WO2019026258A1

WO2019026258A1 - Resin composition

Info

Publication number: WO2019026258A1
Application number: PCT/JP2017/028312
Authority: WO
Inventors: 茂久上村; 浩二大崎; 大崎　和友; 貢平山田; 知也和田
Original assignee: 花王株式会社
Priority date: 2017-08-03
Filing date: 2017-08-03
Publication date: 2019-02-07

Abstract

This resin composition includes: a thermoplastic resin; and 5-70 part by mass of an amorphous cellulose having a relative crystallinity of less than 50%, and 2-20 parts by mass of a compatibilizer (where the thermoplastic resin is polyethylene, the content of a compatibilizer is 4-20 parts by mass), with respect to 100 parts by mass of the thermoplastic resin. The resin composition according to the present invention achieves both rigidity and toughness, and can thus be suitably used for various industrial applications such as daily goods, household electrical appliances, packaging materials for home electric appliance parts, automobile parts and the like.

Description

Resin composition

The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition containing a thermoplastic resin and a method for producing the same, and a molded article containing the resin composition and a method for producing the same.

Generally, in order to impart rigidity to a resin, a method of adding a reinforcing filler is taken, and in fact, a reinforcing resin by glass fiber or carbon fiber is put to practical use. However, since glass fiber (GF) is a non-combustible material, GF reinforcing material is not only difficult to thermally recycle, but also high in density, so it is not suitable for applications requiring light weight and high strength. On the other hand, carbon fibers have a low density compared to GF, and carbon fiber reinforced materials exhibit high rigidity, but carbon fibers are flame retardant materials, and in addition to the price, there are problems with recycling as well as GF. On the other hand, vegetable fibers are pulped and further nano-fibrillated cellulose nanofibers (CNF) are lightweight, have five times the strength of steel or more, and low linear thermal expansion of 1/50 of glass. It is very promising as a reinforcing fiber and has been actively studied in recent years.

However, CNF has a large number of hydroxyl groups, has low affinity with many general purpose thermoplastic resins such as polyethylene and polypropylene, interfacial peeling and aggregation occur, and toughness and impact resistance are greatly reduced. Therefore, attempts have been actively made to improve the heat resistance of CNF by chemically modifying the surface of CNF, to improve the affinity to the target resin, and to develop additives such as a compatibilizer.

For example, in Patent Document 1, by blending a cellulose having a crystallinity of less than 50% with a polyolefin resin and / or a styrenic resin, the obtained molded product has both strength and flexibility, and further, it has an impact resistance. It has been reported that the superior effect of superiority is achieved. Further, Patent Document 2 reports that toughness is improved by adding non-crystallized cellulose and an elastomer to a matrix resin.

JP, 2011-137094, A JP, 2015-155535, A

That is, the present invention relates to the following [1] to [4].
[1] 5 parts by mass or more and 70 parts by mass or less of non-crystallized cellulose having a relative crystallinity degree of less than 50% and 100 parts by mass of the thermoplastic resin in 100 parts by mass of the thermoplastic resin A resin composition comprising: at least 20 parts by mass but not less than 4 parts by mass and at most 20 parts by mass of a compatibilizer when the thermoplastic resin is polyethylene.
[2] 5 parts by mass or more and 70 parts by mass or less of non-crystallized cellulose having a relative crystallinity degree of less than 50% and 100 parts by mass of the thermoplastic resin in 100 parts by mass of the thermoplastic resin A method for producing a resin composition, comprising: at least 20 parts by mass, but in the case where the thermoplastic resin is polyethylene, at least 4 parts by mass and not more than 20 parts by mass of a compatibilizer.
[3] A molded article containing the resin composition of the above-mentioned [1].
[4] A method for producing a molded article, wherein the resin composition according to the above [1] is processed into a molded article.

FIG. 1 is a view showing a SEM image of a cross section of a sheet of the resin composition of Example 3. Arrows in the figure indicate the state in which non-crystallized cellulose is dispersed. FIG. 2 is a view showing a SEM image of the sheet cross section of the resin composition of Comparative Example 3.

Detailed Description of the Invention

There is a need for a resin composition that is more excellent in toughness and rigidity than the resin composition obtained by the method of Patent Document 1. Moreover, it turned out that sufficient rigidity can not be ensured with the method of Patent Document 2.

Therefore, the present invention relates to a resin composition having both toughness and rigidity and a method for producing the same, and a molded article containing the resin composition and a method for producing the same.

Therefore, as a result of intensive studies by the present inventors, it is possible to improve the rigidity without lowering the toughness of the resulting molded body by adding a specific amount of each of the non-crystallized cellulose and the compatibilizer to the thermoplastic resin. The present invention has been completed.

That is, the resin composition of the present invention relates to those having the excellent effect of achieving both toughness and rigidity.

[Resin composition]
The resin composition of the present invention is characterized by containing a specific amount of a cellulose having a specific relative degree of crystallinity and a compatibilizer with respect to a thermoplastic resin.

In general, amorphous cellulose is said to be more reactive than crystalline cellulose. The compatibilizer has a functional group capable of reacting or interacting with cellulose, interacts only with the cellulose surface when the compatibilizer acts on crystalline cellulose, and stabilizes the interface between the matrix resin and the cellulose, Elastic modulus is improved. On the other hand, when the compatibilizer acts on the non-crystalline cellulose, the compatibilizer penetrates to the inside of the cellulose to suppress the strong interaction between the cellulose, so the interface between the matrix resin and the cellulose is stabilized. It is considered that the dispersion state of the cellulose in the resin is improved and the breaking strain is improved not only by the improvement of the elastic modulus by the hardening, but also by the weak mechanical force such as ordinary kneading. However, these guesses do not limit the present invention.

[Thermoplastic resin]
The thermoplastic resin in the present invention is not particularly limited, and polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyamide resin, nylon resin, vinyl chloride resin, vinyl ether resin, polyvinyl alcohol resin, polycarbonate resin, polysulfone resin, etc. It can be mentioned. These can be used singly or in combination of two or more. Among them, from the viewpoint of improving toughness, those containing one or more selected from polyolefin resins, polystyrene resins, polyester resins, and polyamide resins as a constituent resin are preferable, and those selected from polyolefin resins and polyamide resins 1 It is more preferable to contain the species or two as the constituent resin, and it is more preferable to contain at least the polyolefin resin.

As polyolefin resin, 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), etc. are illustrated. Among these, it is preferable to contain one or both selected from polyethylene and polypropylene. The content of the polyolefin resin in the thermoplastic resin is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more is there. The upper limit is not particularly limited, and may be a polyolefin resin, that is, 100% by mass.

The content of the thermoplastic resin in the resin composition of the present invention is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, from the viewpoint of improving the toughness of the molded body obtained. More preferably, it is 65 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more. Further, from the viewpoint of improving the rigidity of the obtained molded product, it is preferably 93% by mass or less, more preferably 90% by mass or less, still more preferably 87% by mass or less, still more preferably 85% by mass or less, still more preferably 83% by mass % Or less.

[cellulose]
Cellulose fiber is a fibrous reinforcing material which can be expected to be reduced in weight and thermal recyclability, but when its content is increased, the viscosity of the resin composition is increased, so that the formability is reduced, fiber aggregation, polymer matrix and the like Decrease in toughness due to interface instability with the Thus, the cellulose used in the present invention is non-crystallized cellulose having a relative crystallinity of less than 50%. Hereinafter, it may be described simply as "non-crystallized cellulose".

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

Although the non-crystallized cellulose in the present invention has a relative crystallinity of less than 50%, it is preferably 49% or less, more preferably 40% or less, still more preferably 30% or less from the viewpoint of the toughness of the resulting molded body It is. Further, from the viewpoint of improving the rigidity of the obtained molded product, it is preferably -70% or more, more preferably -60% or more, and still more preferably -50% or more. It should be noted that the smaller the value of relative crystallinity, the larger the ratio of the noncrystalline portion to the crystalline portion.

Such non-crystallized cellulose is obtained by treating at least one cellulose-containing material selected from woods, pulps, papers, plant stems / leaves, plant shells and the like with a grinder to obtain cellulose crystals. It can be obtained by reducing the degree of For example, the method described in JP-A-2011-1547 can be referred to. The cellulose I-type crystallinity of commercially available pulp is usually 60% or more.

Specifically, if necessary, the cellulose-containing raw material is adjusted in size to a size of preferably 0.1 to 70 mm by using a shredder or the like, and then treated with a media crusher or extruder. Roughness obtained by adjusting the bulk density to 50 to 600 kg / m ³ or the specific surface area to 0.2 to 750 m ² / kg by conducting, drying, or performing any treatment. The ground cellulose is stirred for 0.5 minutes to 24 hours using an impact-type grinder to obtain non-crystallized cellulose with a reduced degree of crystallinity. The relative crystallinity degree of the obtained non-crystallized cellulose can be controlled by adjusting the circumferential speed of the rotor, the sample supply speed, the stirring time and the like. In addition, it is preferable that the water content of a raw material will be 1.8 mass% or less from a viewpoint of performing a grinding process efficiently.

The lower limit of the average fiber diameter of the non-crystallized cellulose thus obtained is not particularly set, but it is preferably 0.01 μm or more, more preferably 1 μm or more, still more preferably 5 μm or more, from the viewpoint of dispersibility in the resin. More preferably, it is 10 micrometers or more, More preferably, it is 20 micrometers or more. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, and still more preferably 100 μm or less from the viewpoint of toughness. Incidentally, the non-crystallized cellulose after being dispersed in the resin composition of the present invention is refined by the dispersion at the time of mixing the raw materials described later, and it is finer than the above-mentioned average fiber diameter, for example, an average fiber diameter The In the present specification, the average fiber diameter of cellulose fibers is the volume-based median diameter, and can be measured according to the method described in the examples below.

The content of the non-crystallized cellulose in the resin composition of the present invention is 5 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, preferably from the viewpoint of the rigidity of the obtained molded body Is 7 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 13 parts by mass or more, still more preferably 15 parts by mass or more, preferably 60 parts by mass or less from the viewpoint of toughness of the obtained molded body The amount is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass or less.

The content of non-crystallized cellulose in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, from the viewpoint of improving the rigidity of the molded article obtained. More preferably, it is 10 mass% or more, More preferably, it is 12 mass% or more. Further, from the viewpoint of toughness of the resulting molded body, it is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less It is.

[Compatibilizer]
Known compatibilizers can be used as the compatibilizer that can be used in the present invention, but from the viewpoint of improving the dispersibility of the non-crystallized cellulose and stabilizing the interface between the non-crystallized cellulose and the thermoplastic resin, It is preferable to contain one or more selected from the following compatibilizers.
Compatibilizer (1): ethylene / vinyl acetate copolymer compatibilizer (2): ethylene / (meth) acrylate copolymer compatibilizer (3): acid anhydride group, carboxyl group, amino group, Polyolefin resin compatibilizer (4) having at least one functional group (substituent) selected from the group consisting of imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group: acid Acrylic having at least one functional group (substituent) selected from the group consisting of anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group, and epoxy group Resin or Styrene Resin Compatibilizer (5): Polyester Resin Compatibilizer (6): Ionomer Resin

Although these can be used singly or in combination of two or more, among them, from the viewpoint of achieving both the rigidity and toughness of the obtained molded product, it is selected from among the compatibilizer (3) and the compatibilizer (4) 1 type, or 2 or more types are preferable, and 1 type or 2 or more types selected from a compatibilizer (3) are more preferable.

The polyolefin resin in the compatibilizer (3) 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 , Copolymers with methacrylic acid, acrylic acid etc.), propylene polymers [polypropylene, copolymers of propylene and one or more other vinyl compounds, etc.], ethylene propylene copolymer, polybutene and the like Poly-4-methylpentene-1 and the like, and more preferred are ethylene polymers and propylene polymers.

Further, the functional group in the polyolefin resin is at least one selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group. Although it is a species, it is preferably an acid anhydride group or an epoxy group, more preferably an acid anhydride group. Specifically, maleic anhydride, maleic acid, succinic anhydride, succinic acid and glycidyl methacrylate are exemplified.

As preferable examples of such a compound, "bond first 7M" (copolymer of polyethylene having an epoxy group and (meth) acrylic acid) manufactured by Sumitomo Chemical Co., Ltd., "Rexpearl" (having an epoxy group) manufactured by Japan Polyethylene Corporation Polyolefin resin), Nippon Oil & Fats Co., Ltd. "Modiper" (polyolefin resin having an epoxy group), Sanyo Chemical Industries, Ltd. "Yumex" (polypropylene having maleic anhydride), Arkema "Olevac" (maleic anhydride Polyethylene), “Rotader” (polyolefin resin having acid anhydride) by Orchem, “bondine” (polyolefin resin having acid anhydride) by Sumitomo Chemical Co., Ltd., “Nuclel” by Mitsui Dupont (Polyolefin resin having a carboxyl group), Dow Chemical Co., Le "etc. (polyolefin resin having a carboxyl group).

The weight average molecular weight (Mw) of the compatibilizer is preferably 1000 or more, more preferably 5000 or more, still more preferably 10000 or more, and still more preferably 20000 or more from the viewpoint of the rigidity of the resulting molded article. Further, from the viewpoint of the toughness of the obtained molded product, it is preferably 100,000 or less, more preferably 90000 or less, still more preferably 80000 or less, still more preferably 70000 or less, still more preferably 60000 or less. In the present specification, the weight average molecular weight can be measured according to the method described in the following examples.

In the resin composition of the present invention, the content of the compatibilizer is 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, but both the rigidity and the toughness of the obtained molded body are achieved. From the viewpoint, it is preferably 5 parts by mass or more. In addition, from the same viewpoint, the content is preferably 17 parts by mass or less, more preferably 14 parts by mass or less, still more preferably 11 parts by mass or less, and still more preferably 8 parts by mass or less. However, when the thermoplastic resin is polyethylene, the amount is 4 parts by mass or more and 20 parts by mass or less. In the case of polyethylene, unlike other thermoplastic resins such as polypropylene, the desired effect may not be sufficiently exhibited if the compatibilizer is less than 4 parts by mass. On the other hand, when the thermoplastic resin is other than polyethylene, specifically, polypropylene, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylic acid ester, polybutadiene, polyisoprene, polychloroprene, etc. In the case of polypropylene, preferably, the desired effect is sufficiently exhibited even when the amount of the compatibilizer is in a range of small amount, for example, in a range of 2 parts by mass or more and less than 4 parts by mass. When the elastic modulus of the compatibilizer is lower than the elastic modulus of the thermoplastic resin, as in the case of polypropylene, the rigidity of the resin compound decreases as the amount of the compatibilizer added increases. On the other hand, when the elastic modulus of the thermoplastic resin and the elastic modulus of the compatibilizer are equal to each other as in polyethylene, the rigidity of the resin compound is unlikely to decrease even if the addition amount of the compatibilizer is increased.

In addition, the content of the compatibilizer in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass, from the viewpoint of achieving both the rigidity and the toughness of the molded body obtained. The above, more preferably 4% by mass or more. In addition, from the same viewpoint, the content is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less.

The mass ratio of the compatibilizer to the non-crystallized cellulose (compatibilizer / non-crystallized cellulose) is preferably 0.8 or less, more preferably 0. It is 6 or less, more preferably 0.4 or less, and still more preferably 0.3 or less. Moreover, from the same viewpoint, it is preferably 0.06 or more, more preferably 0.08 or more, further preferably 0.1 or more, and still more preferably 0.15 or more.

Crystal nucleating agent
In addition to the above components, a crystal nucleating agent can be further used in the resin composition of the present invention from the viewpoint of the rigidity of the resulting molded body.

Examples of crystal nucleating agents include inorganic crystal nucleating agents and organic crystal nucleating agents. Examples of inorganic crystal nucleating agents include natural or synthetic silicate compounds, titanium oxide, barium sulfate, tricalcium phosphate, calcium carbonate, sodium phosphate, kaolinite, halloysite, talc, smectite, vermeulite, mica, etc. Be Examples of the organic crystal nucleating agent include amides, organic acid metal salts, sorbitol derivatives, nonitol derivatives, etc. From the viewpoint of improving rigidity, organic acid metal salts and sorbitol derivatives are preferable. Examples of the organic acid metal salt include sodium benzoate, aluminum dibenzoate, potassium benzoate, lithium benzoate, sodium β · naphthalate, sodium cyclohexane carboxylate, zinc phenylphosphonate and the like, and examples of the sorbitol derivative include 1,3: Examples thereof include 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol, and a sorbitol derivative is preferable from the viewpoint of achieving both rigidity and toughness.

The content of the crystal nucleating agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, with respect to 100 parts by mass of the thermoplastic resin, from the viewpoint of improving the rigidity and the degree of crystallinity. Preferably it is 3.0 mass parts or less, More preferably, it is 2.0 mass parts or less.

The resin composition of the present invention contains, as components other than the above, a plasticizer; a filler (inorganic filler, organic filler); a hydrolysis inhibitor; a flame retardant; an antioxidant; a hydrocarbon wax and an anion -Type surfactant: lubricant, UV absorber, antistatic agent, anti-fogging agent, light stabilizer, pigment, anti-mold agent, antibacterial agent, foaming agent, surfactant, polysaccharides such as starches, alginic acid, gelatin Natural proteins such as pomace, casein, etc .; Inorganic compounds such as tannins, zeolites, ceramics, metal powders, etc .; perfumes; flow control agents; leveling agents; conductive agents; ultraviolet light dispersants; Can be contained in the range which does not impair. Moreover, it is also possible to add other polymeric materials and other resin compositions in the range which does not inhibit the effect of this invention. The content ratio of the optional additive may be suitably contained within the range not impairing the effects of the present invention, but for example, 20% by mass or less in the resin composition is preferable, and about 10% by mass or less is more preferable. About 5 mass% or less is still more preferable.

The resin composition of the present invention can be prepared without particular limitation as long as it contains a specific amount of non-crystallized cellulose and a specific amount of a compatibilizer with respect to the thermoplastic resin, for example, as described above The raw materials containing various additives in addition to the three components are optionally stirred with a Henschel mixer or the like, or using a known kneader such as a closed kneader, single- or twin-screw extruder, or open-roll type kneader It can be prepared by melt-kneading or solvent casting. The raw materials can also be subjected to melt-kneading after being uniformly mixed in advance using a Henschel mixer, a super mixer, etc., and the resin composition of the present invention improves the dispersibility of non-crystallized cellulose by the compatibilizer. In some cases, the raw materials can be mixed at once and melt-kneaded instead of being separately mixed in advance. In addition, in order to promote the plasticity of a thermoplastic resin when preparing a resin composition, a supercritical gas may be present and melt mixed. After the melt-kneading, the melt-kneaded product may be dried according to a known method.

The melt-kneading temperature is preferably 180 ° C. or more, more preferably 190 ° C. or more, still more preferably 200 ° C. or more, still more preferably 220 ° C. or more, further preferably from the viewpoint of improving the moldability of the resin composition and the prevention of deterioration. The temperature is 225 ° C. or more, more preferably 230 ° C. or more, preferably 300 ° C. or less, more preferably 290 ° C. or less, still more preferably 280 ° C. or less. The melt-kneading time can not be determined generally depending on the melt-kneading temperature and the type of the kneader, but is preferably 15 seconds or more and 900 seconds or less.

[Method of producing resin composition]
The present invention also provides a method of producing the resin composition of the present invention.

As a method for producing the resin composition of the present invention, 5 parts by mass to 70 parts by mass of non-crystallized cellulose, and 2 parts by mass to 20 parts by mass of compatibilization with respect to 100 parts by mass of the above-mentioned thermoplastic resin There is no particular limitation on the agent, provided that it includes the step of mixing 4 parts by mass or more and 20 parts by mass or less of the compatibilizing agent when the thermoplastic resin is polyethylene. For example, the raw material containing various additives as necessary in addition to the thermoplastic resin, the non-crystallized cellulose, and the compatibilizer is preferably 180 ° C. or more, more preferably 190 ° C. or more, still more preferably 200 ° C. or more An embodiment of mixing at a temperature of preferably 300 ° C. or less, more preferably 290 ° C. or less, still more preferably 280 ° C. or less is exemplified. In addition, in the case of mixing, it is preferable to mix a raw material at once from a viewpoint of productivity. The mixing time is not set according to the composition of the raw material or the mixing temperature, and is, for example, 15 seconds or more and 900 seconds or less. In addition, the method of the preparation of non-crystallized cellulose can refer to the term of the resin composition of this invention. As described above, when the thermoplastic resin is polyethylene, when the amount of the compatibilizer is small, that is, less than 4 parts by mass, the desired effect may not be sufficiently exhibited. On the other hand, when the thermoplastic resin is other than polyethylene, the desired effect is sufficiently exhibited even when the amount of the compatibilizer is in a range of small amount, for example, in the range of 2 parts by mass to less than 4 parts by mass.

The resin composition of the present invention thus obtained is excellent in toughness and rigidity. For example, a No. 2 test piece is produced based on JIS K 7127, and the tensile elastic modulus (GPa) and the tensile breaking strain (%) are measured From the viewpoint of improving the appearance of the molded product, the breaking strain improvement rate calculated from the following formula (I) is preferably 120% or more, more preferably 150% or more, and still more preferably 200% or more. Further, from the viewpoint of improving the rigidity, the elastic modulus improvement rate calculated from the following formula (II) is preferably 120% or more, more preferably 150% or more, and further preferably 200% or more.
Breaking strain improvement rate (%) = (ES / EB) x 100 (I)
ES: Average value of tensile breaking strain of 5 sample test pieces EB: Average value of tensile breaking strain of 5 control test pieces A control test piece is a resin composition having a composition in which only the compatibilizer is removed from the sample resin composition It is a test piece of a thing.
Modulus improvement rate (%) = (MS / MB) × 100 (II)
MS: Average value of tensile elastic modulus of 5 sample test pieces MB: Average value of tensile elastic modulus of 5 blank test pieces The blank resin piece has the same thermoplastic resin composition of Comparative Example 1 or Comparative Example 13 described later. The test piece of the resin composition of

The resin composition of the present invention is suitable for daily goods, household appliances parts, automobile parts, etc. by using various molding processing methods such as injection molding, extrusion molding, thermoforming, etc. because the rigidity and toughness are compatible. It can be used for

[Molded Product and Method of Manufacturing Molded Product]
The present invention also provides a molded article 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 It can be prepared by suitably using For example, after injection or application to a package type, a mold or the like, a molded body according to the application can be obtained by drying and curing.

In the case of preparing a sheet-like formed product, the thickness is preferably 0.05 mm or more, more preferably 0.1 mm or more, and still more preferably 0.15 mm or more from the viewpoint of processability. Moreover, 1.5 mm or less is preferable, 1.0 mm or less is more preferable, and 0.5 mm or less is still more preferable.

The molded article of the resin composition of the present invention thus obtained is excellent in toughness and rigidity, and thus, it is used as a packaging material for various purposes, for example, daily necessities, cosmetics, home appliances, blister packs, trays, lids for lunch boxes, etc. It can be suitably used for food containers of the above, industrial trays used for transportation and protection of industrial parts, and the like.

Moreover, regarding embodiment mentioned above, this invention further discloses the following resin composition, the manufacturing method of this resin composition, the molded object containing this resin composition, and the manufacturing method of this molded object.

<1> Thermoplastic resin, 5 parts by mass or more and 70 parts by mass or less of non-crystallized cellulose having a relative crystallinity degree of less than 50%, and 2 parts by mass of a compatibilizer with respect to 100 parts by mass of the thermoplastic resin A resin composition comprising: at least 20 parts by mass but not less than 4 parts by mass and at most 20 parts by mass of a compatibilizer when the thermoplastic resin is polyethylene.

<2> The relative crystallinity of the non-crystallized cellulose is preferably 49% or less, more preferably 40% or less, still more preferably 30% or less, preferably -70% or more, more preferably -60% or more The resin composition according to <1>, more preferably -50% or more.
The content of non-crystallized cellulose in the <3> resin composition is preferably 7 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 13 parts by mass or more, with respect to 100 parts by mass of the thermoplastic resin. The above <1> or <2> is preferably 15 parts by mass or more, preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less The resin composition as described.
The content of the compatibilizer in the <4> resin composition is preferably 5 parts by mass or more, preferably 17 parts by mass or less, more preferably 14 parts by mass or less, more preferably 100 parts by mass of the thermoplastic resin. The resin composition according to any one of <1> to <3>, which is 11 parts by mass or less, more preferably 8 parts by mass or less.
When the thermoplastic resin is polyethylene, the content of the compatibilizer in the resin composition is preferably 5 parts by mass or more, preferably 17 parts by mass or less, more preferably 100 parts by mass of the thermoplastic resin. The resin composition according to any one of <1> to <3>, which is 14 parts by mass or less, more preferably 11 parts by mass or less, still more preferably 8 parts by mass or less.
The content of the polyolefin resin in the thermoplastic resin is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass The resin composition according to any one of the above <1> to <5>, which is% or more.
The upper limit of the content of the polyolefin resin in the thermoplastic resin is not particularly limited, and it is made of a polyolefin resin, that is, may be 100% by mass, the resin according to any one of <1> to <6> Composition.
The content of the thermoplastic resin in the <8> resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass or more, still more preferably 70 % By mass, more preferably 75% by mass or more, preferably 93% by mass or less, more preferably 90% by mass or less, still more preferably 87% by mass or less, still more preferably 85% by mass or less, still more preferably 83% by mass The resin composition according to any one of the above <1> to <7>, which is at most%.
<9> The non-crystallized cellulose is treated with a crusher by treating at least one cellulose-containing raw material selected from woods, pulps, papers, plant stems and leaves, plant shells, etc. The resin composition according to any one of the above <1> to <8>, which is obtained by reducing the degree of crystallinity of
<10> If necessary, the cellulose-containing raw material is adjusted to a size of preferably 0.1 to 70 mm by using a shredder or the like, and then treated with a medium-type crusher or extruder. Dried, or subjected to any treatment to obtain a bulk density of preferably 50 to 600 kg / m ³ or a specific surface area of preferably 0.2 to 750 m ² / kg. The resin according to the above <9>, wherein the coarsely pulverized cellulose can be stirred using an impact crusher for 0.5 minutes to 24 hours to obtain non-crystallized cellulose having a reduced degree of crystallinity. Composition.
The resin composition as described in said <9> or <10> whose water content of <11> cellulose containing raw material is preferably 1.8 mass% or less.
The average fiber diameter of the <12> non-crystallized cellulose is preferably 0.01 μm or more, more preferably 1 μm or more, still more preferably 5 μm or more, still more preferably 10 μm or more, still more preferably 20 μm or more, preferably 200 μm or less The resin composition according to any one of the above <1> to <11>, which is more preferably 150 μm or less, further preferably 100 μm or less.
The content of non-crystallized cellulose in the <13> resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, still more preferably It is 12% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less The resin composition according to any one of 1> to <12>.
The weight average molecular weight of the <14> compatibilizer is preferably 1000 or more, more preferably 5000 or more, still more preferably 10000 or more, still more preferably 20000 or more, preferably 100000 or less, more preferably 90000 or less, more preferably The resin composition according to any one of <1> to <13>, wherein the resin composition is 80000 or less, more preferably 70000 or less, further preferably 60000 or less.
<15> The resin composition according to any one of <1> to <14>, wherein the compatibilizer preferably contains one or more selected from the following compatibilizers:
Compatibilizer (1): ethylene / vinyl acetate copolymer compatibilizer (2): ethylene / (meth) acrylate copolymer compatibilizer (3): acid anhydride group, carboxyl group, amino group, Polyolefin resin compatibilizer (4) having at least one functional group (substituent) selected from the group consisting of imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group and epoxy group: acid Acrylic having at least one functional group (substituent) selected from the group consisting of anhydride group, carboxyl group, amino group, imino group, alkoxysilyl group, silanol group, silyl ether group, hydroxyl group, and epoxy group Resin based resin or styrene resin compatibilizer (5): polyester resin compatibilizer (6): ionomer resin.
<16> The resin composition according to any one of <1> to <14>, wherein the compatibilizer more preferably contains at least one selected from the group shown below:
Compatibilizer: having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group Polyolefin resin.
The polyolefin resin in the <17> compatibilizer (3) 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-olefins, Copolymers etc. with vinyl acetate, methacrylic acid, acrylic acid etc.], propylene polymers [polypropylene, copolymers etc. of propylene and one or more other vinyl compounds], ethylene propylene copolymer, The resin composition according to <15>, which is polybutene and poly-4-methylpentene-1 or the like, more preferably an ethylene polymer or a propylene polymer:
The functional group of the polyolefin resin in the <18> compatibilizer (3) is preferably an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and It is at least one selected from the group consisting of epoxy groups, more preferably an acid anhydride group and an epoxy group, still more preferably an acid anhydride group, still more preferably maleic anhydride, maleic acid and succinic anhydride The resin composition according to <15> or <17>, which is an acid, succinic acid or glycidyl methacrylate.
The content of the compatibilizer in the <19> resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 4% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less Resin composition.
The mass ratio of the <20> compatibilizer to the non-crystallized cellulose (compatibilizer / non-crystallized cellulose) is preferably 0.8 or less, more preferably 0.6 or less, still more preferably 0.4 or less, and further preferably The above <1> to <19> is preferably 0.3 or less, preferably 0.06 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and still more preferably 0.15 or more. The resin composition as described in any one.

<21> At least one thermoplastic resin selected from the group consisting of polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyamide resin, nylon resin, vinyl chloride resin, vinyl ether resin, polyvinyl alcohol resin, polycarbonate resin and polysulfone resin The resin composition according to any one of the above <1> to <20>.
<22> The resin composition according to any one of <1> to <21>, wherein the thermoplastic resin contains one or more selected from polyolefins, polystyrenes, polyesters, and polyamides.
<23> The resin composition according to any one of the above <1> to <22>, wherein the thermoplastic resin comprises a polyolefin.
<24> The resin composition according to any one of <21> to <23>, wherein the polyolefin is one or two selected from polyethylene and polypropylene.
<25> The resin composition according to any one of <1> to <24>, wherein a crystal nucleating agent is further used.
<26> The crystal nucleating agent is preferably an inorganic crystal nucleating agent and an organic crystal nucleating agent, and the inorganic crystal nucleating agent is more preferably a natural or synthetic silicate compound, titanium oxide, barium sulfate, phosphoric acid Tricalcium, calcium carbonate, sodium phosphate, kaolinite, halloysite, talc, smectite, vermeulite, mica, etc. As the organic crystal nucleating agent, more preferably amide, organic acid metal salt, sorbitol derivative, nonitol The resin composition according to <25>, which is a derivative or the like, more preferably an organic acid metal salt and a sorbitol derivative.
The metal salt of an organic acid <27> is preferably sodium benzoate, aluminum dibenzoate, potassium benzoate, lithium benzoate, sodium β · naphthalate, sodium cyclohexane carboxylate, zinc phenylphosphonate and the like, and as a sorbitol derivative, The resin composition according to the above <26>, which is preferably 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol or the like, more preferably a sorbitol derivative.
The content of the <28> crystal nucleating agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably 3.0 parts by mass or less, based on 100 parts by mass of the thermoplastic resin. The resin composition according to any one of <25> to <27>, which is more preferably 2.0 parts by mass or less.
<29> As other components, plasticizers; fillers (inorganic fillers, organic fillers); hydrolysis inhibitors; flame retardants; antioxidants; lubricants that are hydrocarbon waxes and anionic surfactants; UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, surfactants, polysaccharides such as starches and alginic acid, and natural proteins such as gelatin, glue, casein, etc. Inorganic compounds such as tannins, zeolites, ceramics, metal powders, perfumes, flow control agents, leveling agents, conductive agents, ultraviolet light dispersants, deodorants, etc., or other polymer materials The resin composition as described in any one of the above <1> to <28>, to which a resin composition or any other resin composition can be added.
<30> The resin according to the above <29>, wherein the content ratio of the other components is preferably 20% by mass or less, more preferably about 10% by mass or less, still more preferably about 5% by mass or less in the resin composition. Composition.
<31> In addition to the above three components, if necessary, raw materials containing various additives are preferably stirred with a Henschel mixer etc., or a closed kneader, a single screw or twin screw extruder, an open roll kneader The resin composition according to any one of the above <1> to <30>, which can be prepared by melt-kneading or solvent casting using a known kneader or the like.
<32> The resin composition according to the above <31>, wherein the raw materials are preferably uniformly mixed in advance using a Henschel mixer, a super mixer, etc., and then subjected to melt-kneading or mixed at once and melt-kneaded object.
<33> The resin composition according to <31> or <32>, which is preferably dried according to a known method after melt-kneading.
<34> Melt-kneading temperature is preferably 180 ° C. or more, more preferably 190 ° C. or more, still more preferably 200 ° C. or more, still more preferably 220 ° C. or more, still more preferably 225 ° C. or more, still more preferably 230 ° C. or more C., preferably 300.degree. C. or less, more preferably 290.degree. C. or less, still more preferably 280.degree. C. or less, and the melt-kneading time is preferably 15 seconds or more, preferably 900 seconds or less. 33> The resin composition as described in any one.
<35> Thermoplastic resin, 5 parts by mass to 70 parts by mass of non-crystallized cellulose having a relative crystallization degree of less than 50%, and 2 parts by mass of a compatibilizer with respect to 100 parts by mass of the thermoplastic resin A method for producing a resin composition, comprising: at least 20 parts by mass, but in the case where the thermoplastic resin is polyethylene, at least 4 parts by mass and not more than 20 parts by mass of a compatibilizer.
<36> A raw material containing various additives as necessary in addition to the thermoplastic resin, non-crystallized cellulose, and the compatibilizer, preferably 180 ° C. or more, more preferably 190 ° C. or more, still more preferably 200 ° C. or more The method for producing a resin composition according to <35>, wherein the mixing is performed at a temperature of preferably 300 ° C. or less, more preferably 290 ° C. or less, still more preferably 280 ° C. or less.
<37> The method for producing a resin composition according to <36>, wherein the mixing time is preferably 15 seconds or more, preferably 900 seconds or less.
<38> The relative crystallinity of the non-crystallized cellulose is preferably 49% or less, more preferably 40% or less, still more preferably 30% or less, preferably -70% or more, more preferably -60% or more The method for producing a resin composition according to any one of <35> to <37>, more preferably -50% or more.
The content of non-crystallized cellulose in the <39> resin composition is preferably 7 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 13 parts by mass or more, with respect to 100 parts by mass of the thermoplastic resin. The amount is preferably 15 parts by mass or more, preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less. The manufacturing method of the resin composition in any one description.
The content of the compatibilizer in the <40> resin composition is preferably 5 parts by mass or more, preferably 17 parts by mass or less, more preferably 14 parts by mass or less, more preferably 100 parts by mass of the thermoplastic resin. The method for producing a resin composition according to any one of <35> to <39>, which is 11 parts by mass or less, more preferably 8 parts by mass or less.

<41> When the thermoplastic resin is polyethylene, the content of the compatibilizer in the resin composition is preferably 5 parts by mass or more, preferably 17 parts by mass or less, more preferably 100 parts by mass of the thermoplastic resin. The method for producing a resin composition according to any one of <35> to <39>, which is 14 parts by mass or less, more preferably 11 parts by mass or less, still more preferably 8 parts by mass or less.
The weight average molecular weight of the <42> compatibilizer is preferably 1000 or more, more preferably 5000 or more, still more preferably 10000 or more, still more preferably 20000 or more, preferably 100000 or less, more preferably 90000 or less, more preferably The method for producing a resin composition according to any one of the above <35> to <41>, wherein the ratio is 80000 or less, more preferably 70000 or less, still more preferably 60000 or less.
<43> The method for producing a resin composition according to any one of <35> to <42>, wherein the compatibilizer more preferably contains at least one selected from the group shown below:
Compatibilizer: having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group Polyolefin resin.
The weight ratio of the <44> compatibilizer to the non-crystallized cellulose (compatibilizer / non-crystallized cellulose) is preferably 0.8 or less, more preferably 0.6 or less, still more preferably 0.4 or less, and further preferably The above <35> to <43> is preferably 0.3 or less, preferably 0.06 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and still more preferably 0.15 or more. The manufacturing method of the resin composition in any one description.
<45> The method for producing a resin composition according to any one of <35> to <44>, wherein the thermoplastic resin comprises a polyolefin.
The manufacturing method of the resin composition of the said <45> description whose <46> polyolefin is 1 type or 2 types chosen from polyethylene and a polypropylene.
<47> The method for producing a resin composition according to any one of <35> to <46>, wherein a crystal nucleating agent is further used.
<48> A molded article containing the resin composition according to any one of the above <1> to <34>.
The <49> molded article is a sheet-like molded article, and 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, preferably 1.5 mm or less The molded article according to <48>, more preferably 1.0 mm or less, further preferably 0.5 mm or less.
<50> Preferably, it can be used as a packaging material for daily necessities, cosmetics, household appliances, etc., for food containers such as blister packs and trays, lids for lunch boxes, and industrial trays used for transportation and protection of industrial parts, The molded object as described in <48> or <49>.
<51> Based on JIS K7127, the No. 2 test piece of a molded object was produced, and when the tensile elastic modulus (GPa) and the tensile breaking strain (%) were measured, it computed from the above-mentioned formula (I) The molded article according to any one of the above <48> to <50>, wherein the breaking strain improvement rate is preferably 120% or more, more preferably 150% or more, and still more preferably 200% or more.
<52> Based on JIS K7127, the No. 2 test piece of a molded object was produced, and when it measured the tensile elasticity modulus (GPa) and the tensile breaking strain (%), it computed from the above-mentioned formula (II) The molded article according to any one of <48> to <51>, wherein the elastic modulus improvement rate is preferably 120% or more, more preferably 150% or more, and still more preferably 200% or more.
<53> The resin composition according to any one of <1> to <34> is preferably processed by extrusion molding, injection molding, press molding, cast molding, or solvent casting to obtain a molded article. 48. A method for producing a molded body according to any one of <52>.

Hereinafter, the present invention will be specifically described by way of examples. Note that this example is merely an example of the present invention and does not mean any limitation. Parts in the examples are parts by weight unless otherwise stated.

[Average fiber diameter of cellulose fiber]
The average fiber diameter is measured using a laser diffraction / scattering type particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.). As measurement conditions, ultrasonic waves are treated for 1 minute before measurement, water is used as a dispersion medium at the time of measurement, and a volume-based median diameter is measured at a temperature of 25 ° C.

[Confirmation of Crystal Structure of Cellulose Fiber]
The crystal structure of the cellulose fiber is confirmed by measurement under the following conditions using “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation. Measurement conditions are: X-ray source: Cu / Kα-radiation, tube voltage: 40 kv, tube current: 120 mA, measurement range: diffraction angle 2θ = 5-45 °, X-ray scan speed: 10 ° / min. The measurement sample is produced by compressing a pellet of area 320 mm ² × thickness 1 mm. Moreover, the crystallinity degree of a cellulose I-type crystal structure calculates the obtained X-ray-diffraction intensity based on the following formula (A).
Cellulose type I crystallinity (%) = [(I 22.6-I 18.5) / I 22.6] × 100 (A)
[Wherein, I22.6 indicates the diffraction intensity of the grating surface (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, I18.5 indicates the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5 °)]

[Weight average molecular weight of compatibilizer]
The weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography) under the following measurement conditions.
<Measurement conditions>
Column: Showa Denko Shodex HT-806M x 1 + Shodex HT- 803 x 2 columns Column temperature: 130 ° C
Detector: RI
Eluent: o-dichlorobenzene flow rate: 1.0 mL / min
Sample concentration: 1 mg / mL
Injection volume: 0.1 mL
Conversion standard: polystyrene

Production Example 1: Amorphous Cellulose 1
(1) Cutting process As a cellulose-containing raw material, sheet-like pulp (manufactured by Tembec, Biofloc HV +, relative crystallinity: 82%, water content: 8.5% by mass) was cut using a cutting machine [Superno Cutter, manufactured by Kuwano Seiki Co., Ltd.] Using RK6-800], it was cut into chips of about 3 mm × 1.5 mm × 1 mm.
(2) Drying treatment The chip-like pulp obtained from the above (1) is continuously treated using a twin-screw horizontal stirring dryer [two-axis paddle dryer NPD-3W (1/2), manufactured by Nara Machinery Co., Ltd.] It dried with At this time, the heating medium of the dryer used steam at 150 ° C., and the feed rate of pulp was 45 kg / h. The water content of the dried pulp obtained by the continuous treatment was 0.5% by mass.
(3) Cellulose coarse pulverization treatment The dried pulp obtained from the above (2) is coarsely treated using a continuous vibration mill (Vibro Mill YAMT-200, volume of first and second pulverizing chambers: 112 L, manufactured by Eurus Techno Co., Ltd.). Crushed. In the first and second grinding chambers, 80 pieces of stainless steel round rod-shaped grinding media having a diameter of 30 mm and a length of 1300 mm were accommodated. The dry pulp was charged at 20 kg / h under the conditions of a continuous vibration mill at a frequency of 16.7 Hz and an amplitude of 13.4 mm, and the pulp was roughly crushed. The bulk density of the obtained coarsely pulverized cellulose was 223 kg / m ³ .
(4) Cellulose Amorphization Treatment The coarsely pulverized cellulose obtained from the above (3) was treated using a high-speed rotary pulverizer (manufactured by Dalton, Atomizer AIIW-7.5 type). A 1.0 mm screen was attached, the rotor peripheral speed was driven at 91 m / s, and coarsely pulverized cellulose was supplied from the raw material supply section at a supply speed of 20 kg / h. The obtained cellulose had a relative crystallinity of -9.4% and a median diameter of 62.5 μm.

Production Example 2: Amorphous Cellulose 2
(1) Cutting treatment As a cellulose-containing raw material, sheet-like pulp (manufactured by Tembec, Biofloc HV +, relative crystallinity: 82%, water content: 8.5% by mass) was added to a cutting machine [sheet pelletizer manufactured by Horai, The resultant was cut into chips of about 3 mm × 1.5 mm × 1 mm using SG (E) -220].
(2) Drying treatment The chip-like pulp obtained from the above (1) was subjected to a twin-screw horizontal stirring dryer [made by Nara Machinery Co., Ltd., a twin-paddle dryer NPD-1.6 W (1/2)]. It dried by continuous processing. At this time, the heating medium of the dryer used steam at 150 ° C., and the feed rate of the pulp was 20 kg / h. The water content of the dried pulp obtained by the continuous treatment was 0.5% by mass.
(3) Cellulose Coarse Grinding Treatment The dried pulp obtained from the above (2) was roughly ground using a batch-type vibration mill [FV-10 manufactured by Chuo Kakoki Co., Ltd .; volume of grinding chamber: 33 L]. The grinding chamber contained 63 stainless steel round rod-like grinding media having a diameter of 30 mm and a length of 510 mm. Under the conditions of a frequency of 20 Hz and an amplitude of 8 mm, 920 g of dry pulp was charged, and the pulp was roughly crushed. The bulk density of the obtained coarsely pulverized cellulose was 235 kg / m ³ .
(4) Cellulose Amorphization Treatment The coarsely pulverized cellulose obtained from the above (3) was treated using a high-speed rotary pulverizer [Sample Mill KIIW-1 manufactured by Dalton, Inc.]. A 1.0 mm screen was attached, the rotor peripheral speed was driven at 80 m / s, and coarsely pulverized cellulose was supplied from the raw material supply portion at a supply speed of 18 kg / h. The obtained cellulose had a relative crystallinity of 43.2% and a median diameter of 27.8 μm.

Production Example 3: Amorphous Cellulose 3
(1) Cutting treatment As a cellulose-containing raw material, a sheet-like pulp (manufactured by APRIL (Asia Pacific Resources International), RIAU ACACIA PULP, relative crystallinity: 80%, water content: 9.8 mass%), a cutting machine It was cut into chips of about 3 mm × 1.5 mm × 1 mm using a sheet pelletizer SG (E) -220 manufactured by Horai Co., Ltd.
(2) Drying treatment The chip-like pulp obtained from the above (1) was subjected to a twin-screw horizontal stirring dryer [made by Nara Machinery Co., Ltd., a twin-paddle dryer NPD-1.6 W (1/2)]. It dried by continuous processing. At this time, the heating medium of the dryer used steam at 150 ° C., and the feed rate of the pulp was 20 kg / h. The water content of the dried pulp obtained by the continuous treatment was 0.5% by mass.
(3) Cellulose Coarse Grinding Treatment The dried pulp obtained from the above (2) was roughly ground using a batch-type vibration mill [FV-10 manufactured by Chuo Kakoki Co., Ltd .; volume of grinding chamber: 33 L]. The grinding chamber contained 63 stainless steel round rod-like grinding media having a diameter of 30 mm and a length of 510 mm. Under the conditions of a frequency of 20 Hz and an amplitude of 8 mm, 920 g of dry pulp was charged, and the pulp was roughly crushed. The bulk density of the obtained coarsely pulverized cellulose was 230 kg / m ³ .
(4) Cellulose Amorphization Treatment The coarsely pulverized cellulose obtained from the above (3) was treated using a high-speed rotary pulverizer [Cryptron Eddy KTE0 type manufactured by Earth Technica Co., Ltd.]. While driving the rotor circumferential speed at 145 m / s, coarsely pulverized cellulose was fed from the raw material feed section at a feed rate of 7 kg / h. The obtained cellulose had a relative crystallinity of 4.1% and a median diameter of 10.1 μm.

Production Example 4: Amorphous Cellulose 4
(1) Cutting treatment As a cellulose-containing material, sheet-like wood pulp ("Blue Bear Ultra Ether" manufactured by Borregard, 800 mm x 600 mm x 1.5 mm, the cellulose content 96% by weight (the remainder obtained by removing water from the cellulose-containing material) The content in the ingredients, cellulose type I crystallinity 81%, water content 7.0 wt%, bulk density 200 kg / m ³ ) was applied to a sheet pelletizer ("SG (E) -220" manufactured by Horai) , Roughly 4 mm × 4 mm × 1.5 mm.
(2) Drying treatment The pulp obtained in the above (1) was treated with a shelf drier (vacuum constant temperature drier "DRV 320 DA" manufactured by ADVANTEC, Inc.), and the water content of the pulp after drying was 0.8. It dried so that it might become mass%.
(3) Coarse grinding and decrystallization treatment 50 g of the pulp obtained in the above (2) is charged into a vibrating mill ("MB-1" manufactured by Chuo Kakoki Co., Ltd., container total volume 3.5 L) as a grinder. , 11 rods (cross-sectional shape: circular, diameter: 30 mm, length: 218 mm, material: stainless steel) in a vibrating mill (filling rate 48%), amplitude 8 mm, rotation speed 1200 rpm / min, The treatment was performed for 40 minutes. The temperature during the operation was 30.degree.
After completion of the treatment, no fixed matter of pulp was found on the wall surface or bottom of the crusher. The resulting pulverized product was removed from the pulverizer and sieved with a 75 μm mesh to obtain non-crystallized cellulose having a median diameter of 30 μm and a relative crystallinity of -34.3%.
(4) Mixing and grinding treatment 50 g of the non-crystallized cellulose obtained by the above (3) and 5 g of MA-PP (maleic acid modified polypropylene, Yumex 1010, manufactured by Sanyo Chemical Industries, Ltd.) as a grinding aid are mixed, The whole of the mixture is introduced into a vibratory mill ("MB-1", manufactured by Chuo Kakoki Co., Ltd., "MB-1", total container volume 3.5 L) as a crusher, and a rod (cross-sectional shape: circular, outer diameter: 30 mm, length: 218 mm) Material: 11 stainless steels are packed in a vibrating mill (filling rate 48%), and crushed for 15 minutes under the conditions of amplitude 8 mm, rotation speed 1200 rpm, median diameter 12.0 μm, relative crystallization Amorphous cellulose 4 with a degree of -40.8% was obtained. )

Examples 1 to 8 and Comparative Examples 1 to 14
The composition raw materials shown in Tables 1 and 2 are melt-kneaded for 8 minutes at a rotation number of 90 rpm and a temperature shown in Tables 1 and 2 using a kneader (Laboplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a resin composition Obtained (The amounts of use of the raw materials described in Tables 1 and 2 are parts by mass, and mass% is calculated from their total amount).

The resulting resin composition is pressed using a heat press (lab press made by Toyo Seiki Seisakusho, Ltd., 240 ° C. for 1 minute at 0.4 MPa, 1 minute at 20 MPa, and then cooled to 20 ° C. The sheet having a thickness of 0.4 mm was formed.

The raw materials in Tables 1 and 2 are as follows.
<Thermoplastic resin>
Polyethylene resin: Novatec LL UF 641
Polypropylene resin: Novatec PP EA9
<Cellulose fiber>
KC floc: Nippon Paper Chemicals Co., Ltd., relative crystallinity 78.5%, median 28.0 μm
<Compatibilizer>
Yumex 1001: Sanyo Chemical Industries, Ltd., maleic anhydride modified polypropylene, weight average molecular weight 40000
Umex 1010: Sanyo Chemical Industries, Ltd., maleic acid modified polypropylene, weight average molecular weight 30000
<Elastomer>
HYBLER 7311: Kuraray Plastics Co., Ltd., polystyrene-polyvinyl isoprene-polystyrene block copolymer, weight average molecular weight 140000
<Crystal nucleating agent>
Gelall MD: New Japan Chemical Co., Ltd., methyl dibenzylidene sorbitol

The properties of the obtained molded body were evaluated in accordance with the method of Test Example 1 below. The results are shown in Tables 1 and 2.

Test example 1 (breaking strain improvement rate, elastic modulus improvement rate)
In a temperature-controlled room at 25 ° C., five sheets of No. 2 test pieces are prepared based on JIS K 7127, and a tensile test is conducted to check the tensile modulus (GPa) and the tensile breaking strain (%). The improvement rate and the elastic modulus improvement rate were obtained from the following formulas (I) and (II). For the tensile test, a 5-point test was performed per sample according to JIS K7127 using an automatic graph precision universal tester (AGS-10 kNX) manufactured by SHIMADZU. The increase in breaking strain indicates that the greater the numerical value, the better the toughness, and the increase in elastic modulus indicates that the larger the numerical value, the superior in rigidity. In addition, when the tensile elastic modulus is 0.9 GPa or more, excellent strength is exhibited. In addition, as a control test piece at the time of calculating the breaking strain improvement rate, Comparative Example 2 for Examples 1 and 2 and Comparative Example 3 for Example 3 and Examples 4 and 5 The test piece of the resin composition of Comparative Example 14 was used for Comparative Example 12 and Comparative Example 11 and Example 7 and 8 for Example 6, respectively.
Breaking strain improvement rate (%) = (ES / EB) x 100 (I)
ES: Average value of tensile breaking strain of 5 sample test pieces EB: Average value of tensile breaking strain of 5 control test pieces A control test piece is a resin composition having a composition in which only the compatibilizer is removed from the sample resin composition It is a test piece of a thing.
Modulus improvement rate (%) = (MS / MB) × 100 (II)
MS: Average value of tensile elastic modulus of 5 sample test pieces MB: Average value of tensile elastic modulus of 5 blank test pieces The blank test piece is a test piece of the resin composition of Comparative Example 1 or Comparative Example 13 described later It is

From Tables 1 and 2, while the resin compositions of the examples have high tensile modulus and high improvement rate, the improvement rate of breaking strain is also high, good toughness is exhibited, and rigidity and toughness are compatible. Know that it is Further, FIG. 1 shows the sheet cross section of Example 3 and FIG. 2 shows the sheet cross section of Comparative Example 3. From this comparison, the addition of the compatibilizer makes the non-crystallized cellulose finer and disperses. It is also understood that the properties are improved, and the interface between the thermoplastic resin and the cellulose fiber is stabilized.

The resin composition of the present invention can be suitably used in various industrial applications such as household goods, household electric appliance parts, packaging materials for household electric appliance parts, automobile parts, etc. since it is a combination of rigidity and toughness. .

Claims

5 parts by mass to 70 parts by mass of non-crystallized cellulose having a relative crystallinity of less than 50% and 100 parts by mass of the thermoplastic resin, and 2 parts by mass or more of a compatibilizer to 20 parts by mass of the thermoplastic resin A resin composition comprising not more than 4 parts by mass but not less than 4 parts by mass and not more than 20 parts by mass of the compatibilizer when the thermoplastic resin is polyethylene.
The resin composition according to claim 1, wherein the weight average molecular weight of the compatibilizer is 1,000 or more and 100,000 or less.
The resin composition of Claim 1 or 2 in which a compatibilizer contains at least 1 sort (s) out of the group shown below.
Compatibilizer: having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, an amino group, an imino group, an alkoxysilyl group, a silanol group, a silyl ether group, a hydroxyl group, and an epoxy group Polyolefin resin
The resin composition according to any one of claims 1 to 3, wherein the mass ratio of the compatibilizer to the non-crystallized cellulose (compatibilizer / non-crystallized cellulose) is 0.8 or less.
The resin composition according to any one of claims 1 to 4, wherein the thermoplastic resin comprises one or more selected from polyolefins, polystyrenes, polyesters, and polyamides.
The resin composition according to any one of claims 1 to 5, wherein the thermoplastic resin comprises a polyolefin.
The resin composition according to claim 6, wherein the polyolefin is one or two selected from polyethylene and polypropylene.
5 parts by mass to 70 parts by mass of non-crystallized cellulose having a relative crystallinity of less than 50% and 100 parts by mass of the thermoplastic resin, and 2 parts by mass or more of a compatibilizer to 20 parts by mass of the thermoplastic resin The manufacturing method of the resin composition which mix | blends 4 parts by mass or more and 20 parts by mass or less of the compatibilizing agent if the thermoplastic resin is polyethylene.
A molded article comprising the resin composition according to any one of claims 1 to 7.
A method for producing a molded article, wherein the resin composition according to any one of claims 1 to 7 is processed to form a molded article.