JP7041510B2 - Method for producing low crystalline cellulose - Google Patents

Description

The present invention relates to a method for producing low crystalline cellulose and a cellulose-containing powder.

Conventionally, petroleum-derived plastic materials, which are a finite resource, have been widely used, but in recent years, technologies with less environmental impact have come into the limelight, and under such technological background, biomass is naturally present in large quantities. Materials using cellulose fibers are attracting attention.

For example, in Patent Document 1, a molded product of a composition obtained by blending a polyolefin resin and / or a styrene resin with cellulose having a crystallinity of less than 50% has both strength and flexibility, and further has impact resistance. It has been reported to have an excellent effect of being excellent. The cellulose used here is disclosed to be prepared by reducing the crystallinity to less than 50% by pulverization treatment, but the flexibility and resistance while maintaining the strength of the obtained molded product are disclosed. From the viewpoint of further improving the impact resistance, the cellulose having a reduced degree of crystallinity is pulverized by adding a pulverizing aid to reduce the average particle size to 30 μm or less. It is also disclosed.

Further, in Patent Document 2, 0.1 to 100 parts by mass of a specific pulverizing aid is added to 100 parts by mass of a low crystalline cellulose raw material having a cellulose I-type crystallization degree of 33% or less, and a dry pulverization treatment is performed. By doing so, a method for producing cellulose particles having an average particle size of preferably 50 μm or less is disclosed. On the other hand, in Patent Document 3, when a cellulose-containing raw material having a cellulose I-type crystallinity of more than 33% is used and the cellulose content in the residual component obtained by removing water from the cellulose-containing raw material is 20% by mass or more. Further discloses a method for producing low crystalline cellulose having an average particle size of 10 to 200 μm by treating the cellulose-containing raw material with a pulverizing aid in a pulverizer.

Japanese Unexamined Patent Publication No. 2011-137094 Japanese Unexamined Patent Publication No. 2010-155982 Japanese Unexamined Patent Publication No. 2010-37526

However, in recent years, it is expected that such low crystalline cellulose will be used for a wider range of applications, and there is a demand for a technique for easily preparing a cellulose having better physical properties.

The present invention relates to a method for easily preparing a cellulose-containing powder, which is a low-crystalline cellulose capable of providing a resin composition having both rigidity and toughness when blended in a resin, and a cellulose-containing powder.

The present invention relates to the following [1] and [2].
[1] One selected from the group consisting of the following (A), (B), and (C) with respect to 100 parts by mass of the cellulose-containing raw material having a cellulose I-type crystallization index of 10% or more and less than 100%. Production of a cellulose-containing powder having a cellulose I-type crystallization index of -20% or more and less than 50%, which comprises a step of adding two or more kinds of additives by 0.1 part by mass or more and 100 parts by mass or less and pulverizing by a dry method. Method.
(A) Polymer compound having acid anhydride
(B) Small molecule compound with acid anhydride
(C) Silane coupling agent [2] Cellulose type I crystallization index is -20% or more and less than 50%, and the following (A), (B), and (C) are used with respect to 100 parts by mass of the cellulose-containing raw material. A cellulose-containing powder containing 0.1 part by mass or more and 100 parts by mass or less of one or more kinds of additives selected from the group consisting of.
(A) Polymer compound having acid anhydride
(B) Small molecule compound with acid anhydride
(C) Silane coupling agent

The low crystalline cellulose obtained by the present invention has an excellent effect of being able to provide a resin composition having both rigidity and toughness when blended with a resin.

The higher the crystallinity of cellulose, the higher the strength. However, in low crystallinity cellulose, since there are many amorphous portions and the abundance ratio of hydrogen bonds decreases, the strength is excellent and the toughness is also excellent. Such low crystalline cellulose can be produced, for example, by subjecting the raw material cellulose to a pulverization treatment as described in the above-mentioned Patent Documents 1 to 3, but in the present invention, a specific addition is made during the pulverization treatment. It has been found that the presence of the agent makes it possible to easily prepare low-crystalline cellulose that can impart rigidity and toughness when blended in a resin. As the components coexisting during the pulverization treatment, the pulverizing aids and the like in Patent Documents 1 to 3 are already known, but in the present invention, (A) a polymer compound having an acid anhydride and (B) an acid anhydride are known. By using a component different from the conventional pulverizing aid for cellulose, such as a small molecule compound having (C) silane coupling agent, the detailed reason is unknown, but the affinity between the additive and cellulose is good. It is presumed that this is because the additive easily penetrates into the inside of the cellulose crystal and the crushing force is easily transmitted, so that the structure is also destroyed from the inside of the cellulose crystal. However, these speculations do not limit the invention. In the present specification, the crystallinity of cellulose is a cellulose I-type crystallization index calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is specifically described in Examples described later. It is defined by the formula of.

The method for producing cellulose of the present invention comprises (A), (B), and (C) described later with respect to 100 parts by mass of a cellulose-containing raw material having a cellulose I-type crystallization index of 10% or more and less than 100%. It is characterized by including a step of adding 0.1 part by mass or more and 100 parts by mass or less of one or more kinds of additives selected from the group and pulverizing by a dry method. By such a production method, a cellulose-containing powder having a cellulose type I crystallization index of −20% or more and less than 50% can be obtained. In the present specification, the cellulose-containing powder is referred to as low crystalline cellulose.

[Cellulose-containing raw material]
The cellulose-containing raw material used in the present invention is not particularly limited as long as the cellulose type I crystallization index is 10% or more and less than 100%, but is preferably 20% from the viewpoint of mixing of cellulose and additives. The above is more preferably 30% or more, still more preferably 40% or more, still more preferably 50% or more, still more preferably 60% or more. From the viewpoint of being inexpensively available, those having a crystallization index of, for example, 50% or more may be used. Specifically, wood-based (coniferous and broad-leaved trees), herbaceous (grass, gramineous, legume plant raw materials, palm family plant non-wood raw materials), pulps (from fibers around cotton seeds) (Cotton linter pulp obtained, etc.), papers (newspaper, cardboard, magazines, woodfree paper, etc.) are exemplified.

In the present invention, the size and shape of the cellulose-containing raw material are particularly limited because low crystalline cellulose can be easily obtained without going through a complicated multi-step process by the pulverization treatment in the presence of an additive described later. do not have. For example, fibrous, powdery, spherical, chip-like, and flake-like ones can be used. Moreover, it may be a mixture of these. Alternatively, if necessary, the shape may be prepared in advance by using a cutting machine such as a shredder. Specifically, for example, the shape having a size included in the range of 0.1 to 70 mm, preferably 0.5 to 70 mm, more preferably 1 to 50 mm, still more preferably 1 to 30 mm on one side. Things are illustrated. The size of the cellulose-containing raw material can be measured using a caliper.

The composition of the cellulose-containing raw material is not particularly limited, and for example, the cellulose content in the raw material is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more. To. Further, from the viewpoint of availability, the upper limit is 100% by mass, and 99% by mass or less is exemplified. Here, the cellulosic content in the cellulosic-containing raw material is the cellulosic content in the residual component excluding water in the cellulosic raw material.

The water content in the cellulose-containing raw material is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0. 5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2.0% by mass or more is exemplified. Further, from the viewpoint of handleability, those having an amount of preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less can be used.

The cellulose-containing raw material used in the present invention may be dried. The treatment method is not limited, and a known drying method may be appropriately selected. For example, a hot air heat receiving drying method, a conduction heat receiving drying method, a dehumidified air drying method, a cold air drying method, a microwave drying method, an infrared drying method, and a heavenly method. Examples include a sun drying method, a vacuum drying method, and a freeze drying method. These drying methods may be performed alone or in combination of two or more, and the drying device can be appropriately selected according to the drying method. In addition, the drying process can be either batch process or continuous process.

The temperature in the drying treatment cannot be unconditionally determined depending on the drying means, the drying time, etc., but is preferably 10 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C. or higher. Further, it is preferably 250 ° C. or lower, more preferably 150 ° C. or lower. As for the treatment time, the lower limit is preferably 0.01 hr or more, more preferably 0.02 hr or more, and the upper limit is preferably 2 hr or less, more preferably 1 hr or less. If necessary, the drying treatment may be carried out under reduced pressure, and the pressure is exemplified by about 1 to 120 kPa.

The water content in the cellulose-containing raw material after the drying treatment is preferably 4.5% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.5% by mass or less, still more preferably 3.0. It is less than mass%. With such a water content, even in the pulverization treatment in the presence of an additive, the treatment can be performed satisfactorily without becoming lumpy.

Since the drying treatment does not affect the crystallization of the cellulose-containing raw material, the crystallization index of the cellulose-containing raw material after the drying treatment has a crystallization index similar to that of the crystallization index before the treatment.

〔Additive〕
In the present invention, one or more additions selected from the group consisting of (A) a high molecular weight compound having an acid anhydride, (B) a low molecular weight compound having an acid anhydride, and (C) a silane coupling agent. Use an agent. When two or more kinds are used, two or more kinds in (A), two or more kinds in (B), or two or more kinds in (C) may be used, and (A). ) And (B), (B) and (C), (A) and (C), and (A) and (B) and (C). Among them, the combination of (A) and (C) is preferable from the viewpoint of the affinity with the resin when blended with the resin in addition to the affinity with cellulose.

(A) Polymer compound having acid anhydride
The acid anhydride in the compound (A) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, and glutaric anhydride.

Examples of the polymer in the compound (A) include resins such as polyolefin resins, acrylic resins, and styrene resins, and polyolefin resins are preferable from the viewpoint of compatibility with the resin to be blended.

Polyolefin-based resins include ethylene-based polymers [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.). Polymers, etc.], propylene-based polymers [polypolymers, copolymers of propylene and one or more other vinyl compounds, etc.], polyethylene-propylene copolymers, polyethylene, poly-4-methylpentene-1, etc. Is exemplified, but a propylene-based polymer is preferable.

Specific examples of the compound (A) include maleic anhydride-modified polyolefin, and more specifically, maleic anhydride-modified polypropylene.

The compound (A) may be prepared according to a known method, or a commercially available product may be used. Suitable commercial products include, for example, "Umex" manufactured by Sanyo Kasei Kogyo Co., Ltd. (polypropylene having maleic anhydride), "OREVAC G" manufactured by Alchema (polypropylene having maleic anhydride), and "rotada" manufactured by Alchema (acid). Examples thereof include "polyolefin-based resin having an anhydride) and "bondine" (polyolefin-based resin having an acid anhydride) manufactured by Sumitomo Chemical Industries, Ltd.

The weight average molecular weight (Mw) of the compound (A) is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 20, from the viewpoint of affinity with cellulose. It is over 000. Further, from the viewpoint of pulverizability, it is preferably 150,000 or less, more preferably 140,000 or less, still more preferably 130,000 or less. In the present specification, the weight average molecular weight of the polymer compound can be measured according to the method described in Examples described later.

Further, the compound (A) has a melting point of preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower, still more preferably 170 ° C., from the viewpoint of suppressing deterioration of cellulose when compounded with the resin. The following are preferable. The lower limit is not particularly limited, and is, for example, about 100 ° C. In the present specification, the melting point can be measured according to the method described in Examples described later.

(B) Small molecule compound with acid anhydride
The acid anhydride in the compound (B) is not particularly limited, and the same as the acid anhydride in the compound (A) can be exemplified.

Examples of the small molecule in the compound (B) include a hydrocarbon group.

Examples of the hydrocarbon group include a chain-type saturated hydrocarbon group, a chain-type unsaturated hydrocarbon group, a ring-type saturated hydrocarbon group, and an aromatic hydrocarbon group.

The chain saturated hydrocarbon group may be linear or branched. From the viewpoint of greasability, the number of carbon atoms of the chain saturated hydrocarbon group is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, further preferably 10 or more, still more preferably 15 or more. Further, from the viewpoint of reactivity with cellulose, 30 or less is preferable, 24 or less is more preferable, 20 or less is further preferable, and 18 or less is further preferable.

Specific examples of the chain saturated hydrocarbon group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group and a tert-pentyl group. Examples thereof include an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, an octadecyl group, a docosyl group and an octacosanyl group. Among them, preferably 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, octacosyl group, more preferably 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.

The chain unsaturated hydrocarbon group may be linear or branched. The carbon number of the chain unsaturated hydrocarbon group is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, still more preferably 10 or more, from the viewpoint of greasability. Further, from the viewpoint of reactivity with cellulose, 30 or less is preferable, 24 or less is more preferable, 20 or less is further preferable, and 18 or less is further preferable.

Specific examples of the chain unsaturated hydrocarbon group include an ethenyl group, a propenyl group, a butenyl group, an isobutenyl group, an isoprenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group and a dodecenyl group. , Tridecenyl group, tetradecenyl group, octadecenyl group. Among them, an isopentenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group and an octadecenyl group are preferable, and a decenyl group, a dodecenyl group and a tridecenyl group are more preferable. Group, tetradecenyl group, octadecenyl group.

The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, from the viewpoint of greasability. Further, from the viewpoint of reactivity with cellulose, 20 or less is preferable, 16 or less is more preferable, 12 or less is further preferable, and 8 or less is further preferable.

Specific examples of the cyclic saturated hydrocarbon group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a cyclotridecyl group, and the like. Examples thereof include a cyclotetradecyl group and a cyclooctadecyl group. Among them, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group and a cyclododecyl group are preferable, and a cyclopentyl group, a cyclohexyl group and a cycloheptyl group are more preferable. , Cyclooctyl group.

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

The total number of carbon atoms of the aryl group may be 6 or more, preferably 24 or less, more preferably 20 or less, still more preferably 14 or less, still more preferably 12 or less, still more preferably 10 or less, from the viewpoint of greasability. be.

The total number of carbon atoms of the aralkyl group is 7 or more, preferably 8 or more from the viewpoint of pulverizability, and preferably 24 or less, more preferably 20 or less, still more preferably, from the viewpoint of reactivity with cellulose. Is 14 or less, 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 the like.

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 the like.

The above-mentioned hydrocarbon group may have a substituent, and for example, it is preferable that the total number of carbon atoms of the entire hydrocarbon group including the substituent is within the above range. Examples of the substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group and the like. An alkoxy group having 1 to 6 carbon atoms; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group. An alkoxy-carbonyl group having 1 to 6 carbon atoms such as a group and an alkoxy group such as an isopentyloxycarbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and 1 carbon number such as an acetyl group and a propionyl group. Examples thereof include an acyl group of up to 6; an aralkyl group; an aralkyloxy group; an alkylamino group having 1 to 6 carbon atoms; and a dialkylamino group having 1 to 6 carbon atoms in the alkyl group. The above-mentioned hydrocarbon group itself may be bonded as a substituent. These may be introduced individually by 1 type or by 2 or more types at arbitrary ratios.

Specific examples of the compound (B) include alkyl or alkenyl succinic anhydride such as dodecenyl succinic anhydride and hexadecenyl succinic anhydride, hexadecyl glutaric acid anhydride, octadecyl glutaric acid anhydride and the like alkyl or alkenyl hydride glutaric acid. Can be mentioned. These may be prepared according to a known method or commercially available products may be used. As described above, the number of carbon atoms of the alkyl and alkenyl is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 10 or more, and from the viewpoint of reactivity with cellulose, from the viewpoint of pulverizability. , 30 or less is preferable, 24 or less is more preferable, 20 or less is further preferable, and 18 or less is further preferable.

The molecular weight of the compound (B) is preferably 50 or more, more preferably 100 or more, still more preferably 200 or more, from the viewpoint of greasability. Further, from the viewpoint of affinity with cellulose, it is preferably 600 or less, more preferably 500 or less, still more preferably 400 or less. In the present specification, the molecular weight of a small molecule compound can be calculated based on the atomic weight of a constituent atom.

(C) Silane coupling agent
Examples of the compound (C) include coupling agents such as isocyanatesilane, aminosilane, mercaptosilane, epoxysilane, vinylsilane, methacrylsilane, and epoxysilane. Of these, a coupling agent of isocyanate silane, amino silane, mercapto silane, and epoxy silane is preferable from the viewpoint of reactivity with cellulose.

Examples of the isocyanate silane include 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, tris- (3-trimethoxysilylpropyl) isocyanurate and the like.

Examples of the aminosilane include 3-aminopropyltriethoxysilane and n-β (aminoethyl) γ-aminopropyltriethoxysilane.

Examples of the mercaptosilane include 3-mercaptopropyltrimethoxysilane.

Examples of the epoxy silane include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and the like.

The amount of the additive used is 0.1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the cellulose-containing raw material from the viewpoint of achieving both rigidity and toughness when blended in the resin, but the additive and cellulose are used. From the viewpoint of increasing the mixing property and improving the rigidity when blended in the resin, it is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass. From the viewpoint of reducing the crystallinity and improving the toughness when blended in the resin, it is preferably 75 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 25 parts by mass or less, still more preferably. Is 20 parts by mass or less.

The amount of the additive used is 0.1 parts by mass or more and 100 parts by mass or less, preferably 0.5 parts by mass with respect to 100 parts by mass of the cellulose-containing raw material from the viewpoint of achieving both rigidity and toughness when blended in the resin. 75 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less, further preferably 1 part by mass or more and 25 parts by mass or less, still more preferably 1 part by mass or more and 20 parts by mass or less, still more preferably 3 parts by mass. It is 20 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less.
When two or more kinds of additives are used, the amount used means the total amount.

[Grinding process]
Using the above-mentioned cellulose-containing raw material and additives, pulverization is performed in a dry manner. In the present specification, pulverizing a cellulose-containing raw material in the presence of an additive is referred to as "mixed pulverization".

As the crusher used in the dry crushing treatment, a medium type crusher is preferable. Medium-type crushers include container-driven crushers and medium-stirring crushers. Examples of the container-driven crusher include a rolling mill, a vibration mill, a planetary mill, and a centrifugal flow mill. As the medium stirring type crusher, a tower type crusher such as a tower mill; a stirring tank type crusher such as an attritor, an aquamizer, or a sand grinder; a distribution tank type crusher such as a viscomill or a pearl mill; a distribution tube type crusher; An annual type crusher such as a coball mill; a continuous type dynamic type crusher and the like can be mentioned. In these crushers, the crystallinity of cellulose obtained can be controlled by appropriately adjusting the peripheral speed of the rotor, the sample supply speed, the stirring time, and the like.

The material of the medium that can be used is not particularly limited, and examples thereof include iron, stainless steel, alumina, zirconia, silicon carbide, silicon carbide, and glass. The shape of the medium is not particularly limited, and examples thereof include balls, rods, and tubes. The rod is a rod-shaped medium, and a rod having a cross section of a polygon such as a quadrangle or a hexagon, a circle, or an ellipse can be used.

The filling rate of the medium varies depending on the model of the crusher and the shape of the medium. For example, in the case of a rod, it is preferably 10% or more, more preferably 15% or more, and preferably 70% or less. More preferably, it is 60% or less. When the filling rate is within this range, the contact frequency between the cellulose-containing raw material and the rod can be improved, and the pulverization efficiency can be improved. Here, the filling factor means the apparent volume of the medium with respect to the volume of the stirring portion of the crusher. Further, from the viewpoint of increasing the contact frequency between the cellulose-containing raw material and the rod and improving the pulverization efficiency, it is preferable to use a plurality of rods.

The treatment time cannot be unconditionally determined depending on the type of the pulverizer, the type of the medium, the size, the filling rate, etc., but from the viewpoint of reducing the crystallinity, it is preferably 0.01 hr or more, more preferably 0.05 hr. The above is more preferably 0.1 hr or more, and from the viewpoint of productivity, it is preferably 10 hr or less, more preferably 5 hr or less, still more preferably 2 hr or less, still more preferably 1 hr or less, still more preferably 0.5 hr or less. be. The treatment temperature is not particularly limited, but is usually about 5 to 250 ° C. from the viewpoint of preventing deterioration due to heat.

Difference in I-type crystallization index (A) of cellulose before and after the pulverization treatment [I-type crystallization index (A) of cellulose before pulverization treatment-I-type crystallization index (A) of cellulose after pulverization treatment] From the viewpoint of achieving both rigidity and toughness when blended in a resin, it is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, and preferably 120% or less from the viewpoint of pulverization efficiency. It is more preferably 100% or less, still more preferably 90% or less. From these viewpoints, the difference in the type I crystallization index (A) of cellulose before and after the crushing treatment [I type crystallization index (A) of cellulose before crushing treatment-type I crystallization index of cellulose after crushing treatment (A)] is preferably 30 to 120%, more preferably 40 to 100%, and even more preferably 50 to 90%.

According to the above treatment method, strong aggregation of crushed cellulose particles can be suppressed, and low crystalline cellulose can be efficiently and productively produced. Further, during the crusher treatment, the low crystalline cellulose raw material does not adhere to the inside of the crusher and can be treated by a dry method.

Thus, a cellulose-containing powder having a reduced crystallinity and a cellulose type I crystallization index of −20% or more and less than 50% can be obtained. The degree of reduction in the degree of crystallization cannot be unconditionally determined depending on the conditions of the crushing treatment and the raw materials used for the crushing treatment, but the cellulose type I crystallization index of the obtained cellulose-containing powder is the raw material used for the treatment. It is smaller than the cellulose type I crystallization index of. The cellulose type I crystallization index of the cellulose-containing powder having a reduced crystallinity is preferably -20% or more, more preferably -10% or more, and 0% or more from the viewpoint of improving the rigidity when blended with the resin. Is more preferable, and from the viewpoint of improving toughness when blended in the resin, 50% or less is preferable, 40% or less is more preferable, 30% or less is further preferable, 25% or less is further preferable, and when blended in the resin. From the viewpoint of achieving both rigidity and toughness, it is preferably -20% or more and 50% or less, more preferably -10% or more and 40% or less, further preferably 0% or more and 30% or less, and further preferably 0% or more and 25%. It is as follows.

Further, the obtained cellulose-containing powder preferably has a sharp particle size distribution from the viewpoint of achieving both rigidity and toughness when blended in the resin, and is more than 250 μm from the viewpoint of improving the rigidity when blended in the resin. The content of the particles having a particle size (also referred to as “particle ratio”) is preferably 50% by volume or less, more preferably 45% by volume or less, and 40% by volume in the total powder (of the obtained cellulose-containing powder). The following is further preferable, 30% by volume or less is further preferable, 20% by volume or less is further preferable, and from the viewpoint of production efficiency, 0.1% by volume or more is preferable, and 1% by volume or more is more preferable. Therefore, the content of the particles having a particle size of more than 250 μm is preferably 0.1 to 50% by volume, more preferably 0.1 to 45% by volume, still more preferably 0.1 to 40% by volume in the total powder. , 0.1 to 30% by volume, more preferably 0.1 to 20% by volume, still more preferably 1 to 20% by volume.

Further, from the viewpoint of improving the rigidity when blended in the resin, the content of the particles having a particle size of 32 μm or less is preferably 30% by volume or less, more preferably 25% by volume or less, and more preferably 20% by volume in the total powder. The following is more preferable, 10% by volume or less is further preferable, 5% by volume or less is further preferable, 0.01% by volume or more is preferable, and 0.1% by volume or more is preferable from the viewpoint of improving production efficiency and toughness when blended in the resin. The above is more preferable, and 0.3% by volume or more is even more preferable. Therefore, the content of the particles having a particle size of 32 μm or less is preferably 0.01 to 30% by volume, more preferably 0.01 to 25% by volume, still more preferably 0.01 to 20% by volume in the total powder. , 0.01 to 10% by volume, more preferably 0.01 to 5% by volume, further preferably 0.1 to 5% by volume, still more preferably 0.3 to 5% by volume.

Further, from the viewpoint of achieving both rigidity and toughness when blended in the resin, the content of particles having a particle size of more than 32 μm and 150 μm or less is preferably 40% by volume or more, more preferably 45% by volume or more in the total powder. , 50% by volume or more, preferably 98% by volume or less, more preferably 95% by volume or less, further preferably 90% by volume or less, and from these viewpoints, 40 to 98% by volume is preferable. , 45-95% by volume, more preferably 50-90% by volume.

Further, from the viewpoint of achieving both rigidity and toughness when blended in the resin, the content of particles having a particle size of more than 32 μm and 250 μm or less is preferably 40% by volume or more, more preferably 45% by volume or more in the total powder. , 50% by volume or more is further preferable, 60% by volume or more is further preferable, 98% by volume or less is preferable, 95% by volume or less is more preferable, and 90% by volume or less is further preferable from the viewpoint of production efficiency. , 40-98% by volume, more preferably 45-95% by volume, even more preferably 50-90% by volume, even more preferably 60-90% by volume.

The median diameter of the obtained cellulose-containing powder is preferably 32 μm or more, more preferably 50 μm or more, still more preferably 80 μm or more, and more preferably 80 μm or more in the total powder from the viewpoint of achieving both rigidity and toughness when blended in the resin. It is 100 μm or more, and from the same viewpoint, it is preferably 400 μm or less, more preferably 300 μm or less, further preferably 250 μm or less, still more preferably 200 μm or less, preferably 32 to 400 μm, more preferably 50 to 300 μm, and 80. It is more preferably ~ 250 μm, and even more preferably 100 to 200 μm. The above-mentioned particle size distribution and median diameter can be obtained by the method described in Examples.

INDUSTRIAL APPLICABILITY According to the present invention, low crystalline cellulose containing an additive can be easily produced without going through a complicated process.

The cellulose-containing powder of the present invention has a cellulose type I crystallization index of -20% or more and less than 50%, and is composed of the following (A), (B), and (C) with respect to 100 parts by mass of the cellulose-containing raw material. It contains 0.1 part by mass or more and 100 parts by mass or less of one or more kinds of additives selected from the group.
(A) Polymer compound having acid anhydride
(B) Small molecule compound with acid anhydride
(C) Silane coupling agent

The cellulose-containing powder of the present invention preferably has a particle size of 32 μm or less and a particle ratio of 10% by volume or less in the entire cellulose-containing powder. Further, the cellulose-containing powder of the present invention preferably contains 40% by volume or more of particles having a particle size of more than 32 μm and 150 μm or less in the cellulose-containing powder.
The cellulose-containing powder of the present invention can be produced, for example, by the above-mentioned production method of the present invention, and the details and properties of each component, specific examples of numerical values and numerical ranges are the same as those in the above-mentioned production method of the present invention. The same is true.

The low-crystalline cellulose obtained from the present invention and the cellulose-containing powder of the present invention can be used as a substitute for the conventionally used cellulose, and can be blended with various resins, rubbers, asphalt, etc. to form machine tool parts. It can be suitably used for various applications such as home appliance parts, automobile parts, and tires.

Examples of the resin to which the low crystalline cellulose obtained from the present invention and the cellulose-containing powder of the present invention can be blended include polyethylene (PE resin), polypropylene (PP resin), polystyrene (PS resin), and 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), and Poly. One or more selected from chloroprene (PCP resin) and the like are preferable, and polypropylene resin is more preferable.

The blending ratio of the resin and the low crystalline cellulose, that is, the resin and the cellulose-containing powder of the present invention is preferably 5 parts by mass or more of the low crystalline cellulose or the cellulose-containing powder of the present invention with respect to 100 parts by mass of the resin. More than parts is more preferable, 15 parts by mass or more is further preferable, 70 parts by mass or less is preferable, 50 parts by mass or less is more preferable, 40 parts by mass or less is further preferable, 30 parts by mass or less is further preferable, and 5 to 70 parts by mass is preferable. Parts, more preferably 5 to 50 parts by mass, still more preferably 5 to 40 parts by mass, still more preferably 5 to 30 parts by mass, still more preferably 10 to 30 parts by mass, still more preferably 15 to 30 parts by mass. be.

With respect to the above-described embodiment, the present invention further discloses the following method for producing a cellulose-containing powder and a cellulose-containing powder.

<1> One selected from the group consisting of the following (A), (B), and (C) with respect to 100 parts by mass of the cellulose-containing raw material having a cellulose I-type crystallization index of 10% or more and less than 100%. Production of a cellulose-containing powder having a cellulose I-type crystallization index of -20% or more and less than 50%, which comprises a step of adding two or more kinds of additives by 0.1 part by mass or more and 100 parts by mass or less and pulverizing by a dry method. Method.
(A) Polymer compound having acid anhydride
(B) Small molecule compound with acid anhydride
(C) Silane coupling agent

<2> The cellulose type I crystallization index of the cellulose-containing raw material is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, still more preferably 50% or more, still more preferably 60% or more. , The method for producing a cellulose-containing powder according to <1>.
<3> The amount of the additive used is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass with respect to 100 parts by mass of the cellulose-containing raw material. The method for producing a cellulose-containing powder according to the above <1> or <2>, which is more than one part.
<4> With respect to 100 parts by mass of the cellulose-containing raw material, the amount of the additive used is preferably 75 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less. The method for producing a cellulose-containing powder according to any one of <1> to <3>.
<5> The amount of the additive used is preferably 0.5 parts by mass or more and 75 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less, still more preferably, with respect to 100 parts by mass of the cellulose-containing raw material. 1 part by mass or more and 25 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, further preferably 3 parts by mass or more and 20 parts by mass or less, still more preferably 5 parts by mass or more and 20 parts by mass or less. > To <4> The method for producing a cellulose-containing powder according to any one of the following items.
<6> The item according to any one of <1> to <5>, wherein the cellulose content in the raw material is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more. Method for producing cellulose-containing powder.
<7> The method for producing a cellulose-containing powder according to any one of <1> to <6> above, wherein the upper limit of the cellulose content in the raw material is preferably 100% by mass, more preferably 99% by mass or less. ..
<8> The water content in the cellulose-containing raw material is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1.0% by mass. The method for producing a cellulose-containing powder according to any one of <1> to <7>, which is more preferably 1.5% by mass or more, still more preferably 2.0% by mass or more.
<9> The water content in the cellulose-containing raw material is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less. ~ <8> The method for producing a cellulose-containing powder according to any one of the following items.
<10> The water content in the cellulose-containing raw material after the drying treatment is preferably 4.5% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.5% by mass or less, still more preferably 3. The method for producing a cellulose-containing powder according to any one of <1> to <9>, which is 0.0% by mass or less.
<11> When two or more kinds of additives are used, two or more kinds in (A), two or more kinds in (B), two or more kinds in (C), (A) and ( The combination of B), the combination of (B) and (C), the combination of (A) and (C), and the combination of (A) and (B) and (C) are preferable, as described above <1> to <10>. The method for producing a cellulose-containing powder according to any one of the following items.
<12> The cellulose-containing powder according to any one of <1> to <11>, wherein the additive is preferably one or more selected from the group consisting of (A) and (C). Production method.
<13> The method for producing a cellulose-containing powder according to any one of <1> to <12> above, wherein the acid anhydride in the compound (A) is preferably maleic anhydride, succinic anhydride and glutaric anhydride. ..
<14> The method for producing a cellulose-containing powder according to any one of <1> to <13> above, wherein the polymer in the compound (A) is preferably a polyolefin resin, an acrylic resin and a styrene resin.
<15> The polyolefin-based resin is preferably an ethylene-based 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, etc.). Polymers with acrylic acid, etc.], propylene-based polymers [polymers of polypropylene, propylene and one or more other vinyl compounds, etc.], ethylene-propylene copolymers, polybutene, and poly-4-methyl. The method for producing a cellulose-containing powder according to any one of <1> to <14>, which is Penten-1.
<16> The weight average molecular weight of the compound (A) is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, still more preferably 20,000 or more. ~ <15> The method for producing a cellulose-containing powder according to any one of the following items.
<17> Any one of <1> to <16>, wherein the weight average molecular weight of the compound (A) is preferably 150,000 or less, more preferably 140,000 or less, still more preferably 130,000 or less. The method for producing a cellulose-containing powder according to.
<18> Any of the above <1> to <17>, wherein the melting point of the compound (A) is preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower, still more preferably 170 ° C. or lower. The method for producing a cellulose-containing powder according to item 1.
<19> The method for producing a cellulose-containing powder according to any one of <1> to <18>, wherein the preferable lower limit of the melting point of the compound (A) is 100 ° C.
<20> Production of the cellulose-containing powder according to any one of <1> to <19> above, wherein the compound (A) is preferably maleic anhydride-modified polyolefin, and more preferably maleic anhydride-modified polypropylene. Method.
<21> The method for producing a cellulose-containing powder according to any one of <1> to <20> above, wherein the acid anhydride in the compound (B) is preferably maleic anhydride, succinic anhydride and glutaric anhydride. ..
<22> The small molecule in the compound (B) is preferably a hydrocarbon group, more preferably a chain-type saturated hydrocarbon group, a chain-type unsaturated hydrocarbon group, a cyclic-type saturated hydrocarbon group, and an aromatic hydrocarbon group. The method for producing a cellulose-containing powder according to any one of <1> to <21>.
<23> The number of carbon atoms of the chain saturated hydrocarbon group is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, further preferably 10 or more, still more preferably 15 or more, as described above <1> to <22. > The method for producing a cellulose-containing powder according to any one of the following items.
<24> The number of carbon atoms of the chain saturated hydrocarbon group is preferably 30 or less, more preferably 24 or less, further preferably 20 or less, still more preferably 18 or less, according to any one of <1> to <23>. The method for producing a cellulose-containing powder according to the above.
<25> The chain saturated hydrocarbon group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, a tert-pentyl group and an isopentyl. <1> ~ <24> The method for producing a cellulose-containing powder according to any one of the following items.
<26> The number of carbon atoms of the chain unsaturated hydrocarbon group is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, still more preferably 10 or more, any one of <1> to <25>. The method for producing a cellulose-containing powder according to.
<27> The number of carbon atoms of the chain unsaturated hydrocarbon group is preferably 30 or less, more preferably 24 or less, further preferably 20 or less, still more preferably 18 or less, any one of the above <1> to <26>. The method for producing a cellulose-containing powder according to.
<28> The chain unsaturated hydrocarbon group is preferably an ethenyl group, a propenyl group, a butenyl group, an isobutenyl group, an isopenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, and the like. The method for producing a cellulose-containing powder according to any one of <1> to <27>, which is a tridecenyl group, a tetradecenyl group, or an octadecenyl group.
<29> The cellulose-containing powder according to any one of <1> to <28>, wherein the cyclic saturated hydrocarbon group preferably has 3 or more carbon atoms, more preferably 4 or more, and even more preferably 5 or more. Production method.
<30> The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, still more preferably 8 or less, according to any one of <1> to <29>. The method for producing a cellulose-containing powder according to the above.
<31> The cyclic saturated hydrocarbon group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a cyclotridecyl group, or a cyclo. The method for producing a cellulose-containing powder according to any one of <1> to <30>, which is a tetradecyl group or a cyclooctadecyl group.
<32> The method for producing a cellulose-containing powder according to any one of <1> to <31> above, wherein the aromatic hydrocarbon group is preferably selected from the group consisting of an aryl group and an aralkyl group.
<33> The method for producing a cellulose-containing powder according to any one of <1> to <32>, wherein the total carbon number of the aryl group is preferably 6 or more.
<34> The total carbon number of the aryl group is preferably 24 or less, more preferably 20 or less, still more preferably 14 or less, still more preferably 12 or less, still more preferably 10 or less. The method for producing a cellulose-containing powder according to any one of the following items.
<35> The method for producing a cellulose-containing powder according to any one of <1> to <34>, wherein the total carbon number of the aralkyl group is preferably 7 or more, more preferably 8 or more.
<36> The total carbon number of the aralkyl group 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. The method for producing a cellulose-containing powder according to any one of the following items.
<37> The aryl group is preferably a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group and a terphenyl group, and an aralkyl group is preferably a benzyl group, a phenethyl group and a phenylpropyl group. The method for producing a cellulose-containing powder according to any one of <1> to <36> above, which is a phenylpentyl group, a phenylhexyl group, a phenylheptyl group and a phenyloctyl group.
<38> The hydrocarbon group has a substituent, and the substituent is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group. , Pentyloxy group, isopentyloxy group, hexyloxy group and other alkoxy groups having 1 to 6 carbon atoms; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, An alkoxy-carbonyl group having 1 to 6 carbon atoms in an alkoxy group such as a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, or an isopentyloxycarbonyl group; a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Halogen atoms such as; acetyl group, acyl group having 1 to 6 carbon atoms such as propionyl group; aralkyl group; aralkyloxy group; alkylamino group having 1 to 6 carbon atoms; dialkylamino having 1 to 6 carbon atoms in the alkyl group. The method for producing a cellulose-containing powder according to any one of <1> to <37>, which is a group.
<39> Production of the cellulose-containing powder according to any one of <1> to <38>, wherein the molecular weight of the compound (B) is preferably 50 or more, more preferably 100 or more, still more preferably 200 or more. Method.
<40> Production of the cellulose-containing powder according to any one of <1> to <39>, wherein the molecular weight of the compound (B) is preferably 600 or less, more preferably 500 or less, still more preferably 400 or less. Method.
<41> The compound (B) is preferably one or more selected from alkyl or alkenyl succinic anhydride and alkyl or alkenyl succinic anhydride, and more preferably dodecenyl succinic anhydride, hexadecenyl succinic anhydride, hexadecyl glutaric acid anhydride. The method for producing a cellulose-containing powder according to any one of <1> to <40> above, which is a compound and an octadecylglutaric anhydride.
<42> In any one of <1> to <41> above, the compound (C) is preferably a coupling agent such as isocyanatesilane, aminosilane, mercaptosilane, epoxysilane, vinylsilane, methacrylsilane and epoxysilane. The method for producing a cellulose-containing powder according to the above.
<43> Isocyanate silane is preferably 3-isocyanate propyltrimethoxysilane, 3-isocyanapropyltriethoxysilane and tris- (3-trimethoxysilylpropyl) isocyanurate, and aminosilane is preferably γ-aminopropyltri. Ethoxysilane and n-β (aminoethyl) γ-aminopropyltriethoxysilane, mercaptosilane is preferably 3-mercaptopropyltrimethoxysilane, and epoxysilane is preferably 2- (3,4-epoxy). The cellulose-containing powder according to any one of <1> to <42> above, which is cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Method.
<44> The method for producing a cellulose-containing powder according to any one of <1> to <43>, wherein the dry pulverization treatment is preferably performed by a medium pulverizer.
<45> The method for producing a cellulose-containing powder according to any one of <1> to <44> above, wherein the medium-type crusher is preferably a container-driven crusher and a medium-stirring crusher.
<46> The method for producing a cellulose-containing powder according to any one of <1> to <45> above, wherein the container-driven crusher is preferably a rolling mill, a vibration mill, a planetary mill, or a centrifugal flow mill.
<47> The medium stirring type crusher is preferably a tower type crusher such as a tower mill; a stirring tank type crusher such as an attritor, an aquamizer, or a sand grinder; a distribution tank type crusher such as a viscomill or a pearl mill; a distribution tube type. The method for producing a cellulose-containing powder according to any one of <1> to <46> above, which is a crusher; an annual type crusher such as a coball mill; a continuous dynamic type crusher.
<48> The item according to any one of <1> to <47>, wherein the processing time of the pulverization treatment is preferably 0.01 hr or more, more preferably 0.05 hr or more, still more preferably 0.1 hr or more. A method for producing a cellulose-containing powder.
<49> The treatment time of the pulverization treatment is preferably 10 hr or less, more preferably 5 hr or less, still more preferably 2 hr or less, still more preferably 1 hr or less, still more preferably 0.5 hr or less. 48> The method for producing a cellulose-containing powder according to any one of the following items.
<50> The method for producing a cellulose-containing powder according to any one of <1> to <49>, wherein the treatment temperature of the pulverization treatment is preferably 5 ° C. or higher.
<51> The method for producing a cellulose-containing powder according to any one of <1> to <50>, wherein the treatment temperature of the pulverization treatment is preferably 250 ° C. or lower.
<52> Any of the above <1> to <51>, wherein the produced cellulose-containing powder has a cellulose I-type crystallization index of -20% or more, more preferably -10% or more, still more preferably 0% or more. The method for producing a cellulose-containing powder according to item 1.
<53> The cellulose type I crystallization index of the produced cellulose-containing powder is preferably 50% or less, more preferably 40% or less, further preferably 30% or less, still more preferably 25% or less, the above <1>. ~ <52> The method for producing a cellulose-containing powder according to any one of the following items.
<54> The cellulose type I crystallization index of the produced cellulose-containing powder is preferably -20% or more and 50% or less, more preferably -10% or more and 40% or less, and further preferably 0% or more and 30% or less. The method for producing a cellulose-containing powder according to any one of <1> to <53>, which is more preferably 0% or more and 25% or less.
<55> The proportion of particles having a particle size of 32 μm or less in the whole produced cellulose-containing powder is preferably 30% by volume or less, more preferably 25% by volume or less, further preferably 20% by volume or less, and 10% by volume or less. The method for producing a cellulose-containing powder according to any one of <1> to <54>, further preferably 5% by volume or less.
<56> The proportion of particles having a particle size of 32 μm or less in the whole produced cellulose-containing powder is preferably 0.01% by volume or more, more preferably 0.1% by volume or more, still more preferably 0.3% by volume or more. The method for producing a cellulose-containing powder according to any one of <1> to <55>, which is preferable.
<57> The content of particles having a particle size of 32 μm or less in the whole produced cellulose-containing powder is preferably 0.01 to 30% by volume, more preferably 0.01 to 25% by volume, in the total powder. 0.01 to 20% by volume is more preferable, 0.01 to 10% by volume is further preferable, 0.01 to 5% by volume is further preferable, 0.1 to 5% by volume is further preferable, and 0.3 to 5% by volume is more preferable. The method for producing a cellulose-containing powder according to any one of <1> to <56>, wherein% is more preferable.
<58> The content of particles having a particle size of more than 250 μm in the whole produced cellulose-containing powder is preferably 50% by volume or less, preferably 45% by volume or less, based on the total powder (of the obtained cellulose-containing powder). The method for producing a cellulose-containing powder according to any one of <1> to <57>, wherein 40% by volume or less is further preferable, 30% by volume or less is further preferable, and 20% by volume or less is further preferable.
<59> The content of particles having a particle size of more than 250 μm in the whole produced cellulose-containing powder is preferably 0.1% by volume or more in the total powder (of the obtained cellulose-containing powder), and is preferably 1% by volume. The method for producing a cellulose-containing powder according to any one of <1> to <58>, wherein the above is more preferable.
<60> The content of particles having a particle size of more than 250 μm in the whole produced cellulose-containing powder is preferably 0.1 to 50% by volume, more preferably 0.1 to 45% by volume, in the total powder. 0.1 to 40% by volume is further preferable, 0.1 to 30% by volume is further preferable, 0.1 to 20% by volume is more preferable, and 1 to 20% by volume is further preferable. The method for producing a cellulose-containing powder according to any one of the following items.
<61> The proportion of particles having a particle size of more than 32 μm and 150 μm or less in the whole produced cellulose-containing powder is preferably 40% by volume or more, more preferably 45% by volume or more, still more preferably 50% by volume or more. > To <60> The method for producing a cellulose-containing powder according to any one of the following items.
<62> The proportion of particles having a particle size of more than 32 μm and 150 μm or less in the whole produced cellulose-containing powder is preferably 98% by volume or less, more preferably 95% by volume or less, still more preferably 90% by volume or less. > To <61> The method for producing a cellulose-containing powder according to any one of the following items.
<63> The proportion of particles having a particle size of more than 32 μm and 150 μm or less in the whole produced cellulose-containing powder is preferably 40 to 98% by volume, more preferably 45 to 95% by volume, still more preferably 50 to 90% by volume. The method for producing a cellulose-containing powder according to any one of <1> to <62>.
<64> The resin to which the produced cellulose-containing powder can be blended is preferably polypropylene resin, polyethylene resin, polystyrene resin, polyvinyl acetate resin, polyvinyl chloride resin, vinylidene chloride resin, polyacrylic acid resin, polyacrylic acid. The cellulose-containing powder according to any one of <1> to <63> above, which is one or more selected from an ester resin, a polybutadiene resin, a polyisoprene resin and a polychloroprene resin, and more preferably a polypropylene resin. Method.
<65> The blending ratio of the resin and the produced cellulose-containing powder is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 15 parts by mass or more with respect to 100 parts by mass of the resin. The method for producing a cellulose-containing powder according to any one of <1> to <64>, wherein is more preferable.
<66> The blending ratio of the resin and the produced cellulose-containing powder is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and 40 parts by mass with respect to 100 parts by mass of the resin. The method for producing a cellulose-containing powder according to any one of <1> to <65>, wherein the following is more preferable, and 30 parts by mass or less is further preferable.
<67> The method for producing a cellulose-containing powder according to any one of <1> to <66>, wherein the obtained molded product has a tensile elastic modulus (GPa) of preferably 1.9 GPa or more.
<68> The tensile breaking strain (%) of the obtained molded body is preferably 4% or more when the resin type is made of PP, and preferably 50% or more when the resin type is made of PE. The method for producing a cellulose-containing powder according to any one of <1> to <67>.
<69> The yield point stress (MPa) of the obtained molded product is preferably 35 MPa or more when the type of resin is made of PP, and preferably 11 MPa or more when the type of resin is made of PE. <1> The method for producing a cellulose-containing powder according to any one of <68>.
<70> Difference in I-type crystallization index (A) of cellulose before and after the crushing treatment [I-type crystallization index (A) of cellulose before crushing treatment-I-type crystallization index (A) of cellulose after crushing treatment )] Is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more, the method for producing a cellulose-containing powder according to any one of <1> to <69>.
<71> The difference in the type I crystallization index (A) of cellulose before and after the pulverization treatment step is preferably 120% or less, more preferably 100% or less, still more preferably 90% or less. <70> The method for producing a cellulose-containing powder according to any one of the following items.
<72> Difference in I-type crystallization index (A) of cellulose before and after the pulverization treatment [I-type crystallization index (A) of cellulose before pulverization treatment-I-type crystallization index (A) of cellulose after pulverization treatment )] Is preferably 30 to 120%, more preferably 40 to 100%, still more preferably 50 to 90%, according to any one of <1> to <71> above. ..
<73> The content of particles having a particle size of more than 32 μm and 250 μm or less in the whole produced cellulose-containing powder is preferably 40% by volume or more, more preferably 45% by volume or more, and more preferably 50% by volume or more in the total powder. The method for producing a cellulose-containing powder according to any one of <1> to <72>, wherein 60% by volume or more is further preferable.
<74> The content of particles having a particle size of more than 32 μm and 250 μm or less in the whole produced cellulose-containing powder is preferably 98% by volume or less, more preferably 95% by volume or less, and 90% by volume or less in the total powder. The method for producing a cellulose-containing powder according to any one of <1> to <73>, wherein is more preferable.
<75> The content of particles having a particle size of more than 32 μm and 250 μm or less in the whole produced cellulose-containing powder is preferably 40 to 98% by volume, more preferably 45 to 95% by volume, and 50 to 90% by volume. The method for producing a cellulose-containing powder according to any one of <1> to <74>, further preferably 60 to 90% by volume.

<76> Cellulose type I crystallization index is -20% or more and less than 50%, and is selected from the group consisting of the following (A), (B), and (C) with respect to 100 parts by mass of the cellulose-containing raw material. A cellulose-containing powder containing 0.1 parts by mass or more and 100 parts by mass or less of seeds or two or more kinds of additives.
(A) Polymer compound having acid anhydride
(B) Small molecule compound with acid anhydride
(C) Silane coupling agent

<77> The cellulose-containing powder according to <76>, which is produced by the method for producing a cellulose-containing powder according to any one of <1> to <75>.
<78> The cellulose-containing powder according to <76> or <77>, wherein the cellulose-containing powder has a cellulose I-type crystallization index of -10% or more, more preferably 0% or more.
<79> The cellulose type I crystallization index of the cellulose-containing powder is preferably 50% or less, more preferably 40% or less, further preferably 30% or less, still more preferably 25% or less, as described above <76> to <78>. > The cellulose-containing powder according to any one of the items.
<80> The cellulose type I crystallization index of the cellulose-containing powder is preferably -20% or more and 50% or less, more preferably -10% or more and 40% or less, still more preferably 0% or more and 30% or less, still more preferably. Item 2. The cellulose-containing powder according to any one of <76> to <79>, which is 0% or more and 25% or less.
<81> The additive is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more with respect to 100 parts by mass of the cellulose-containing raw material. The cellulose-containing powder according to any one of <76> to <80>.
<82> The additive is preferably 75 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the cellulose-containing raw material. The cellulose-containing powder according to any one of <76> to <81>.
<83> The amount of the additive used is preferably 0.5 parts by mass or more and 75 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less, still more preferably, with respect to 100 parts by mass of the cellulose-containing raw material. 1 part by mass or more and 25 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, further preferably 3 parts by mass or more and 20 parts by mass or less, still more preferably 5 parts by mass or more and 20 parts by mass or less. > To <82> The cellulose-containing powder according to any one of the following items.
<84> The proportion of particles having a particle size of 32 μm or less in the entire cellulose-containing powder is preferably 30% by volume or less, more preferably 25% by volume or less, further preferably 20% by volume or less, still more preferably 10% by volume or less. Item 2. The cellulose-containing powder according to any one of <76> to <83>, more preferably 5% by volume or less.
<85> The proportion of particles having a particle size of 32 μm or less in the entire cellulose-containing powder is preferably 0.01% by volume or more, more preferably 0.1% by volume or more, still more preferably 0.3% by volume or more. <76> The cellulose-containing powder according to any one of <84>.
<86> The content of particles having a particle size of 32 μm or less in the entire cellulose-containing powder is preferably 0.01 to 30% by volume, more preferably 0.01 to 25% by volume, and 0.01 in the total powder. -20% by volume is more preferable, 0.01 to 10% by volume is further preferable, 0.01 to 5% by volume is further preferable, 0.1 to 5% by volume is further preferable, and 0.3 to 5% by volume is further preferable. The cellulose-containing powder according to any one of <76> to <85>, which is preferable.
<87> The content of particles having a particle size of more than 250 μm in the entire cellulose-containing powder is preferably 50% by volume or less, more preferably 45% by volume or less, based on the total powder (of the obtained cellulose-containing powder). The cellulose-containing powder according to any one of <76> to <86>, wherein 40% by volume or less is further preferable, 30% by volume or less is further preferable, and 20% by volume or less is further preferable.
<88> The content of particles having a particle size of more than 250 μm in the entire cellulose-containing powder is preferably 0.1% by volume or more, more preferably 1% by volume or more, any one of <76> to <87>. The cellulose-containing powder according to the section.
<89> The content of particles having a particle size of more than 250 μm in the entire cellulose-containing powder is preferably 0.1 to 50% by volume, more preferably 0.1 to 45% by volume, and 0.1 to 40% by volume. More preferably, 0.1 to 30% by volume is further preferable, 0.1 to 20% by volume is more preferable, and 1 to 20% by volume is further preferable, according to any one of <76> to <88>. Cellulose-containing powder.
<90> The content of particles having a particle size of more than 32 μm and 250 μm or less in the whole cellulose-containing powder is preferably 40% by volume or more, more preferably 45% by volume or more, further preferably 50% by volume or more, and even more preferably 60% by volume. The cellulose-containing powder according to any one of <76> to <89>, wherein the above is more preferable.
<91> The content of particles having a particle size of more than 32 μm and 250 μm or less in the whole cellulose-containing powder is preferably 98% by volume or less, more preferably 95% by volume or less, still more preferably 90% by volume or less, the above <76>. > To <90> The cellulose-containing powder according to any one of Items.
<92> The content of particles having a particle size of more than 32 μm and 250 μm or less in the whole cellulose-containing powder is preferably 40 to 98% by volume, more preferably 45 to 95% by volume, still more preferably 50 to 90% by volume. Item 3. The cellulose-containing powder according to any one of <76> to <91>, more preferably 60 to 90% by volume.
<93> The proportion of particles having a particle size of more than 32 μm and 150 μm or less in the entire cellulose-containing powder is preferably 40% by volume or more, more preferably 45% by volume or more, still more preferably 50% by volume or more. 92> The cellulose-containing powder according to any one of the following items.
<94> The proportion of particles having a particle size of more than 32 μm and 150 μm or less in the entire cellulose-containing powder is preferably 98% by volume or less, more preferably 95% by volume or less, still more preferably 90% by volume or less. 93> The cellulose-containing powder according to any one of the following items.
<95> The proportion of particles having a particle size of more than 32 μm and 150 μm or less in the entire cellulose-containing powder is preferably 40 to 98% by volume, more preferably 45 to 95% by volume, still more preferably 50 to 90% by volume. > To <94> The cellulose-containing powder according to any one of Items.
<96> The resin to which the cellulose-containing powder can be blended is preferably polypropylene resin, polyethylene resin, polystyrene resin, polyvinyl acetate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic acid resin, polyacrylic acid ester resin, etc. Item 2. The cellulose-containing powder according to any one of <76> to <95>, which is one or more selected from a polybutadiene resin, a polyisoprene resin, and a polychloroprene resin, and more preferably a polypropylene resin.
<97> The mixing ratio of the resin and the cellulose-containing powder is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more with respect to 100 parts by mass of the resin. The cellulose-containing powder according to <96>.
<98> The mixing ratio of the resin and the cellulose-containing powder is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the resin. The cellulose-containing powder according to <96> or <97>, which is more preferably by mass or less.
<99> The mixing ratio of the resin and the cellulose-containing powder is preferably 5 to 70 parts by mass, more preferably 5 to 50 parts by mass, still more preferably 5 to 40 parts by mass, based on 100 parts by mass of the resin. Item 3. The cellulose-containing powder according to any one of <96> to <98>, which is more preferably 5 to 30 parts by mass, still more preferably 10 to 30 parts by mass, and even more preferably 15 to 30 parts by mass.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The part in the example is a mass part unless otherwise specified. The "normal pressure (atmospheric pressure)" indicates 101.3 kPa.

[Particle size distribution of cellulose-containing powder]
The particle size of the cellulose-containing powder is measured by sieving classification, and using an electromagnetic sieve AS-200 (manufactured by Letze), a 250 μm test sieve, a 150 μm test sieve, and a 32 μm test sieve specified in JIS Z8801 are used, respectively. The particle size distribution was measured by classifying with a sieve, and the powder remaining on the 250 μm test sieve passed through the test sieve having a particle size of “particles exceeding 250 μm” and 150 μm, and remained on the 32 μm test sieve. The powder is defined as "particles having a particle size of more than 32 μm and 150 μm or less", and the powder that has passed through a 32 μm test sieve is defined as “particles having a particle size of 32 μm or less”. Further, the particle ratio (volume%) of the "particles having a particle size of more than 32 μm and 250 μm or less" is 100% by volume of the entire cellulose-containing powder, and 100% by volume-(volume% of "particles having a particle size of more than 250 μm")-(" It is a value obtained by volume%) of "particles of 32 μm or less". The above-mentioned test sieves are utility model types manufactured by Iida Seisakusho Co., Ltd.

[Confirmation of cellulose crystal structure]
The crystal structure of cellulose is confirmed by measuring under the following conditions using "MiniFlex 600" manufactured by Rigaku. The measurement conditions are X-ray source: Cu / Kα-radiation, tube voltage: 30 kv, tube current: 15 mA, measurement range: diffraction angle 2 θ = 5 to 35 °, and X-ray scan speed: 40 ° / min. The sample for measurement is prepared by compressing pellets having an area of 320 mm ² × thickness of 1 mm. Further, the crystallinity of the cellulose type I crystal structure is calculated by calculating the obtained X-ray diffraction intensity based on the following formula (A).
Cellulose type I crystallization index (%) = [(I22.6-I18.5) /I22.6] × 100 (A)
[In the equation, I22.6 indicates the diffraction intensity of the lattice plane (002 surface) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I18.5 indicates the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5 °)].

[Moisture content of cellulose]
Using an infrared heating / drying mass measuring device (MOC-120H, manufactured by Shimadzu Corporation), 1 g of sample was measured at a constant temperature of 150 ° C. every 30 seconds, and the weight loss from the previous measured value was 0.1% or less. The weight reduction value from the initial value at the time of becoming is taken as the water content.

[Melting point of additive]
The melting point is measured by raising the temperature from 20 ° C. to 500 ° C. at a heating rate of 10 ° C./min using a DSC device (Diamond DSC manufactured by PerkinElmer).

[Weight average molecular weight of additives]
The weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography) under the following measurement conditions.
<Measurement conditions>
Column: Showa Denko Co., Ltd. Shodex HT-806M x 1 + Shodex HT-803 x 2 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

[Median diameter of cellulose-containing powder]
The average particle size (volume-based median diameter) of the cellulose-containing powder is measured dry using a laser diffraction / scattering method particle size distribution measuring device (manufactured by Beckman Coulter, model number: LS13 320).

Examples 1-5, Comparative Example 3
(Cellulose treatment)
[Cut processing]
Sheet-shaped wood pulp [Tembeck's "HV +", 800 mm x 600 mm x 1.0 mm, crystallization index 81%, α-cellulose content 96% by mass, water content 8.0% by mass], which is a cellulose-containing raw material, It was cut into a rectangular parallelepiped having a size of about 3 mm × 1.5 mm × 1.0 mm by applying it to a sheet pelletizer [“SG (E) -220” manufactured by Horai Co., Ltd.], which is a slitter cutter.

[Drying process]
The chip-shaped cellulose-containing raw material obtained by the cutting treatment was dried using a twin-screw horizontal stirring dryer [two-screw paddle dryer "NPD-1.6W (1/2)" manufactured by Nara Machinery Co., Ltd.]. The drying temperature was 140 ° C., 8 kg of the raw material was charged in advance, and the raw material was dried by batch treatment for 60 minutes under atmospheric pressure to bring the water content of the raw material to 0.8% by mass. Then, the apparatus was tilted by 2 °, and the raw material was dried by continuous treatment. At this time, the supply speed of the raw material was 18 kg / h. The water content of the dried raw material obtained by the continuous treatment was also 0.8% by mass. The obtained raw material after the drying treatment was stored in an aluminum bag until immediately before the pulverization treatment in order to prevent moisture absorption during storage. The type I crystallization index of the raw material cellulose after the drying treatment calculated from the X-ray diffraction intensity was 81%.

[Grinding process]
Inside the container of a batch type vibration mill [“MB-1” manufactured by Chuo Kakoki Co., Ltd., inner diameter 142 mm, axial length 220 mm of cylindrical space inside the container, container capacity 3.6 L], diameter 30 mm, length Thirteen 211 mm stainless steel columnar media were placed and crushed. The amount of the additives shown in Tables 1 and 2 is shown in Tables 1 and 2 with respect to 100 parts by mass of the chip-shaped cellulose-containing raw material (apparent specific gravity (hardening) 0.18 g / mL) obtained by the drying treatment. The addition was carried out, and the vibration mill was operated under the conditions of an amplitude of 8 mm and a frequency of 20 Hz for the time shown in Tables 1 and 2, and pulverized to obtain low crystalline cellulose. The total mass of the cellulose-containing raw material and the additive inside the container was 100 g.

(Resin composition)
The composition raw materials shown in Tables 1 and 2, that is, low crystalline cellulose and resin are combined as shown in Tables 1 and 2, and a kneader (Laboplast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used to rotate at 90 rpm. , Melt-kneaded at 200 ° C. for 8 minutes to obtain a resin composition.

(Molded body)
The obtained resin composition was injection-molded using an injection molding machine (J110AD-180H manufactured by Japan Steel Works, Ltd., cylinder temperature setting at 6 locations). The cylinder temperature was set to 270 ° C. from the nozzle tip side to the 5th unit, 230 ° C. for the remaining 1 unit, and 45 ° C. under the hopper. The mold temperature was set to 80 ° C., and a flat plate test piece (127 mm × 12.7 mm × 1.6 mm) was molded to obtain a molded body of a resin composition.

Example 6
As the raw material cellulose, powdered cellulose (median diameter 31.4 μm) was used instead of the chip-shaped cellulose-containing raw material. Was used to obtain a resin composition and a molded product thereof in the same manner as in Example 1.

Comparative Examples 1-2
In the cellulose treatment of Example 2 or Example 5, the pulverization treatment was carried out without adding an additive. Next, the resin composition was prepared in the same manner as in Example 1 by using the pulverized cellulose (“non-mixed pulverized cellulose” in Table 2), the resin and the additive as the raw materials for the composition as shown in Table 2. And its molded body.

Comparative Example 4
As the raw material cellulose, instead of the chip-shaped cellulose-containing raw material, the chips used in Example 1 were further pulverized into fibers with a coffee mill. In addition, as a crushing device, a planetary ball mill (P-6 type made by Fritsch, using 100 φ10 mm alumina balls as a medium, the total amount of crushed material is 40 g) is used, and the rotation speed is 250 rpm, 50 min crushing, and 10 min stop are repeated for 24 cycles. A resin composition and a molded product thereof were obtained in the same manner as in Example 1 using the composition raw materials shown in Table 2.

The raw materials in Tables 1 and 2 are as follows.
<Additives>
Youmex 1001: Manufactured by Sanyo Chemical Industries, Ltd., maleic anhydride-modified polypropylene, weight average molecular weight 40,000, melting point 142 ° C.
OREVAC G CA 100: Arkema, maleic anhydride-modified polypropylene, weight average molecular weight 116,000, melting point 161 ° C.
ASAN-PT: Kao Corporation, dodecenyl succinic anhydride, molecular weight 266
Z-6011: manufactured by Toray Dow Corning Co., Ltd., 3-aminopropyltriethoxysilane <resin>
PP: Polypropylene resin, manufactured by Japan Polypropylene Corporation, Product name: Novatec PP EA9
PE: Polyethylene resin, manufactured by Japan Polyethylene Corporation, trade name: Novatec LL UF641

The characteristics of the obtained molded body were evaluated according to the method of Test Example 1 below. The results are shown in Tables 1 and 2.

Test Example 1
A tensile test was carried out using five obtained molded bodies in a constant temperature room at 25 ° C., and the tensile elastic modulus (GPa), tensile fracture strain (%) and yield point stress (MPa) were examined. 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, and the average value was taken as the measured value, and the measured value of 5 samples. Was calculated. Although it cannot be unconditionally determined by the composition of the constituent resin, the tensile elastic modulus shows excellent rigidity when the resin type is 1.9 GPa or more when the resin type is made of PP, and the yield point stress is determined by the resin type. If it is made of PP, it is 35 MPa or more, if it is made of PE, it is 11 MPa or more, and if the resin type is 4% or more if it is made of PP, and if it is made of PE, it is judged that it shows excellent toughness. Can be done.

(Note 1): The cycle described in Comparative Example 4 was carried out.
(Note 2): Due to the presence of coarse particles, the median diameter could not be measured.
(Note 3): Coarse particles were confirmed on the surface of the resin composition, and the appearance as a product was poor, so the molded product was not evaluated.

From Tables 1 and 2, from the comparison between Example 2 and Comparative Example 1 and the comparison between Example 5 and Comparative Example 2, even if the composition of the resin composition is the same, cellulose in the presence of an additive is used. It can be seen that Example 2 or Example 5 having the pulverization treatment of the above has higher rigidity and excellent toughness of the molded product of the resin composition. In Comparative Example 3, the pulverization time was shorter than that of the example in order to prepare a cellulose type I crystallization index of 50% or more after the pulverization treatment. As a result, in Comparative Example 3, the powder after pulverization was coarse and clogging occurred in the apparatus, so that the median diameter could not be measured. In addition, coarse particles that could be visually confirmed were observed on the surface of the resin compounded with the resin.

The cellulose-containing powder obtained by the production method of the present invention can be suitably used for various industrial applications such as daily miscellaneous goods, home electric appliances parts, and automobile parts.

Claims (12)

One or more selected from the group consisting of the following (A), (B), and (C) with respect to 100 parts by mass of the cellulose-containing raw material having a cellulose I-type crystallization index of 10% or more and less than 100%. The cellulose type I crystallization index is -20% or more and less than 50%, which comprises a step of adding 0.1 part by mass or more and 100 parts by mass or less of the additive and pulverizing by a dry method. A method for producing a cellulose-containing powder, wherein the proportion of particles having a particle size of 32 μm or less is 10% by volume or less .
(A) Polyolefin resin having acid anhydride
(B) A small molecule compound having an acid anhydride , comprising one or more selected from alkyl or alkenyl succinic anhydride and alkyl or alkenyl anhydride glutaric acid .
(C) Aminosilane coupling agent The production method according to claim 1, wherein the additive is one or more selected from the group consisting of (A) and (C). The production method according to claim 1 or 2, wherein the dry pulverization treatment is performed by a medium pulverizer. The production method according to any one of claims 1 to 3 , wherein the cellulose-containing raw material has a cellulose I-type crystallization index of 50% or more. The production method according to any one of claims 1 to 4 , wherein the proportion of particles having a particle size of more than 32 μm and 250 μm or less in the entire cellulose-containing powder to be produced is 40% by volume or more. The production method according to any one of claims 1 to 5 , wherein the compound (A) is a maleic anhydride-modified polyolefin. (B) The production method according to any one of claims 1 to 6 , wherein the compound is alkyl or alkenyl succinic anhydride . Cellulose type I crystallization index is -20% or more and less than 50%, and one or 2 selected from the group consisting of the following (A), (B), and (C) with respect to 100 parts by mass of the cellulose-containing raw material. A cellulose-containing powder containing 0.1 parts by mass or more and 100 parts by mass or less of an additive of seeds or more, and having a particle ratio of particles having a particle size of 32 μm or less of 10% by mass or less in the entire cellulose-containing powder.
(A) Polyolefin resin having acid anhydride
(B) A small molecule compound having an acid anhydride , comprising one or more selected from alkyl or alkenyl succinic anhydride and alkyl or alkenyl anhydride glutaric acid .
(C) Aminosilane coupling agent The cellulose-containing powder according to claim 8 , wherein the proportion of particles having a particle size of more than 32 μm and 250 μm or less in the entire cellulose-containing powder is 40% by volume or more. The cellulose-containing powder according to claim 8 or 9, wherein the compound (A) is a maleic anhydride-modified polyolefin. (B) The cellulose-containing powder according to any one of claims 8 to 10, wherein the compound is alkyl or alkenyl succinic anhydride. A resin composition containing the cellulose-containing powder according to any one of claims 8 to 11.