 5 minutes under pressure of 20 MPa under pressure for 5 minutes to prepare a sheet having a thickness of about 0.1 mm. The sheet thus produced was photographed at a magnification of 50 with an industrial microscope "ECLIPSE LV100ND" manufactured by Nikon Corporation. In the image | photographed image, the part counted by the brightness | luminance of 0-80 was made into the aggregate of a cellulose.
The area of the field of view was 1.3 mm × 1.7 mm, the field of view was n1, and nine spots were observed at random. The area of the cellulose aggregate was computed by image-analyzing the part counted by the brightness | luminance of 0-80 obtained by Nikon Co., Ltd. "NIS-Elemenets D".
The target pass level is obtained when the area of each of the nine cellulose aggregates calculated is less than 20000 μm ² , and the rejection level is obtained when any of the areas is 20000 μm ² or more.
In Tables 1 and 2, among the nine cellulose aggregates, the maximum area and the minimum area are described as “maximum value” and “minimum value”, respectively.
The fact that the area of any of the cellulose aggregates is less than 20000 μm ² indicates that the cellulose fibers are refined without aggregation even if they are refined, and the elastic modulus is further added to the short side length of the cellulose fibers It means that it is improved and the reinforcement efficiency of the thermoplastic resin is high.

(Appearance of injection molded product (bumper with resin part))
The produced injection molded article (bumper provided with a resin part) was visually observed, and the uniformity of the cellulose dispersion was evaluated by the presence or absence of the aggregate of cellulose fiber. When no cellulose fiber aggregate is present, it can be determined that a bumper provided with a resin portion that is lightweight and has high strength, and is excellent in recyclability, surface smoothness, and adhesion performance is obtained.

(Measurement of Apparent Elastic Modulus of Cellulose Contained in Thermoplastic Resin Composition)
The apparent elastic modulus of the cellulose contained in each cellulose reinforced thermoplastic resin composition was measured as follows in each manufactured cellulose reinforced thermoplastic resin composition.

It injection-molded using each manufactured cellulose reinforced thermoplastic resin composition, and produced the bending test piece (thickness 4 mm x length 80 mm). In addition, injection conditions were implemented on the shaping | molding conditions made generally appropriate. The flexural modulus was calculated according to JIS K 7171. The density conformed to JIS K7112. However, the measuring solvent was not water but ethanol was used. The volume fraction of each component of synthetic resin and cellulose was calculated from the obtained density. The density and elastic modulus of the synthetic resin alone were separately calculated according to JIS K 7112 and JIS K 7171. The apparent elastic modulus Ef of cellulose was determined from Formula (2.2) obtained by modifying Formula (2.1) below.
In addition, Em was calculated | required as being a type | formula (4.2) from following formula (4.1) based on a compound rule.
Among the obtained results, the results in Example 8 and Comparative Example 3 are representatively shown in Table 3 below.

Here, Ec is a Young's modulus (elastic modulus) of a bending test piece which is a composite material, Em is a Young's modulus (elastic modulus) of a thermoplastic synthetic resin which is a base material, and Ef is a Young of cellulose which is a fiber. It is a modulus (elastic modulus).
Vm is a volume fraction of the thermoplastic synthetic resin as a base material, and Vf is a volume fraction of cellulose as a fiber. These volume fractions are determined from the density.
Ep is the Young's modulus (elastic modulus) of the component p, and Vp is the volume fraction of the component p, which is obtained from the density. There are 1 to n components, and n is the maximum value of the number of components present.

The obtained results are summarized in Tables 1 to 3 below.
Here, the thermoplastic synthetic resin and the cellulose composition in the table are parts by mass, and "-" indicates that it is unused, that is, 0 parts by mass. Moreover, cellulose and the ionic compound which are breakdown of a cellulose composition show the ratio of these mass parts. "-" Shows unused as in the above, that is, 0 parts by mass.
On the other hand, in the measurement result, "-" can not be measured and indicates that it is not evaluated.
In addition, A and B in a cellulose composition show that the used cellulose is A or B.

From Tables 1 and 2 above, in all the thermoplastic resin compositions of Examples 1 to 12, the abundance ratio of cellulose fibers having a short side length of 2 μm or less is 15% or more, and the area of cellulose aggregates is less than 20000 μm ² Met.
On the other hand, in the thermoplastic resin composition of Comparative Example 1, the compounding amount of the ionic compound to be added to the cellulose is too large and the cellulose fiber is dissolved, so that the form observation as a dispersion becomes impossible. . On the other hand, in the thermoplastic resin composition of Comparative Example 2, although it can be confirmed that the blending amount of cellulose is too large and partial refinement is progressing partially, at the same time, a cellulose aggregate having an area of 20,000 μm ² or more Aggregates were present, and the proportion of cellulose fibers having a short side length of 2 μm or less was less than 15%. In the thermoplastic resin composition of Comparative Example 3, the proportion of cellulose fibers having a short side length of 2 μm or less was less than 15%, and the area of cellulose aggregates was 20,000 μm ² or more.
In the composition in which 15% or more of the cellulose is refined to 2 μm or less as in Example 8 representatively shown in Table 3, the reinforcing effect of the resin can be seen more strongly. This phenomenon is considered to be due to the improvement of the elastic modulus of cellulose due to the refinement of cellulose.

  The thermoplastic resin compositions of Examples 1 to 12 are found to be useful as a bumper provided with a resin portion as a cellulose reinforced resin because the elastic modulus is improved and the reinforcing efficiency of the thermoplastic resin is high.

  While the present invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified, which is contrary to the spirit and scope of the invention as set forth in the appended claims. I think that it should be interpreted broadly without.

  Although the bumper 100 in FIGS. 1 and 2 illustrates the case where the whole is integrally formed by the resin portion 10 in the above embodiment, the present invention is not limited to this, and a part of a vehicle bumper, for example, a bumper main body A part may be molded with a resin portion, and a bumper for a vehicle may include a portion formed of a material other than the resin portion. Moreover, a bumper main body may be formed using the said thermoplastic resin composition, and the bracket may be separately formed by the member different from the said thermoplastic resin composition on the other hand.

  Further, in the above embodiment, although the bumper 100 of FIGS. 1 and 2 is a vehicle bumper, the vehicle bumper may be either a front bumper or a rear bumper. Furthermore, the bumper provided with the resin portion according to the present invention is not limited to the bumper for a vehicle, and can be applied to various bumpers serving as an impact absorbing member.

1 bumper body 2 bracket 2a bolt through hole 2a
10 resin part 100 bumper

Claims (7)

  A thermoplastic synthetic resin, cellulose and an ionic compound are contained, the content of the cellulose is 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic synthetic resin, and the content of the ionic compound is 0% of the cellulose A bumper provided with a resin portion formed of a thermoplastic resin composition that is not less than 001 times and not more than 1.000 times. The bumper according to claim 1, wherein the ionic compound is represented by the following general formula (1) or (2).

In the general formulas (1) and (2), Z ¹ represents = C (Ra)-or = N-. Here, Ra represents a hydrogen atom or a substituent. L ¹ represents a divalent linking group. Each of R ^{1 to} R ⁵ independently represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of R ^{2 to} R ⁵ may bond to each other to form a ring. X < ^- > shows an anion. The bumper according to claim 2, wherein the compound represented by the general formula (1) or (2) is represented by any one of the following general formulas (1a), (1b), (2a) to (2c).

Formula (1a), in (1b), (2a) ~ (2c), R 1, R 2 and X ^- is, ^R 1 in the general formula (1) or (2), ^{R 2} and X ^- synonymous It is. R ¹¹ and R ¹² each independently represent a substituent. n ¹¹ is an integer of 0 to 3, and n ¹² is an integer of 0 to 5. Here, when R ¹¹ is 2 or more, plural R ^{11 s} may be the same as or different from each other. In addition, at least two R ¹¹ may be bonded to each other to form a ring.
R ¹³ to R ¹⁵ each independently represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. However, at least two of R ² and R ^{13 to} R ¹⁵ are not bonded to each other to form a ring. R ²¹ has the same meaning as R ² . Z ² is a single bond, a methylene group, -C (= O)-, -O-, -S-, -S (= O)-, -SO _2- , -N (Rα1)-or -N ⁺ (Rα1 ) (Rα2)-, Rα1 represents a hydrogen atom or a substituent, and Rα2 represents a substituent. Here, Rα1 and Rα2 may be bonded to each other to form a ring. The bumper according to claim 2 or 3, wherein the X ^- is a halogen ion, a carboxylate anion, a sulfonate anion, a phosphate anion, a phosphonate anion, a dicyanamide ion or a bis (trifluoromethanesulfonyl) imide ion.   The bumper according to any one of claims 1 to 4, wherein the cellulose is fibrous cellulose of plant origin.   The bumper according to any one of claims 1 to 5, wherein 15% or more of the cellulose has a short side length of 2 μm or less. Bumper according to any one of claims 1 to 6 area of cellulose aggregate of the thermoplastic resin composition is less than 20000μm ^2.

Images