JP6691759B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition. More specifically, it relates to a resin composition containing a thermoplastic recycled resin, a method for producing the same, a molded article containing the resin composition, a method for producing the same, and a method for improving the physical properties of the resin composition.

  Many packaging materials use thermoplastic composite materials and / or laminated materials, and are formed into, for example, bottle containers, refill pouches, and the like. These materials may be composed of quite different types of polymers for various eco-friendly aspects and functional reasons. For example, thermoplastic composites often combine polymer components having different chemical properties to form a discontinuous phase within a polymer matrix. Also, laminated materials are often designed such that each layer is made of a different polymer to impart specific barrier properties such that each layer has a different permeability. For example, the refill pouch can be a laminated material in which polar and non-polar polymers are included in separate layers and laminated.

  Commonly used polymers for thermoplastic composites and / or laminates include polyamides, polyolefins, polyesters, and ethylene copolymers. Therefore, when a packaging material or the like containing two or more kinds of these resins is recovered and the resin is regenerated, an inhomogeneous blend occurs due to the incompatibility between the polymers in the product. For example, the polyethylene obtained by recovering and regenerating the pouch forms a non-homogeneous blend because it contains a polyamide, but the toughness is remarkably reduced as compared with virgin polyethylene. Therefore, one solution to such a problem is to use an additive that compatibilizes different polymers.

  For example, in Patent Document 1, ethylene / methyl acrylate is used for a polymer blend of a first polymer component such as polyethylene and ethylene copolymer and a second polymer component of a thermoplastic resin containing a hydroxyl group or an amino group. It is described that by combining a polar ethylene copolymer such as / ethyl hydrogen maleate as a compatibilizing agent, the obtained composition becomes a homogeneous polymer blend, which is a useful technique for recycling.

JP, 2009-535452, A

  However, even if the homogenization of the resins having different physical properties depending on the compatibilizing agent is advanced, the compatibilization is also affected by the kneading conditions and the like, so that it is not sufficient to obtain a homogeneous recycled resin, for example, There is a problem that variations in toughness are likely to occur in the composition. Further, from the viewpoint of eco-friendliness, application of recycled resin to various uses is attempted, and further improvement in rigidity and heat resistance is expected.

  The present invention includes a resin composition containing a recycled resin, which has excellent rigidity and heat resistance, and has a good appearance of the obtained molded product, a method for producing the same, and the resin composition. The present invention relates to a molded product, a method for producing the molded product, and a method for improving the physical properties of the resin composition.

The present invention relates to the following [1] to [5].
[1] A) Thermoplastic reclaimed resin 50% by mass or more and 98% by mass or less B) Cellulose fiber 1% by mass or more and 49% by mass or less, and C) Compatibilizer 1% by mass or more and 20% by mass or less object.
[2] Production of a resin composition in which B) 1 part by mass or more and 98 parts by mass or less of C), and C) 1 part by mass or more and 40 parts by mass or less of a compatibilizer are blended with 100 parts by mass of the thermoplastic regenerated resin. Method.
[3] A molded product containing the resin composition according to [1].
[4] A method for producing a molded body, which comprises processing the resin composition according to [1] to obtain a molded body.
[5] A) In a resin composition containing a thermoplastic regenerated resin, B) 1 part by mass or more and 98 parts by mass or less of C), and C) 1 part by mass of a compatibilizer with respect to 100 parts by mass of the thermoplastic regenerated resin. A method for improving the rigidity of the resin composition, which comprises blending 40 parts by mass or more.

  The resin composition of the present invention, while containing a recycled resin, exhibits excellent effects such as excellent rigidity and heat resistance, and a good appearance of the obtained molded body. Further, in addition to the appearance of the obtained molded product being good, the composition is homogeneous, so that an excellent effect that there is little variation in toughness is exhibited.

1: is a figure which shows the SEM image of the sheet cross section of the resin composition of Example 1. FIG. FIG. 2 is a view showing a SEM image of a sheet cross section of the resin composition of Comparative Example 4.

[Resin composition]
[Thermoplastic recycled resin]
The thermoplastic regenerated resin in the present invention is a regenerated resin having thermoplasticity, and from the viewpoint of moldability, it is preferable to regenerate the thermoplastic resin. Hereinafter, the thermoplastic recycled resin in the present invention may be simply referred to as a recycled resin. In addition, in the present specification, the recycled resin means a resin in which a plurality of resins are mixed, and is a resin which is collected from a used product according to a known method and then melt-kneaded and molded.

  The thermoplastic resin in the recycled resin is not particularly limited, and may be polyolefin resin, polyester resin, nylon resin, vinyl chloride resin, styrene resin, vinyl ether resin, polyvinyl alcohol resin, polyamide resin, polycarbonate resin, polysulfone resin, or the like. Can be mentioned. Among these, as the recycled resin used in the present invention, from the viewpoint of the amount of the resin used as the packaging material, at least two kinds selected from polyolefin resin, polyester resin, and polyamide resin are contained as constituent resins. Are preferred, and those containing at least a polyolefin resin are more preferred.

  Examples of the polyolefin resin include polyethylene (PE resin), polypropylene (PP resin), polystyrene (PS resin), polyvinyl acetate (PVAc resin), polyvinyl chloride (PVC resin), polyvinylidene chloride (PVDC resin), polyacrylic acid. (PA resin), polyacrylic acid ester (PAE resin), polybutadiene (PB resin), polyisoprene (PIP resin), polychloroprene (PCP resin) and the like. Among these, polyethylene is preferably contained as a main component from the viewpoint of the amount of resin used as a packaging material. The content of the polyolefin resin in the recycled resin is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, and further preferably 80% by mass from the viewpoint of improving the appearance of the obtained molded product. % Or more, more preferably 85% by mass or more. From the viewpoint of productivity, it is preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably 95% by mass or less.

  Examples of the polyester resin include polyethylene terephthalate (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate (PBT resin), polyethylene naphthalate (PEN resin) and polybutylene naphthalate (PBN resin). .. The content of the polyester resin in the recycled resin is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass from the viewpoint of improving the appearance of the obtained molded product. % Or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. Further, as long as the resin other than the polyolefin resin is contained, the polyester resin may not be contained, and the lower limit is not particularly set, but from the viewpoint of productivity, it is preferably 0% by mass or more, and more preferably It is 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 1.5% by mass or more, further preferably 2% by mass or more.

  As the polyamide resin, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polycaproamide / polyhexamethylene adipamide copolymer (polyamide 6/66), polytetramethylene adipamide (polyamide) 46), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamide (polyamide 11), polydodecamide (polyamide 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer ( Polyamide 66 / 6T) and the like are exemplified. The content of the polyamide resin in the recycled resin is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, further preferably 15% by mass from the viewpoint of improving the appearance of the obtained molded product. % Or less, more preferably 10% by mass or less, and further preferably 8% by mass or less. Further, if the resin other than the polyolefin resin is contained, the polyamide resin may not be contained, and the lower limit is not particularly set, but from the viewpoint of the difficulty of separation in the recovery step, preferably 0% by mass. The amount is more preferably 0.5% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4% by mass or more.

  Specific examples of the composition of the recycled resin in the present invention include a polyolefin resin of 60% by mass to 99% by mass, a polyester resin of 0% by mass to 30% by mass, and a polyamide resin of 0% by mass to 30% by mass. % Or less, an embodiment of containing is exemplified.

  In the present invention, as the recycled resin containing such a thermoplastic resin, for example, a recycled resin recovered from a used refill pouch, a detergent bottle or the like by a known method can be preferably used. For example, it can be prepared by recovering a product containing a used polyolefin resin, separating and recovering the polyolefin resin from the recovered product, melt-kneading and regenerating. You may use a commercial item.

  The content of the recycled resin in the resin composition of the present invention is 50% by mass or more and 98% by mass or less, but from the viewpoint of improving the appearance of the obtained molded body, preferably 60% by mass or more, more preferably 70% by mass. % Or more, more preferably 75% by mass or more, further preferably 80% by mass or more, further preferably 85% by mass or more. From the viewpoint of improving the rigidity and heat resistance of the obtained molded product, it is preferably 96 mass% or less, more preferably 94 mass% or less.

[Cellulose fiber]
Cellulose fiber is a fibrous reinforcing material that can be expected to be lightweight and thermal recyclable. However, when the content of cellulose fiber increases, the viscosity of the resin composition increases, resulting in deterioration of moldability, aggregation of fibers or polymer matrix. Deterioration of the toughness due to destabilization of the interface with Therefore, the cellulose fiber in the resin composition of the present invention is selected from the group consisting of the following (i) to (iii) from the viewpoint of interfacial stabilization with the regenerated resin and fine dispersion in the resin composition. One kind or two or more kinds is preferable. In addition, hereinafter, the cellulose fibers of each group will be simply referred to as (i) cellulose fibers, (ii) cellulose fibers, and (iii) cellulose fibers.
(I) Amorphous cellulose fiber having a relative crystallinity of 33% or less (ii) A modified cellulose fiber having a cellulose I type crystal structure in which a hydrocarbon group is bonded to a cellulose fiber through an amide bond. (Iii) A modified cellulose fiber in which a hydrocarbon group is bonded to a cellulose fiber through an ether bond and has a cellulose type I crystal structure.

In the present specification, the relative crystallinity of cellulose is the cellulose I type crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following calculation formula (A). It
Cellulose type I crystallinity (%) = [(I22.6-I18.5) /I22.6] × 100 (A)
[Wherein I22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 is the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5 °). Show]

(I) Amorphous Cellulose Fiber Having a Relative Crystallinity of 33% or Less The cellulose fiber of (i) has a relative crystallinity of 33% or less, but has improved compatibility with a recycled resin, and the obtained molding. From the viewpoint of improving the appearance of the body, it is preferably 20% or less, more preferably 10% or less, further preferably 5% or less, and further preferably substantially 0% in which no type I crystal is detected by analysis. The cellulose I-type crystallinity defined by the calculation formula (A) may have a negative value in calculation, but in the case of a negative value, the cellulose I-type crystallinity is 0%.

  Such amorphous cellulose fibers are obtained by treating one or more cellulose-containing raw materials selected from woods, pulps, papers, plant stems / leaves, plant shells, etc. with a pulverizer to obtain cellulose It can be obtained by reducing the crystallinity. For example, the method described in JP2011-1547A can be referred to. In addition, the cellulose type I crystallinity of commercially available pulp is usually 60% or more.

Specifically, if necessary, the cellulose-containing raw material is subjected to coarse crushing in which the size is preferably adjusted to a size of 1 to 70 mm square by using a cutting machine such as a shredder, and then by an impact crusher or an extruder. The bulk density is adjusted to 50 to 600 kg / m ³ or the specific surface area is 0.2 to 750 m ² / kg by performing a treatment or a drying treatment, and then a medium type crusher is used to adjust the bulk density to 0. By stirring for 5 minutes to 24 hours, it is possible to obtain an amorphous cellulose fiber having a reduced crystallinity. The relative crystallinity of the obtained amorphous cellulose fiber can be controlled by adjusting the type and size of the medium, the filling rate, and the stirring time. From the viewpoint of efficiently performing the pulverization process, the water content of the raw material is preferably 1.8% by mass or less.

  The thus-obtained cellulose fiber (i) has an average fiber diameter of preferably 1 μm or more, more preferably 5 μm or more, further preferably 7 μm or more, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. .. Although the upper limit is not particularly set, it is preferably 100 μm or less, more preferably 70 μm or less, and further preferably 60 μm or less from the viewpoint of handleability. In addition, in this specification, the average fiber diameter of the cellulose fibers can be measured according to the method described in Examples.

(Ii) A modified cellulose fiber in which a hydrocarbon group is bonded to a cellulose fiber through an amide bond and has a cellulose type I crystal structure. The cellulose fiber of (ii) is a cellulose in which a hydrocarbon group is bonded through an amide bond. Bonded to the fiber. The term “via an amide bond” as used herein means a state in which a hydrocarbon group is amide-bonded to a carboxy group present on the surface of a cellulose fiber, and is obtained by subjecting an amine having a hydrocarbon to an amide reaction. ..

  Examples of the hydrocarbon group in the cellulose fiber (ii) include a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group. From the viewpoint of improvement, a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group are preferred.

  The chain saturated hydrocarbon group may be linear or branched. The number of carbon atoms in the chain saturated hydrocarbon group is preferably 1 or more, more preferably 3 or more, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and from the viewpoint of improving the appearance of the obtained molded product. 5 or more is more preferable, 10 or more is more preferable, and 15 or more is further preferable. From the same viewpoint, 30 or less is preferable, 24 or less is more preferable, 20 or less is still more preferable, and 18 or less is still more preferable.

  Specific examples of the chain saturated hydrocarbon group include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, tert-pentyl group, Isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, octadecyl group, docosyl group, octacosanyl group, and the like can be obtained. From the viewpoint of improving the rigidity and heat resistance of the resin composition, and from the viewpoint of improving the appearance of the obtained molded product, preferably a pentyl group, a tert-pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group. Group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group , Tetradecyl, octadecyl group. These may be introduced alone or in any combination of two or more thereof.

  The chain unsaturated hydrocarbon group may be linear or branched. The number of carbon atoms of the chain unsaturated hydrocarbon group is preferably 2 or more, and more preferably 3 or more from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product. It is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more. From the same viewpoint, 30 or less is preferable, 24 or less is more preferable, 20 or less is still more preferable, and 18 or less is still more preferable.

  Specific examples of the chain unsaturated hydrocarbon group include, for example, ethenyl group, propenyl group, butenyl group, isobutenyl group, isoprenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group. , Tridecenyl group, tetradecenyl group, octadecenyl group, rigidity of the resulting resin composition, from the viewpoint of improving the heat resistance, and from the viewpoint of improving the appearance of the resulting molded article, preferably a decenyl group, dodecenyl group, A tridecenyl group, a tetradecenyl group, and an octadecenyl group. These may be introduced alone or in any combination of two or more thereof.

  The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 3 or more, more preferably 4 or more from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product. 5 or more is more preferable. From the same viewpoint, it is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less, still more preferably 8 or less.

  Specific examples of the cyclic saturated hydrocarbon group include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, cyclotridecyl group, Cyclotetradecyl group, cyclooctadecyl group and the like, preferably, a cyclopentyl group, a cyclohexyl group, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, and improving the appearance of the obtained molded body, A cycloheptyl group and a cyclooctyl group. These may be introduced alone or in any combination of two or more thereof.

  The aromatic hydrocarbon group is, for example, selected from the group consisting of an aryl group and an aralkyl group. The aryl group and aralkyl group may be substituted or unsubstituted on the aromatic ring itself.

  The total carbon number of the aryl group may be 6 or more, and is preferably 24 or less, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and from the viewpoint of improving the appearance of the resulting molded body. It is preferably 20 or less, more preferably 14 or less, further preferably 12 or less, and further preferably 10 or less.

  The total carbon number of the aralkyl group is 7 or more, and is preferably 8 or more from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product, and From the same viewpoint, it is preferably 24 or less, more preferably 20 or less, still more preferably 14 or less, still more preferably 13 or less, still more preferably 11 or less.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group, a terphenyl group, and a group in which these groups are substituted with any substituent. One kind may be introduced alone or two kinds or more may be introduced at an arbitrary ratio. Among them, a phenyl group, a biphenyl group and a terphenyl group are preferable, and a phenyl group is more preferable, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product.

  Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, and an aromatic group of these groups substituted with an arbitrary substituent. And the like. These may be introduced singly or in combination of two or more at an arbitrary ratio. Among them, a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylpentyl group are preferable from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product.

  The average bond amount (mmol / g) of the hydrocarbon group in the cellulose fiber of (ii) is the resin composition obtained for the chain saturated hydrocarbon group, the chain unsaturated hydrocarbon group, and the cyclic saturated hydrocarbon group. From the viewpoint of improving the rigidity and heat resistance of the product and improving the appearance of the obtained molded product, preferably 0.001 mmol / g or more, more preferably 0.005 mmol / g or more, and further preferably 0.01 mmol. / G or more. From the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, still more preferably 1.5 mmol / g or less. Further, regarding the aromatic hydrocarbon group, the average amount of the hydrocarbon group is preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, and from the viewpoint of improving the appearance of the obtained molded body. 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, further preferably 0.5 mmol / g or more, further preferably 0.7 mmol / g or more, further preferably 0.9 mmol / g or more, further preferably It is 1.0 mmol / g or more. From the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, still more preferably 2.0 mmol / g or less. Here, even when a hydrocarbon group selected from a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, and a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group are simultaneously introduced. The average binding amount of each is preferably within the above range.

  The introduction rate of the hydrocarbon group is a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, and a cyclic saturated hydrocarbon group, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, And from the viewpoint of improving the appearance of the obtained molded product, it is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, further preferably 60% or more, further preferably 70% or more, From the viewpoint of economic efficiency, it is preferably 99% or less, more preferably 97% or less, further preferably 95% or less, further preferably 90% or less. Regarding the aromatic hydrocarbon group, the introduction rate of the hydrocarbon group is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, further preferably 60% or more, from the same viewpoint. It is more preferably 70% or more, further preferably 75% or more, and from the viewpoint of economy, preferably 99% or less, more preferably 97% or less, further preferably 95% or less, further preferably 90% or less. .. Here, when a hydrocarbon group selected from a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, and a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group are simultaneously introduced, introduction In the range where the total of the rates does not exceed the upper limit of 100%, it is preferably within the above range.

  In the present specification, the average amount of hydrocarbon groups bonded can be adjusted by the amount of amine added, the type of amine, reaction temperature, reaction time, solvent and the like. Further, the average bond amount (mmol / g) and the introduction rate (%) of the hydrocarbon group in the modified cellulose fiber are the amount and ratio of the introduction of the hydrocarbon group to the carboxy group on the surface of the cellulose fiber, It can be calculated by measuring the carboxy group content of the cellulose fiber according to a known method (eg, titration, IR measurement, etc.).

The cellulose fiber (ii) can be produced according to a known method without particular limitation, for example, a method described in JP-A-2015-143337, as long as a hydrocarbon group can be introduced into the cellulose fiber through an amide bond. it can. Specifically, for example, it can be obtained by a manufacturing method including the following steps.
Step (ii-1): Step of oxidizing natural cellulose fiber in the presence of N-oxyl compound to obtain cellulose fiber containing carboxy group Step (ii-2): Containing carboxy group obtained in step (ii-1) Step of amidating a cellulose fiber and an amine having a hydrocarbon group It is to be noted that, as the preferable production method, after the step (ii-1), a micronization step which will be described later is carried out to obtain a carboxy group-containing fine cellulose fiber. Of performing the step (ii-2) (first manufacturing mode), and a method of performing the step (ii-2) after the step (ii-1) and then performing a miniaturization step (second method). Manufacturing form). The amine having a hydrocarbon group used here may be one prepared according to a known method or a commercially available product as long as it is an amine having a hydrocarbon group described above.

  The cellulose fiber (ii) has an average fiber diameter of preferably 5 μm or more, and more preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition when obtained without performing a refining treatment. Is 7 μm or more, more preferably 10 μm or more. Further, the upper limit is not particularly set, but from the viewpoint of improving the toughness of the obtained resin composition, preferably 100 μm or less, more preferably 70 μm or less, further preferably 50 μm or less, further preferably 40 μm or less, further preferably 30 μm or less. Is.

  Further, in the case of being obtained by subjecting to a refinement treatment, the average fiber diameter is preferably 0.1 nm or more, more preferably 0.2 nm or more from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. , More preferably 0.5 nm or more, further preferably 0.8 nm or more, further preferably 1 nm or more. From the same viewpoint, it is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, further preferably 20 nm or less, further preferably 10 nm or less. In addition, in this specification, when the average fiber diameter of the cellulose fibers is a nano-order size, it can be measured according to the method described in Examples.

  The cellulose fiber of (ii) has a cellulose I type crystal structure because the crystallinity does not decrease due to the reaction of the step (ii-2), and has the same degree of crystallinity as the cellulose fiber used. It is preferable to have a crystallinity of. The relative crystallinity is preferably 35% or more, more preferably 45% or more, still more preferably 50% or more, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. From the viewpoint of reactivity, it is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, still more preferably 75% or less.

(Iii) Modified cellulose fiber in which a hydrocarbon group is bonded to a cellulose fiber through an ether bond and has a cellulose type I crystal structure. In the cellulose fiber of (iii), the hydrocarbon group is a cellulose fiber through an ether bond. Bonded to the fiber. The term "via an ether bond" as used herein means a state in which a hydrocarbon group is ether-bonded to a carboxy group present on the surface of a cellulose fiber, and is obtained by subjecting an amine having a hydrocarbon to an etherification reaction. Be done.

As the hydrocarbon group in the cellulose fiber (iii), the same hydrocarbon group as in the cellulose fiber (ii) can be mentioned, and they are as described in the preceding section. Among them, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, and improving the appearance of the obtained molded product, the substituent and the general formula (1) represented by the following general formula (1) One or more substituents selected from the substituents represented by 2) are preferable.
_{-CH 2 -CH (OH) -R 1} (1)
_{-CH 2 -CH (OH) -CH 2} - (OA) n -O-R 1 (2)
[In formula, R < ₁ > in General formula (1) and General formula (2) respectively independently shows a C3 or more and 30 or less linear or branched alkyl group, and n in General formula (2) is 0. And 50 or more and 50 or less, and A represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms]

R ₁ in the general formula (1) is a linear or branched alkyl group having 3 to 30 carbon atoms. The carbon number of the alkyl group is 3 or more and 30 or less, but preferably 4 or more, more preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product. It is preferably 6 or more, and from the viewpoint of improving availability and reactivity, it is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less, still more preferably 10 or less. Specific examples include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a hexadecyl group, an octadecyl group, an icosyl group, and a triacontyl group. It

R ₁ in the general formula (2) is a linear or branched alkyl group having 3 to 30 carbon atoms. The carbon number of the alkyl group is 3 or more and 30 or less, but preferably 4 or more, more preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product. It is preferably 6 or more, and from the viewpoint of improving availability and reactivity, it is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less. Specific examples thereof include the same as R ₁ in the above general formula (1).

  A in the general formula (2) is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms and forms an oxyalkylene group with an adjacent oxygen atom. Although the carbon number of A is 1 or more and 6 or less, it is preferably 2 or more, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and from the viewpoint of improving the appearance of the obtained molded body, and the same. From the viewpoint of, it is preferably 4 or less, more preferably 3 or less. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Of these, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable.

  N in the general formula (2) represents the number of moles of alkylene oxide added. n is a number of 0 or more and 50 or less, but preferably 3 or more, and more preferably 5 from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded body. The above is more preferably 10 or more, and from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, further preferably 15 or less.

  As the combination of A and n in the general formula (2), from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, A is preferably a linear or branched divalent group having 2 to 3 carbon atoms. Saturated hydrocarbon group, n is a combination of 0 or more and 20 or less, more preferably A is a linear or branched divalent saturated hydrocarbon group having 2 or more and 3 or less carbon atoms, and n is 5 or more. It is a combination of numbers 15 or less.

  Specific examples of the substituent represented by the general formula (1) include, for example, 2-hydroxypentyl group, 2-hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 2-hydroxynonyl group, 2 -Hydroxydecyl group, 2-hydroxyundecyl group, 2-hydroxydodecyl group, 2-hydroxyhexadecyl group, 2-hydroxyoctadecyl group, 2-hydroxyicosyl group, 2-hydrochitriacontyl group, etc. are mentioned.

  Specific examples of the substituent represented by the general formula (2) include, for example, 3-hexoxyethyleneoxy-2-hydroxy-propyl group, 3-hexoxy-2-hydroxy-propyl group, 3-octoxyethyleneoxy. 2-Hydroxy-propyl group, 3-octoxy-2-hydroxy-propyl group, 3-detoxyethyleneoxy-2-hydroxy-propyl group, 3-detoxy-2-hydroxy-propyl group, 3-dodetoxyethylene Oxy-2-hydroxy-propyl group, 3-dodetoxy-2-hydroxy-propyl group, 3-hexadetoxyethyleneoxy-2-hydroxy-propyl group, 3-hexadetoxy-2-hydroxy-propyl group, 3-octade Toxyethyleneoxy-2-hydroxy-propyl group, 3-octadetoxy-2-hydroxy- Propyl group, and the like. The number of added moles of alkylene oxide may be 0 or more and 50 or less, and examples of the substituent having an oxyalkylene group such as ethylene oxide have a number of added moles of 10, 12, 13, and 20 moles. To be done.

In addition, in the cellulose fiber (iii), other substituents other than the substituent represented by the general formula (1) and the substituent represented by the general formula (2) may be introduced. As the other substituent, for example, in the substituent represented by the general formula (1) and / or the substituent represented by the general formula (2), the carbon number of R ₁ is preferably 2 or less, more preferably 1 Substituents. Specifically, a 2-hydroxy-propyl group and the like can be mentioned.

  In the cellulose fiber of (iii), the introduction ratio of the substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2) to 1 mol of anhydrous glucose unit of cellulose is: From the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and from the viewpoint of improving the appearance of the obtained molded product, it is preferably 0.001 mol or more, more preferably 0.005 mol or more, and further preferably 0. The amount is 0.01 mol or more, more preferably 0.05 mol or more, further preferably 0.1 mol or more, and further preferably 0.2 mol or more. Further, it has a cellulose type I crystal structure, and from the viewpoint of economy, it is preferably 1.5 mol or less, more preferably 1.3 mol or less, still more preferably 1.0 mol or less, still more preferably 0.8 mol. Or less, more preferably 0.6 mol or less, still more preferably 0.5 mol or less. Here, when both the substituent represented by the general formula (1) and the substituent represented by the general formula (2) are introduced, it means the total introduced mole ratio. Further, the introduction ratio of the other substituents described above is not particularly limited, but it may be 1.5 mol or less from the viewpoint of economy, having a cellulose I type crystal structure. In the present specification, the introduction rate can be measured according to the method described in Examples below, and may also be referred to as the introduction molar ratio or the modification rate.

  In the cellulose fiber of (iii), a hydrocarbon group is bonded to the surface of the cellulose fiber through an ether bond, but the introduction of the substituent can be performed by a known method without particular limitation. Specifically, for example, the cellulosic raw material may be reacted with the compound having the substituent in the presence of a base.

  As the cellulosic material, the same material as the material used for the cellulose fiber (i) can be used. The shape is not particularly limited, but from the viewpoint of handleability, a fibrous shape, a powder shape, a spherical shape, a chip shape, and a flake shape are preferable. Also, a mixture of these may be used.

  The average fiber diameter of the cellulosic raw material is not particularly limited, but from the viewpoint of handleability and economy, it is preferably 5 μm or more, more preferably 7 μm or more, further preferably 10 μm or more, and further preferably 15 μm or more. The upper limit is not particularly set, but from the viewpoint of improving the toughness of the obtained resin composition, it is preferably 10,000 μm or less, more preferably 5,000 μm or less, still more preferably 1,000 μm or less, still more preferably 500 μm or less. , And more preferably 100 μm or less.

  In addition, from the viewpoint of reducing the number of manufacturing steps, a cellulosic material that has been made fine in advance may be used, and the average fiber diameter in that case is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoint of improving heat resistance. It is preferably 3 nm or more, more preferably 10 nm or more. The upper limit is not particularly set, but from the viewpoint of improving the toughness of the obtained resin composition, it is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, still more preferably 100 nm or less, still more preferably 80 nm. It is below.

  The composition of the cellulosic material is not particularly limited, but the content of cellulose in the cellulosic material is preferably 30% by mass or more, more preferably 50% by mass from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. % Or more, more preferably 70% by mass or more, from the viewpoint of availability, preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 95% by mass or less, further preferably 90% by mass or less. Some are preferred. Here, the content of cellulose in the cellulosic material means the content of cellulose in the remaining components of the cellulosic material excluding water.

  The water content in the cellulosic raw material is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.1% by mass from the viewpoint of availability and economy. 5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, further preferably 2.0% by mass or more, and from the viewpoint of handleability, preferably 50% by mass or less, It is more preferably 40% by mass or less, further preferably 30% by mass or less, and further preferably 20% by mass or less.

(base)
A base is mixed with the cellulosic material.

  The base used is not particularly limited, but from the viewpoint of advancing the etherification reaction, an alkali metal hydroxide, an alkaline earth metal hydroxide, a primary to tertiary amine, a quaternary ammonium salt, imidazole and a derivative thereof. One or more selected from the group consisting of pyridine, pyridine and its derivatives, and alkoxide are preferable.

  Examples of the alkali metal hydroxides and alkaline earth metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide and the like.

  The primary to secondary amines are primary amines, secondary amines, and tertiary amines, and specific examples include ethylenediamine, diethylamine, proline, N, N, N ', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, tris (3-dimethylaminopropyl) amine, Examples thereof include N, N-dimethylcyclohexylamine and triethylamine.

  Examples of the quaternary ammonium salt include tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium fluoride, tetraethylammonium bromide and water. Examples thereof include tetramethylammonium oxide, tetramethylammonium chloride, tetramethylammonium fluoride and tetramethylammonium bromide.

  Examples of imidazole and its derivatives include 1-methylimidazole, 3-aminopropylimidazole, carbonyldiimidazole and the like.

  Examples of pyridine and its derivatives include N, N-dimethyl-4-aminopyridine and picoline.

  Examples of the alkoxide include sodium methoxide, sodium ethoxide, potassium-t-butoxide and the like.

  The amount of the base is preferably 0.01 equivalent or more, more preferably 0.05 equivalent or more, further preferably 0.1 with respect to the anhydroglucose unit of the cellulosic raw material, from the viewpoint of proceeding the etherification reaction. Equivalent or more, more preferably 0.2 equivalent or more, from the viewpoint of manufacturing cost, preferably 10 equivalents or less, more preferably 8 equivalents or less, further preferably 5 equivalents or less, further preferably 3 etc. It is less than or equal to the amount.

  The cellulosic material and the base may be mixed in the presence of a solvent. The solvent is not particularly limited and includes, for example, water, isopropanol, t-butanol, dimethylformamide, toluene, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, 1,4-dioxane, and mixtures thereof.

  The mixing of the cellulosic raw material and the base is not particularly limited in temperature and time as long as they can be uniformly mixed.

(Compound having a substituent)
Next, in the mixture of the cellulosic material and the base obtained above, as a compound having a substituent, a compound having a substituent represented by the general formula (1) and a substitution represented by the general formula (2). One or more compounds selected from the group-containing compounds are reacted. Such a compound is not particularly limited as long as it can bond the substituent when it reacts with a cellulosic raw material, and in the present invention, it has reactivity from the viewpoint of reactivity and a non-halogen-containing compound. A compound having a cyclic structure group is preferably used, and a compound having an epoxy group is preferably used. The respective compounds are exemplified below.

  As the compound having a substituent represented by the general formula (1), for example, a nonionic alkylene oxide compound represented by the following general formula (1A) is preferable. As such compounds, those prepared according to known techniques may be used, or commercially available products may be used.

[In the formula, R ₁ represents a linear or branched alkyl group having 3 to 30 carbon atoms]

R ₁ in the general formula (1A) is a linear or branched alkyl group having 3 to 30 carbon atoms. The carbon number of the alkyl group is 3 or more and 30 or less, but preferably 4 or more, more preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product. It is preferably 6 or more, and from the viewpoint of improving reactivity, it is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less, still more preferably 10 or less. Specific examples thereof include those described in the item of R _{1 in} the substituent represented by the general formula (1).

  Specific examples of the compound represented by the general formula (1A) include 1,2-epoxyhexane, 1,2-epoxydecane, and 1,2-epoxyoctadecane.

  As the compound having a substituent represented by the general formula (2), for example, a nonionic glycidyl ether compound represented by the following general formula (2A) is preferable. As such compounds, those prepared according to known techniques may be used, or commercially available products may be used. The total carbon number of the compound is 5 or more, preferably 10 or more, more preferably 20 or more, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, and the toughness of the obtained resin composition. From the viewpoint of improving the molded article and improving the appearance of the obtained molded product, it is 100 or less, preferably 75 or less, more preferably 50 or less, still more preferably 25 or less.

[In the formula, R ₁ is a linear or branched alkyl group having 3 to 30 carbon atoms, A is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and n is 0 or more. Indicates a number of 50 or less]

R ₁ in the general formula (2A) is a linear or branched alkyl group having 3 to 30 carbon atoms. The carbon number of the alkyl group is 3 or more and 30 or less, but preferably 4 or more, more preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded product. It is preferably 6 or more, and from the viewpoint of improving availability and reactivity, it is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less. Specific examples thereof include those described in the item of R _{1 in} the substituent represented by the general formula (2).

  A in the general formula (2A) is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms and forms an oxyalkylene group with an adjacent oxygen atom. Although the carbon number of A is 1 or more and 6 or less, it is preferably 2 or more, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and from the viewpoint of improving the appearance of the obtained molded body, and the same. From the viewpoint of, it is preferably 4 or less, more preferably 3 or less. Specific examples thereof include those described in the item of A in the substituent represented by the general formula (2), and among them, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable.

  N in the general formula (2A) represents the number of added moles of alkylene oxide. n is a number of 0 or more and 50 or less, but preferably 3 or more, and more preferably 5 from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded body. The above is more preferably 10 or more, and from the same viewpoint and the affinity with a low-polarity solvent, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 15 or less.

  Specific examples of the compound represented by the general formula (2A) include stearyl glycidyl ether and polyoxyalkylene alkyl ether.

  The amount of the compound can be determined by the desired introduction ratio of the substituent represented by the general formula (1) and / or the substituent represented by the general formula (2) in the obtained cellulose fiber, From the viewpoint of the property, it is preferably 0.01 equivalent or more, more preferably 0.1 equivalent or more, still more preferably 0.3 equivalent or more, still more preferably 0. It is 5 equivalents or more, more preferably 1.0 equivalent or more, and from the viewpoint of manufacturing cost, preferably 10 equivalents or less, more preferably 8 equivalents or less, further preferably 6.5 equivalents or less, It is preferably 5 equivalents or less.

(Ether reaction)
The ether reaction between the compound and the cellulosic raw material can be carried out by mixing the two in the presence of a solvent. The solvent is not particularly limited, and the solvents exemplified as being usable when the base is present can be used.

  The amount of the solvent used is not unconditionally determined depending on the type of the cellulosic raw material and the compound having the substituent, but is preferably 30 parts by mass or more from the viewpoint of reactivity with respect to 100 parts by mass of the cellulosic raw material, More preferably 50 parts by mass or more, further preferably 75 parts by mass or more, further preferably 100 parts by mass or more, further preferably 200 parts by mass or more, from the viewpoint of productivity, preferably 10,000 parts by mass or less, It is preferably 5,000 parts by mass or less, more preferably 2,500 parts by mass or less, further preferably 1,000 parts by mass or less, and further preferably 500 parts by mass or less.

  The mixing conditions are not particularly limited as long as the cellulosic raw materials and the compounds having the above-mentioned substituents are uniformly mixed and the reaction can proceed sufficiently, and continuous mixing treatment may or may not be performed. When a relatively large reaction vessel having a volume of more than 1 L is used, stirring may be appropriately performed from the viewpoint of controlling the reaction temperature.

  The reaction temperature is not generally determined by the type of the cellulosic raw material or the compound having the substituent and the target introduction rate, but from the viewpoint of improving the reactivity, preferably 40 ° C. or higher, more preferably 50 ° C. As described above, the temperature is more preferably 60 ° C. or higher, and from the viewpoint of suppressing thermal decomposition, it is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 100 ° C. or lower.

  The reaction time is not generally determined by the type of the cellulosic raw material or the compound having a substituent and the target introduction rate, but from the viewpoint of reactivity, preferably 3 hours or more, more preferably 6 hours or more, It is more preferably 10 hours or more, and from the viewpoint of productivity, it is preferably 60 hours or less, more preferably 48 hours or less, still more preferably 36 hours or less.

  When a substituent other than the substituent represented by the general formula (1) and / or the substituent represented by the general formula (2) is introduced, a compound having another substituent is further included. For example, in the case of introducing a 2-hydroxy-propyl group, propylene oxide is added to the reaction system, preferably 30 ° C or higher, more preferably 35 ° C or higher, even more preferably 40 ° C or higher, preferably 90 ° C or higher. ℃ or less, more preferably 80 ℃ or less, more preferably 70 ℃ or less in the temperature range, preferably 3 hours or more, more preferably 6 hours or more, more preferably 10 hours or more, preferably 60 hours or less, More preferable example is a mode in which heating is performed for 48 hours or less, and further preferably for 36 hours or less. The compound having a substituent represented by the general formula (1) and / or the compound having a substituent represented by the general formula (2) and the compound having another substituent may be simultaneously reacted. ..

  Further, the modified cellulose fiber of (iii) may be subjected to a known refining treatment to be refined after the reaction. For example, it can be miniaturized by performing a treatment using a high pressure homogenizer or the like in an organic solvent. Further, it is also possible to obtain a modified cellulose fiber which has been micronized by carrying out the above-mentioned substituent introduction reaction using a cellulosic raw material which has been micronized beforehand, but the rigidity and heat resistance of the obtained resin composition can be improved. From the viewpoint of improving the appearance and improving the appearance of the obtained molded product, it is preferable to carry out a known microfabrication treatment for microfabrication after the reaction for introducing the substituent.

  After the reaction, an appropriate post-treatment can be carried out to remove unreacted compounds, bases and the like. As the method of the post-treatment, for example, an unreacted base can be neutralized with an acid (organic acid, inorganic acid, etc.) and then washed with a solvent in which the unreacted compound and the base are dissolved. If desired, further drying (such as vacuum drying) may be performed.

  The obtained cellulose fiber (iii) is in a state in which the substituent represented by the general formula (1) and / or the substituent represented by the general formula (2) is ether-bonded to the surface of the cellulose fiber. Specifically, a modified cellulose fiber represented by the following general formula (3) is exemplified.

[Wherein, R is the same or different and represents hydrogen or a substituent selected from the substituents represented by the general formula (1) and the general formula (2), and m is 20 The above is an integer of 3000 or less, except when all R's are simultaneously hydrogen.]

  In the modified cellulose fiber represented by the general formula (3), R is the same or different and hydrogen or a substituent represented by the general formula (1) and / or a substitution represented by the general formula (2). It represents a group and has a repeating structure of a cellulose unit into which the substituent is introduced. As the repeating number of the repeating structure, m in the general formula (3) may be an integer of 20 or more and 3000 or less, and is preferably 100 or more and 2000 or less from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition.

  When the cellulose fiber (iii) is obtained without performing a refining treatment, the average fiber diameter is preferably 5 μm or more, and more preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. Is 7 μm or more, more preferably 10 μm or more. Further, the upper limit is not particularly set, but from the viewpoint of improving the toughness of the obtained resin composition, preferably 100 μm or less, more preferably 70 μm or less, further preferably 50 μm or less, further preferably 40 μm or less, further preferably 30 μm or less. Is.

  Further, in the case where it is obtained by performing a refining treatment, the average fiber diameter is preferably 3 nm or more, more preferably 10 nm or more, further preferably from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. From the viewpoint of improving the toughness of the obtained resin composition, it is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 120 nm or less.

  The cellulose fiber of (iii) has a cellulose I type crystal structure because the crystallinity does not decrease due to the etherification reaction, and the crystallinity is similar to that of the cellulose fiber used. It is preferable to have The relative crystallinity is preferably 30% or more, and more preferably 35% or more from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition. Further, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 70% or less, further preferably 60% or less, and further preferably 50% or less.

  The resin composition of the present invention preferably contains one or more selected from the cellulose fibers (i) to (iii) described above, but the content of the cellulose fibers is 100% by weight of the recycled resin. From the viewpoint of improving rigidity and heat resistance of the obtained resin composition, preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 7 parts by mass or more, further preferably 9 parts by mass. From the viewpoint of improving the appearance of the obtained molded product, it is preferably 98 parts by mass or less, more preferably 45 parts by mass or less, further preferably 30 parts by mass or less, and further preferably 20 parts by mass or less. .. Here, when the resin composition of the present invention contains a plurality of cellulose fibers, it means the total content.

  The content of cellulose in the resin composition is 1% by mass or more and 49% by mass or less, but from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, preferably 3% by mass or more, more preferably Is 5% by mass or more, and more preferably 7% by mass or more. Further, from the viewpoint of improving the appearance of the obtained molded body, preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, further preferably 15 mass% or less, further preferably 10 mass%. % Or less.

[Compatibilizer]
As the compatibilizer that can be used in the present invention, known ones can be used, but in addition to strengthening the interface in the regenerated resin, the dispersibility of the cellulose fiber is improved, and the compatibility between the cellulose fiber and the regenerated resin is increased. From the viewpoints of stabilizing the interface, improving the rigidity and heat resistance of the obtained resin composition, and improving the appearance of the obtained molded product, a compound having a polar group and a polyolefin is preferable. The compound having a polar group and polyolefin, while the polyolefin portion has an affinity with the regenerated resin, when the polar group portion contains a cellulose fiber or a regenerated resin polyamide, reacts or interacts with the cellulose fiber, polyamide. Since the affinity is developed by the action, it is considered that the obtained resin composition has a structure with high affinity in the matrix.

  Examples of polar groups include organic isocyanate groups, (anhydrous) carboxylic acid groups, carboxylic acid halide groups, amino groups, hydroxyl groups, and epoxy groups. Among these, from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition, and from the viewpoint of improving the appearance of the obtained molded product, (anhydrous) carboxylic acid group and epoxy group are preferable, and more preferable. Is a (anhydrous) carboxylic acid group. Specific examples thereof include a succinic anhydride group, a succinic acid group, and glycidyl (meth) acrylate.

  The polyolefin is preferably an ethylene polymer [high-density polyethylene, medium-density polyethylene, low-density polyethylene, ethylene and one or more other vinyl compounds (for example, α-olefin, vinyl acetate, methacrylic acid, acrylic acid, etc.). Etc.], propylene-based polymers [polypropylene, copolymers of propylene and one or more other vinyl compounds, etc.], ethylene-propylene copolymers, polybutene, poly-4-methylpentene-1 etc. And more preferably an ethylene polymer or a propylene polymer.

  Examples of such compounds include maleic anhydride-modified polyolefin. Suitable commercially available products include "Bond First 7M" (copolymer of polyethylene having an epoxy group and (meth) acrylic acid) manufactured by Sumitomo Chemical Co., Ltd., "LEX Pearl" (polyolefin having an epoxy group) manufactured by Japan Polyethylene Corporation. System resin), NOF CORPORATION MODIPER (polyolefin resin having an epoxy group), Sanyo Chemical Co., Ltd. `` Umex '' maleic anhydride modified polypropylene), Arkema `` Olevac '' (maleic anhydride modified polyethylene), Arkema's "Rotader" (polyolefin resin with acid anhydride), Sumitomo Chemical Co., Ltd. "Bondaine" (polyolefin resin with acid anhydride), Mitsui DuPont Polychemical Co., Ltd. "Nucrel" (carboxyl group) Polyolefin resin), Dow Chemical's "Primacol" (carboxyl Polyolefin resin) having the like.

  In the resin composition of the present invention, the content of the compatibilizing agent is 100 parts by mass of the recycled resin from the viewpoint of improving the rigidity and heat resistance of the obtained resin composition and improving the appearance of the obtained molded body. On the other hand, it is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, further preferably 2 parts by mass or more, preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and further preferably The amount is 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less. Here, when the resin composition of the present invention contains a plurality of compatibilizers, it means the total content.

  Further, the content of the compatibilizing agent in the resin composition is 1% by mass or more and 20% by mass or less, but from the viewpoint of improving the rigidity and heat resistance of the obtained molded product and improving the appearance of the molded product. Therefore, it is preferably 1.5% by mass or more, and more preferably 2% by mass or more. From the viewpoint of improving the appearance of the obtained molded product, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

  The resin composition of the present invention contains a plasticizer, a crystal nucleating agent, a filler (inorganic filler, organic filler), a hydrolysis inhibitor, a flame retardant, an antioxidant, and a hydrocarbon-based component, in addition to the components described above. Lubricants such as waxes and anionic surfactants; ultraviolet absorbers; antistatic agents; antifogging agents; light stabilizers; pigments; antifungal agents; antibacterial agents; foaming agents; surfactants; starches, alginic acid, etc. Polysaccharides; natural proteins such as gelatin, glue, casein; inorganic compounds such as tannins, zeolites, ceramics, metal powders; fragrances; flow regulators; leveling agents; conductive agents; UV dispersants; deodorants, etc. It may be contained within a range that does not impair the effects of the present invention. It is also possible to add other polymer materials and other resin compositions within the range that does not impair the effects of the present invention. The content ratio of the optional additive may be appropriately contained within a range that does not impair the effects of the present invention, for example, preferably 20% by mass or less in the resin composition, more preferably about 10% by mass or less, It is even more preferably about 5% by mass or less.

  The resin composition of the present invention can be prepared without particular limitation as long as it contains a specific amount of cellulose fibers and a specific amount of a compatibilizer with respect to the thermoplastic regenerated resin. In addition to the three components, a raw material containing various additives as necessary is stirred with a Henschel mixer or the like, or a known kneader such as a closed kneader, a single-screw or twin-screw extruder, and an open roll kneader is used. It can be prepared by melt kneading or solvent casting.

  Therefore, the present invention also provides a method for producing the resin composition of the present invention.

  As the method for producing the resin composition of the present invention, 1 part by mass or more and 98 parts by mass or less of cellulose fiber, and 1 part by mass or more and 40 parts by mass or less of a compatibilizing agent are used with respect to 100 parts by mass of the thermoplastic recycled resin described above. There is no particular limitation as long as it includes a step of mixing. For example, a thermoplastic regenerated resin, a cellulose fiber, and a compatibilizer, as well as a raw material containing various additives if necessary, preferably 150 ° C. or higher, from the viewpoint of improving rigidity, heat resistance, and appearance of the molded body, The temperature is preferably 180 ° C. or higher, and from the viewpoint of improving the appearance of the molded body, an embodiment in which the temperature is preferably 280 ° C. or lower, more preferably 250 ° C. or lower is exemplified. The mixing time is not set depending on the composition of the raw materials and the mixing temperature, and is, for example, about 5 to 10 minutes.

In the method for producing the resin composition of the present invention, the thermoplastic recycled resin itself may be prepared, and, for example, a method including the following steps is exemplified as a preferable production method.
Step (1): Step of recovering used polyolefin resin Step (2): Step of regenerating resin containing polyolefin resin recovered in step (1) Step (3): Resin 100 regenerated in step (2) A step of mixing 1 part by mass or more and 98 parts by mass or less of cellulose fibers and 1 part by mass or more and 40 parts by mass or less of a compatibilizing agent with respect to parts by mass.

  In step (1), there is no particular limitation as long as the polyolefin resin is recovered from the used product according to a known method. For example, the resins may be separately collected by utilizing the difference in the specific gravity of the resins, or the same product may be recovered in advance by recovering the same product. The recovered material may contain a resin other than the polyolefin resin, and a plurality of recovered materials may be mixed so as to have the composition of the thermoplastic resin described in the resin composition of the present invention.

  In step (2), there is no particular limitation as long as the recovered resin is regenerated according to a known method. The method for regenerating the resin is not particularly limited as long as the recovered resin species can be melted and mixed. The mixture may be molded according to a known method, for example, pellet molding. The melting temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher from the viewpoint of improving rigidity, heat resistance, and appearance of the molded body, and preferably 280 ° C. or lower, from the viewpoint of improving the appearance of the molded body. It is preferably 250 ° C or lower.

  The step (3) can be performed by referring to the mixing of the thermoplastic regenerated resin, the cellulose fiber, and the compatibilizer described above.

The resin composition of the present invention thus obtained is excellent in rigidity and heat resistance. For example, a No. 2 test piece was prepared based on JIS K7127, and its tensile modulus (GPa) and tensile breaking strain (%) were measured. From the viewpoint of improving rigidity when measured, the elastic modulus improvement rate calculated from the following (I) is preferably 50% or more, more preferably 100% or more, further preferably 150% or more, further preferably 200% or more. From the viewpoint of improving the appearance of the molded product, the breaking strain change rate calculated from the following (II) is preferably 150% or less, more preferably 125% or less, and further preferably 110% or less. Here, the “modulus of elasticity improvement” is the rate of improvement of the elastic modulus when the resin composition of the present invention and the thermoplastic resin itself are compared, and the rate of improvement is high. The higher the value, the higher the rigidity. Further, the "breaking strain change rate" is, with respect to the breaking strain of the thermoplastic recycled resin itself, the magnitude of the swing range of the breaking strain of the resin composition of the present invention, and the smaller the changing rate is, the resin It shows that the composition is homogeneous and the resulting molded article has a good appearance.
Elastic modulus improvement rate (%) = (MS / MB) × 100−100 (I)
MS: Average value of tensile elastic modulus of five test pieces of thermoformed sheet of resin composition
MB: Average value of tensile elastic modulus of 5 test pieces of thermoformed sheet molded only with thermoplastic recycled resin Break strain change rate (%) = [(EL-ES) / EA)] × 100 (II)
EL: Maximum value of tensile breaking strain of 5 test pieces of thermoformed sheet of resin composition
ES: minimum value of tensile breaking strain of 5 test pieces of thermoformed sheet of resin composition
EA: average value of tensile rupture strain of 5 test pieces of thermoformed sheet molded only with thermoplastic recycled resin

  The resin composition of the present invention is a resin composition containing a recycled resin, but since it has excellent rigidity and heat resistance, as a material that can recycle used pouches and general waste into another molded product, It can be preferably used.

  Therefore, the present invention also provides a technique capable of improving the physical properties of a resin composition containing a recycled resin. Specifically, for example, as a method of improving rigidity, in a resin composition containing A) a thermoplastic regenerated resin, B) 1 part by mass or more of cellulose fiber is added to 100 parts by mass of the thermoplastic regenerated resin. In the method, 1 part by mass or more and 40 parts by mass or less of C) a compatibilizing agent are blended. Regarding the A) thermoplastic regenerated resin, B) cellulose fiber, and C) compatibilizing agent, the details of the resin composition of the present invention can be referred to.

  The present invention also provides a molded product containing the resin composition of the present invention.

  The molded body is not particularly limited as long as it is a molded body of the resin composition of the present invention, and for example, known molding methods such as extrusion molding, injection molding, press molding, cast molding or solvent casting of the resin composition. Can be prepared by appropriately using. For example, it is possible to obtain a molded product according to the application by injecting or applying it to a package mold or a molding mold and then drying and curing it.

  In the case of preparing a sheet-shaped molded product, the thickness thereof is preferably 0.05 mm or more, more preferably 0.1 mm or more, still more preferably 0.15 mm or more, from the viewpoint of workability. Further, it is preferably 1.5 mm or less, more preferably 1.0 mm or less, still more preferably 0.5 mm or less.

  The molded article of the resin composition of the present invention thus obtained is excellent in rigidity and heat resistance and has a good appearance, and thus can be suitably used for various uses mentioned in the above resin composition.

Further, as one aspect of the present invention, there is provided a method for producing a molded body, which comprises processing the resin composition of the present invention into a molded body. There is no particular limitation as long as the resin composition of the present invention is used, and the thermoplastic recycled resin itself may be prepared. For example, a method including the following steps is exemplified as a suitable production method.
Step (1): Step of recovering used polyolefin resin Step (2): Step of regenerating resin containing polyolefin resin recovered in step (1) Step (3): Resin 100 regenerated in step (2) Step (4) of preparing a resin composition by mixing 1 part by mass or more and 98 parts by mass or less of cellulose fibers and 1 part by mass or more and 40 parts by mass or less of a compatibilizing agent with respect to parts by mass: step (3) ) A step of processing and molding the resin composition obtained in

  Regarding the steps (1) to (3), the section of the method for producing the resin composition of the present invention can be referred to.

  As the processing method adopted in the step (4), any known method such as extrusion molding, injection molding, press molding, cast molding or solvent casting method can be used without particular limitation.

  Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that this embodiment is merely an example of the present invention and does not imply any limitation. Parts in the examples are parts by mass unless otherwise specified. In addition, "normal pressure" means 101.3 kPa and "normal temperature" means 25 ° C.

[Average Fiber Diameter of Cellulose Fiber and Modified Cellulose Fiber]
The fiber diameter of the cellulose fiber or the modified cellulose fiber is obtained by the following method. About 0.3 g of absolutely dried cellulose fiber or modified cellulose fiber is weighed and stirred in 1.0 L of ion-exchanged water with a household mixer for 1 minute to dissolve the fiber in water. Thereafter, 4.0 L of ion-exchanged water was further added, and the mixture was stirred so as to be uniform, and about 50 g was collected as a measurement liquid from the obtained aqueous dispersion. The average fiber diameter is obtained by analyzing the obtained measurement liquid with "Kajaani Fiber Lab" manufactured by Metso Automation.

[Average Fiber Diameter of Fine Cellulose Fibers and Refined Modified Cellulose Fibers]
30 fibers obtained by observing a dispersion in which fine cellulose fibers or fine modified cellulose fibers are dispersed with an optical microscope (manufactured by Keyence Corporation, "Digital Microscope VHX-1000") at a magnification of 300 to 1000 times. Measure the average value above (round to the nearest 1 digit). If it is difficult to observe with an optical microscope, a solvent is further added to the dispersion to prepare a 0.0001% by mass dispersion, and the dispersion is dropped onto mica (mica) and dried to obtain an observation sample. As the fiber of the cellulose fiber in the observation sample, an atomic force microscope ("AFM, Nanoscope III Tapping mode AFM" manufactured by Digital instrument Co., Ltd., a probe uses Point Probe (NCH) manufactured by Nanosensors Inc.) is used. Measure the height. At that time, in a microscope image in which the cellulose fibers can be confirmed, five or more fine cellulose fibers are extracted, and the average fiber diameter (fiber diameter in the dispersion) is calculated from the fiber height.

[Confirmation of crystal structure of cellulose fiber]
The crystal structure of the cellulose fiber is confirmed by measuring it under the following conditions using "RigakuRINT 2500VC X-RAY diffractometer" manufactured by Rigaku Corporation.
〔Measurement condition〕
X-ray source: Cu / Kα-radiation,
Tube voltage: 40 kv, tube current: 120 mA,
Measurement range: diffraction angle 2θ = 5 to 45 °, X-ray scanning speed: 10 ° / min.
Measurement sample: Pellets having an area of 320 mm ^{2 and a} thickness of 1 mm (prepared by compressing cellulose fibers).
Crystallinity of cellulose type I crystal structure: The obtained X-ray diffraction intensity is calculated based on the following formula (A).
Cellulose type I crystallinity (%) = [(I22.6-I18.5) /I22.6] × 100 (A)
[Wherein I22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 is the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5 °). Show]

Preparation Example 1 of Cellulose Fiber (Cellulose Fiber of (i))
[Cutting process]
As the cellulose-containing raw material, a sheet-shaped wood pulp ["HV-10" manufactured by Tenbeck Co., Ltd., 800 mm x 600 mm x 1.0 mm, crystallinity 81.5%, cellulose content (residual components remaining after removing water from the cellulose-containing raw material Content in the following, the same below) 96 mass%, water content 8.5 mass%] is applied to a sheet pelletizer ("SG (E) -220" manufactured by Horai Co., Ltd.) to obtain about 4 mm x 4 mm x 1.0 mm. To a size (specific surface area 1.8 m ² / kg).
Measurement of water content The water content was measured using an infrared moisture meter (“MOC-120H” manufactured by Shimadzu Corporation), 5 g of the sample was placed on a weighing dish, and the drying temperature was 120 ° C., and the automatic stop mode (water content change for 30 seconds). The amount of water evaporation was obtained and calculated under the condition of (when the amount becomes 0.05% or less, measurement is completed).
[Drying treatment]
Using a shelf dryer (manufactured by ADVANTEC, vacuum constant temperature dryer "DRV320DA"), the pulp obtained by the cutting treatment is adjusted so that the moisture content of the pulp after drying is 1.0% by mass. Dried. The crystallinity calculated from the X-ray diffraction intensity of the pulp after the drying treatment was 82%. The bulk density of the pulp after the drying treatment was 200 kg / m ³ .
[Amorphization treatment]
100 g of the pulp obtained by the drying treatment was put into a batch type vibration mill (“MB-1” manufactured by Chuo Kakoki Co., Ltd., container total volume 3.5 L), diameter 30 mm, length 218 mm, material stainless steel, cross section Thirteen rods having a circular shape were filled in a vibration mill (filling ratio 57%) and treated for 30 minutes under conditions of an amplitude of 8 mm and a circular rotation of 1200 cpm to obtain amorphous cellulose.

Preparation Example 2 of Cellulose Fiber (Cellulose Fiber of (ii))
[Preparation of carboxyl group-containing fine cellulose fiber]
100 g of bleached kraft pulp fibers of softwood (Fletcher Challenge Canada, "Machenzie", CSF 650 ml) were thoroughly stirred with 9900 g of ion-exchanged water, and then TEMPO (free radical, 98, manufactured by ALDRICH) was added to 100 g of the pulp mass. Mass%) 1.25 mass%, sodium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) 12.5 mass%, sodium hypochlorite (manufactured by Wako Pure Chemical Industries, Ltd.) 28.4 mass% were added in this order. .. Using a pH stud, the pH was maintained at 10.5 by dropwise addition of 0.5M sodium hydroxide. After carrying out the reaction for 120 minutes (20 ° C.), the dropping of sodium hydroxide was stopped to obtain oxidized pulp. The obtained oxidized pulp was thoroughly washed with ion-exchanged water, and then dehydrated. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were subjected to a micronization treatment twice at 245 MPa using a high-pressure homogenizer ("Starburst Lab HJP-2 5005" manufactured by Sugino Machine Ltd.), and a carboxy group-containing fine particle was finely divided. A cellulose fiber dispersion liquid (solid content concentration 1.3% by mass) was obtained. This fine cellulose fiber had an average fiber diameter of 3.3 nm and a carboxy group content of 1.4 mmol / g.
[Acid type treatment]
To the obtained carboxy group-containing fine cellulose fiber dispersion 408.75 g (solid content concentration 1.3% by mass), ion-exchanged water 4085 g was added to prepare a 0.5% by mass aqueous solution, and the mechanical stirrer was operated at room temperature (25 ° C.). It was stirred for 30 minutes. Subsequently, 245 g of a 1 M aqueous hydrochloric acid solution was charged and reacted at room temperature for 1 hour. After the reaction was completed, the precipitate was reprecipitated with acetone, filtered, and then washed with acetone / ion-exchanged water to remove hydrochloric acid and salts. Finally, acetone was added and filtered to obtain an acetone-containing acid type cellulose fiber dispersion liquid (solid content concentration 5.0% by mass) in a state where the carboxy group-containing fine cellulose fibers were swollen. After completion of the reaction, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salts. After solvent substitution with acetone, the solvent substitution with DMF was performed to obtain a DMF-containing acid-type cellulose fiber dispersion liquid (solid content concentration 5.0% by mass) in a state in which carboxy group-containing fine cellulose fibers were swollen. This fine cellulose fiber had an average fiber diameter of 3.3 nm and a carboxy group content of 1.6 mmol / g.
[Introduction of substituent]
A beaker equipped with a magnetic stirrer and a stirrer was charged with 40 g of the acid type carboxy group-containing fine cellulose fiber dispersion obtained above (solid content concentration 5.0% by mass). Subsequently, aniline was charged in an amount corresponding to 1.2 mol of amino groups with respect to 1 mol of carboxy groups of fine cellulose fibers, 0.34 g of 4-methylmorpholine, and 1.98 g of DMT-MM as a condensing agent, and added to 300 g of DMF. Dissolved. The reaction solution was reacted at room temperature (25 ° C) for 14 hours. After completion of the reaction, filtration, washing with ethanol, removal of DMT-MM salt, and further vacuum drying at 50 ° C. overnight, modified cellulose fibers in which phenyl groups are linked to the cellulose fibers through amide bonds are obtained. Obtained (hydrocarbon group bond amount 1.2 mmol / g, introduction rate 80%).

The carboxy group content and the introduction rate of hydrocarbon groups in the cellulose fiber (ii) were determined by the following methods.
[Carboxy group content of cellulose fiber]
A sample with a dry mass of 0.5 g is placed in a 100 mL beaker, ion-exchanged water or a mixed solvent of methanol / water = 2/1 is added to make 55 mL in total, and 5 mL of 0.01 M sodium chloride aqueous solution is added thereto to prepare a dispersion liquid Then, the dispersion was stirred until it was sufficiently dispersed. The pH of the dispersion was adjusted to 2.5 to 3 by adding 0.1 M hydrochloric acid, and a 0.05 M sodium hydroxide aqueous solution was used using an automatic titrator (trade name "AUT-50" manufactured by Toa DKK Co., Ltd.). The dispersion liquid was added dropwise to the dispersion liquid under the condition of waiting time of 60 seconds, the electric conductivity and the pH value were measured every 1 minute, and the measurement was continued until the pH became about 11, to obtain an electric conductivity curve. The sodium hydroxide titer was determined from this conductivity curve, and the carboxy group content of the cellulose fiber or modified cellulose fiber was calculated by the following formula.
Carboxy group content (mmol / g) = Sodium hydroxide titer x Sodium hydroxide aqueous solution concentration (0.05M) / Cellulose fiber mass (0.5g)
[Introduction rate of hydrocarbon groups in cellulose fiber]
The content of carboxy groups in the cellulose fiber before and after the introduction of hydrocarbon groups was determined by the titration method, and the average amount of hydrocarbon groups bonded was calculated by the following formula.
Hydrocarbon group bond amount (mmol / g) = carboxy group content in cellulose fiber before introduction of hydrocarbon group (mmol / g) -carboxy group content in modified cellulose fiber after introduction of hydrocarbon group (mmol) / G)
Hydrocarbon group introduction rate (%) = {bond amount of hydrocarbon groups (mmol / g) / carboxy group content in modified cellulose fiber before introduction of hydrocarbon groups (mmol / g)} × 100

Preparation Example 3 of Cellulose Fiber (Cellulose Fiber of (iii))
[Production of alkali-treated bagasse]
To 100 parts by mass (dry weight) of bagasse (powder of sugar cane), 937 parts by mass of water and 15.2 parts by mass of sodium hydroxide as a whole are added granular sodium hydroxide and ion-exchanged water, A heat treatment was performed at a temperature of 120 ° C. for 2 hours in an autoclave (“LSX-700” manufactured by Tommy Seiko Co., Ltd.). After the treatment, filtration and ion exchange water washing were performed, and vacuum treatment was performed overnight at 70 ° C. to obtain alkali-treated bagasse (fibrous, average fiber diameter 24 μm, cellulose content 70% by mass, water content 3% by mass). ..
[Introduction of substituent]
Into a kneader (“PNV-1 type” manufactured by Irie Shosha Co., Ltd., volume 1.0 L) equipped with a reflux tube and a dropping funnel, 100 g of absolutely dried alkali-treated bagasse was charged, and 100 g of a 6.4 mass% sodium hydroxide aqueous solution was added. (0.26 equivalents / AGU) and 100 g of isopropanol were sequentially added, and then stirred at room temperature and 50 rpm for 30 minutes to uniformly mix. Furthermore, 92.7 g (1.5 equivalents / AGU) of 1,2-epoxyhexane was added dropwise over 1 minute, and the reaction was performed for 24 hours under reflux conditions at 70 ° C. while stirring. After the reaction, neutralized with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), thoroughly washed with a water / isopropanol mixed solvent to remove impurities, and further vacuum dried at 50 ° C. overnight to obtain modified cellulose fiber. Got

The introduction rate of the hydrocarbon group of the cellulose fiber (iii) was determined by the following method.
The content% (mass%) of the hydrophobic ether group contained in the obtained modified cellulose fiber was determined by Analytical Chemistry, Vol. 51, No. Zeisel method known as a method for analyzing the average number of moles of addition of alkoxy groups of cellulose ether, as described in 13, 2172 (1979), "15th Revised Japanese Pharmacopoeia (section of method for analysis of hydroxypropylcellulose)" and the like. Calculated according to The procedure is shown below.
(I) 0.1 g of n-octadecane was added to a 200 mL volumetric flask, and the volume was adjusted to the marked line with hexane to prepare an internal standard solution.
(Ii) 100 mg of the modified and dried modified cellulose fiber and 100 mg of adipic acid were precisely weighed in a 10 mL vial bottle, 2 mL of hydroiodic acid was added, and the container was sealed.
(Iii) The mixture in the vial bottle was heated with a block heater at 160 ° C. for 1 hour while stirring with a stirrer chip.
(Iv) After heating, 3 mL of the internal standard solution and 3 mL of diethyl ether were sequentially poured into the vial, and the mixture was stirred at room temperature for 1 minute.
(V) The upper layer (diethyl ether layer) of the mixture separated into two phases in the vial was analyzed by gas chromatography ("GC2010 Plus" manufactured by SHIMADZU). The analysis conditions were as follows.
Column: DB-5 (12 m, 0.2 mm × 0.33 μm) manufactured by Agilent Technologies
Column temperature: 100 ° C. → 10 ° C./min→280° C. (10 min Hold)
Injector temperature: 300 ° C, Detector temperature: 300 ° C, Injection amount: 1 μL
The content (mass%) of the ether group in the modified cellulose fiber was calculated from the detected amount of the etherification reagent used.
From the obtained ether group content, the molar substitution degree (MS) was calculated using the following (Formula 1).
(Formula 1)
MS = (W1 / Mw) / ((100-W1) /162.14)
W1: Content of ether group in modified cellulose fiber (mass%)
Mw: molecular weight of introduced etherification reagent (g / mol)

Examples 1-5 and Comparative Examples 1-7 (however, Examples 4 and 5 are reference examples)
The raw materials for the composition shown in Table 2 were melt-kneaded using a kneader (manufactured by Toyo Seiki Seisakusho Co., Ltd., "Labo Plastomill") at a rotation speed of 90 rpm for 8 minutes at the temperature shown in Table 2 to obtain a resin composition. ..

  The obtained resin composition was pressed at 240 ° C. for 1 minute at 0.4 MPa and at 20 MPa for 1 minute using a heat press machine (manufactured by Toyo Seiki Seisakusho Ltd., “Labo Press”), and then cooled to 20 ° C. By doing so, a sheet having a thickness of 0.4 mm was formed.

The raw materials in Table 2 are as follows.
<Thermoplastic recycled resin>
Recycled PE: recycled polyethylene resin (composition: 91% by weight polyethylene, 6% by weight polyamide, 3% by weight polyester)
<Cellulose fiber>
Cellulose Fiber (i): Amorphous Cellulose Fiber Prepared in Preparation Example 1 Cellulose Fiber (ii): Modified Cellulose Fiber Prepared in Preparation Example 2 Cellulose Fiber (iii): Preparation Example of Cellulose Fiber Modified cellulose fiber prepared in 3

<Compatibilizer>
Yumex 1001: Sanyo Kasei Co., Ltd., maleic anhydride modified polypropylene, melt viscosity 15000 mPa · s (160 ° C, BL type viscometer)
BF-7M: Sumitomo Chemical Co., Ltd., polyethylene-polyglycidyl methacrylate-polymethyl acrylate copolymer, MFR (190 ° C. × 2.16 kg) 7.0 g / 10 min
Orevac OE808: Arkema, maleic anhydride modified polyethylene, MFR (190 ° C x 2.16kg) 0.6g / 10min

  The characteristics of the obtained molded body were evaluated according to the methods of Test Examples 1 and 2 below. The results are shown in Table 2.

Test example 1 (heat resistance)
Using a dynamic viscoelastic device (“DMS6100” manufactured by SII), the storage elastic modulus of a strip sample cut out from the obtained molded body with a width of 5 mm and a length of 20 mm was measured at a frequency of 66.7 Hz under a nitrogen atmosphere. Then, the temperature was increased from −20 ° C. to 200 ° C. at a rate of 2 ° C. per minute, measurement was performed in the tensile mode, and the temperature at which the storage elastic modulus was 160 MPa or less was set as the heat resistant temperature. The higher the heat resistant temperature is, the better the heat resistance is.

Test Example 2 (break strain change rate, elastic modulus improvement rate)
In a thermostatic chamber at 25 ° C, 5 sheets of No. 2 test piece were prepared from the obtained sheet based on JIS K7127, and a tensile test was conducted to examine the tensile elastic modulus (GPa) and the tensile breaking strain (%), and the elastic modulus was obtained. The improvement rate and the breaking strain change rate were calculated from the following equations (I) and (II). For the tensile test, an autograph precision universal testing machine (AGS-10kNX) manufactured by SHIMADZU was used, and a 5-point test was performed for each sample according to JIS K7127. The higher the numerical value of the elastic modulus improvement rate is, the better the rigidity is, and the smaller the numerical value of the breaking strain change rate is, the better the appearance quality of the molded product is.
Elastic modulus improvement rate (%) = (MS / MB) × 100−100 (I)
MS: Average value of tensile elastic modulus of five test pieces of thermoformed sheet of resin composition
MB: Average value of tensile elastic modulus of 5 test pieces of the thermoformed sheet of Comparative Example 1 Breaking strain change rate (%) = [(EL-ES) / EA)] × 100 (II)
EL: Maximum value of tensile breaking strain of 5 test pieces of thermoformed sheet of resin composition
ES: minimum value of tensile breaking strain of 5 test pieces of thermoformed sheet of resin composition
EA: average value of tensile breaking strain of 5 test pieces of the thermoformed sheet of Comparative Example 1

  From Table 2, the resin compositions of Examples have a high heat resistance temperature, a high rate of improvement in tensile modulus and a high rigidity, and the rate of change in tensile breaking strain (variation range). It can be seen that a small and homogeneous resin composition is obtained. The sheet cross section of Example 1 is shown in FIG. 1 and the sheet cross section of Comparative Example 4 is shown in FIG. 2. From this comparison, it is confirmed that the interface between the regenerated resin and the cellulose fiber is stabilized by adding the compatibilizer. I understand.

  The resin composition of the present invention can be suitably used as a recycled material.

Claims (11)

A) A thermoplastic regenerated resin 50% by mass or more and 88.9 % by mass or less B) Cellulose fiber 7% by mass or more and 10% by mass or less, and C) A compatibilizing agent 2% by mass or more and 5% by mass or less And (B) a cellulose composition in which the cellulose fiber is (iii) below.
(Iii) A modified cellulose fiber in which a hydrocarbon group is bonded to a cellulose fiber through an ether bond and has a cellulose type I crystal structure.   Regarding the thermoformed sheet of the resin composition, the elastic modulus improvement rate calculated from the tensile elastic modulus (GPa) and the tensile breaking strain (%) of the No. 2 test piece measured based on JIS K7127 is 50% or more, and The resin composition according to claim 1, wherein the breaking strain change rate is 150% or less. In the modified cellulose fiber (iii), one or more substituents selected from the substituents represented by the following general formula (1) and the substituents represented by the following general formula (2) are ether bonds. The resin composition according to claim 1 or 2, which is a modified cellulose fiber having a cellulose I type crystal structure bonded to the cellulose fiber via the.
_{-CH 2 -CH (OH) -R 1} (1)
_{-CH 2 -CH (OH) -CH 2} - (OA) n -O-R 1 (2)
[In formula, R < ₁ > in General formula (1) and General formula (2) respectively independently shows a C3 or more and 30 or less linear or branched alkyl group, and n in General formula (2) is 0. And 50 or more and 50 or less, and A represents a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms]   A) The resin composition according to any one of claims 1 to 3, wherein the thermoplastic recycled resin contains 60% by mass or more of polyolefin.   The resin composition according to claim 4, wherein the polyolefin is polyethylene.   The resin composition according to claim 1, wherein the C) compatibilizer is a compound having a polar group and a polyolefin.   The resin composition according to any one of claims 1 to 6, wherein the C) compatibilizer is a maleic anhydride-modified polyolefin. A method for producing a resin composition, comprising: A) a thermoplastic regenerated resin, B) a cellulose fiber, and C) a compatibilizer, wherein the content of the A) thermoplastic regenerated resin in the resin composition is 50% by mass or more. 88.9 mass% or less, B) Cellulose fiber content is 7 mass% or more and 10 mass% or less, C) Compatibilizer content is 2 mass% or more and 5 mass% or less, and B) A method for producing a resin composition, wherein the cellulose fiber is the following (iii).
(Iii) A modified cellulose fiber in which a hydrocarbon group is bonded to a cellulose fiber through an ether bond and has a cellulose type I crystal structure.   A molded body containing the resin composition according to claim 1.   A method for producing a molded body, which comprises processing the resin composition according to claim 1 to obtain a molded body. A method for improving the rigidity of a resin composition, characterized in that B) cellulose fibers and C) a compatibilizer are added to a resin composition containing A) a thermoplastic regenerated resin. In the product, the content of A) the thermoplastic regenerated resin is 50% by mass or more and 88.9 % by mass or less, the content of B) the cellulose fiber is 7% by mass or more and 10% by mass or less, and the content of the C) compatibilizer is 2. A method for improving the rigidity of a resin composition, wherein B) the cellulose fiber is the following (iii), which is blended in an amount of from 5% by mass to 5% by mass.
(Iii) A modified cellulose fiber in which a hydrocarbon group is bonded to a cellulose fiber through an ether bond and has a cellulose type I crystal structure.