JP6479904B2 - Cellulose preparation - Google Patents

Description

  The present invention relates to a cellulose preparation and a resin composition containing the same.

  Thermoplastic resins are light and excellent in processing characteristics, and thus are widely used in various fields such as automobile parts, electric / electronic parts, office equipment housings, precision parts and the like. However, the resin alone often has insufficient mechanical properties, dimensional stability, etc., and a composite of resin and various inorganic materials is generally used.

Microfibrils composed of cellulose type I crystals are known to have excellent mechanical properties, a high elastic modulus comparable to aramid fibers, and a linear expansion coefficient equal to or lower than that of glass fibers. In addition, the cellulose I type crystal has a true density of 1.56 g / cm ³ and is generally used as a reinforcing material for thermoplastic resins (density 2.4 to 2.6 g / cm ³ ) or talc (density 2. 7g / cm ³ ), which is an overwhelmingly light material. Therefore, if cellulose I-type crystals with high L / D (major axis / minor axis ratio) can be dispersed in the resin matrix in the form of microfibrils, they form a network in the resin, and thereby the mechanical properties of the crystalline cellulose are improved. It is expected that it can be granted.

  However, when a cellulose-based substance (microfibril aggregate) is dispersed in the resin, when added in a dry state, the bonds between the microfibrils are strong, so dispersion does not proceed in the resin, and when added in a wet state, the microfibril is added. Due to the water repellency of the water on the surface, there was a problem that the affinity with the resin deteriorated and the dispersion was difficult.

  For example, in Patent Document 1, in order to improve the dispersibility of cellulose particles in a resin, the average particle size is 6 μm or less, the content of particles of 20 μm or more is less than 10% by mass, and It describes that a fine powder of crystalline cellulose composed of rod-like particles having a major axis / minor axis ratio of 4 or more is dispersed in a dispersant and a thermoplastic resin. Patent Document 2 describes that when vegetable fibers such as pulp are dispersed in a thermoplastic resin, the affinity between the thermoplastic resin and the vegetable fibers is increased by adding a rosin resin together. ing. Patent Document 3 describes that an oil and fat component having an iodine value of 50 or more, a silane coupling agent, and a small amount of a radical generator are blended so that cellulose fibers and polyolefin are uniformly dispersed. Patent Document 4 describes that a rosin compound having excellent hydrophobicity is modified on the cellulose surface in order to improve water resistance when cellulose microfibrils are used as a reinforcing material for a polymer composite material. . Patent Document 5 describes blending a nonionic surfactant having an HLB value of 8 to 13 in order to improve the dispersibility of cellulose nanofibers in a thermoplastic resin. Patent Document 6 describes blending a hydrophilic additive having an HLB value of 10 to 20 in order to improve the dispersibility of the refined cellulose fiber in the resin. Patent Document 7 discloses a dispersion having a resin affinity segment and a cellulose affinity segment, and having a block copolymer structure or a gradient copolymer structure in order to improve the dispersibility of the microcrystalline cellulose in the resin. It is described that an agent is blended.

JP 2006-282923 A JP 2002-294080 A JP 2000-264975 A JP 2014-129518 A International Publication No. 2013/122171 International Publication No. 2012/111408 International Publication No. 2014/133019

  Patent Document 1 describes a dispersion of crystalline cellulose fine particles, which are dry-pulverized by an airflow method, in a resin. However, since crystalline cellulose having a large primary particle is used alone, it must be dispersed in a microfibril form. It is difficult.

  Patent Document 2 describes that a thermoplastic resin composition is obtained by stirring and mixing cellulose such as wood powder and other components. Patent Document 3 discloses various types of powdered cellulose and paper powder. It describes that an olefin composition is obtained by kneading additives. However, since the cellulose used in these is not hydrolyzed, the particles are coarse from the beginning, and cannot be dispersed in the form of microfibrils in the resin by ordinary mechanical processing.

  In the modified cellulose in which anhydrous rosin is ester-bonded to the surface of cellulose described in Patent Document 4, the hydrophobic group of the modified cellulose is dispersed on the outside (resin side) and the hydrophilic group is dispersed on the inside. There is a problem that the network formation of cellulose is insufficient and the mechanical properties of the resin are insufficient.

  The cellulose nanofibers disclosed in Patent Documents 5 and 6 have been defibrated using various pulps as raw materials without undergoing hydrolysis. In this treatment, the fiber width is certainly as thin as 4 to 200 nm, but since it does not undergo hydrolysis, the degree of polymerization of cellulose is high and the fiber length is very long. As a result, when dispersed in the resin, the entanglement between the cellulose nanofibers is too close, and in the continuous compound using a biaxial kneader or the like, the dispersion in the resin at the time of melting is insufficient. Even when the obtained resin composite is melt-injection-molded, there is a problem that fluidity is deteriorated and productivity is deteriorated.

  Further, Patent Document 5 discloses a method in which a resin is dried by solvent substitution or the like in a dispersion state and hot-pressed in order to add the resin to a resin once through an aqueous cellulose composition. In this method, since bubbles enter the resin when the solvent is dried, the formation of the interface between the cellulose and the resin is insufficient, and a satisfactory elongation at break in the tensile test cannot be obtained.

  Since the dispersant disclosed in Patent Document 7 is a copolymer having a large molecular weight of 1000 or more, there is a problem that the fluidity of the resin is lowered. In addition, due to its size, heating was required when uniformly mixed with cellulose, resulting in deterioration of the resin and oxidation of a small amount of hemicellulose, resulting in insufficient odor and color tone.

  In view of the above circumstances, the present invention is a resin composition that has good dispersibility in the resin, and is excellent in fluidity at the time of melting, excellent in elongation at the time of pulling, and excellent in dimensional stability. It aims at providing the cellulose formulation from which a thing is obtained.

  As a result of intensive studies to solve the above problems, the present inventors have obtained by combining in advance cellulose and an organic component having a specific surface tension and a boiling point higher than that of water. When the obtained cellulose preparation was added to the resin in a dry powder state and melt-mixed, it was found to be dispersed at the microfibril level, and they formed a network in the resin, and the present invention was made. That is, the present invention is as follows.

[1] A cellulose preparation comprising cellulose particles and an organic component covering at least a part of the surface of the cellulose particles, wherein the organic component has a static surface tension of 20 mN / m or more and a boiling point higher than water. A cellulosic preparation.
[2] The cellulose preparation according to aspect 1, wherein the dynamic surface tension of the organic component is 60 mN / m or less.
[3] The cellulose preparation according to the above aspect 1 or 2, wherein the solubility parameter (SP value) of the organic component is 7.25 or more.
[4] The cellulose preparation according to any one of the above aspects 1 to 3, wherein the 50% cumulative volume particle size measured by a laser diffraction particle size distribution meter is 10 μm or less.
[5] The cellulose preparation according to any one of the above aspects 1 to 4, wherein an average polymerization degree of cellulose constituting the cellulose particles is 1000 or less.
[6] The cellulose preparation according to any one of the above aspects 1 to 5, wherein the cellulose constituting the cellulose particles contains crystalline cellulose.
[7] The cellulose preparation according to the above aspect 6, wherein the crystalline cellulose has a length / diameter ratio (L / D ratio) of less than 30 and / or an average degree of polymerization of less than 500.
[8] The above-described aspects 1 to 7, wherein the cellulose preparation further comprises cellulose fibers, and the length / diameter ratio (L / D ratio) of the cellulose fibers is 30 or more and / or the average degree of polymerization is 300 or more. The cellulose formulation in any one.
[9] The cellulose preparation according to any one of the above aspects 1 to 8, wherein the ratio of crystalline cellulose to the total mass of cellulose present in the cellulose preparation is 50% by mass or more.
[10] The cellulose preparation according to any one of the above aspects 1 to 9, comprising 30 to 99% by mass of cellulose and 1 to 70% by mass of the organic component.
[11] The aspect according to any one of the above aspects 1 to 10, wherein the organic component is selected from the group consisting of rosin derivatives, alkylphenyl derivatives, bisphenol A derivatives, β-naphthyl derivatives, styrenated phenyl derivatives, and hardened castor oil derivatives. Cellulose preparation.
[12] The cellulose preparation according to any one of the above embodiments 1 to 11, wherein the organic component is a polyoxyethylene derivative.
[13] A resin composition comprising 1% by mass or more of the cellulose preparation according to any one of the above aspects 1 to 12.
[14] The resin composition according to the aspect 13, further including an interface forming agent in an amount of 100 parts by mass or more with respect to 100 parts by mass of the cellulose preparation.
[15] The resin composition according to the above aspect 13 or 14, further comprising a thermoplastic resin.
[16] A resin composition comprising a thermoplastic resin, cellulose particles, an organic component, and an interface forming agent,
The organic component has a static surface tension of 20 mN / m or more and a boiling point higher than water;
The resin composition whose quantity of the said interface formation agent is 1 mass part or more with respect to 100 mass parts of cellulose which exists in a resin composition.
[17] The resin composition according to the above aspect 16, wherein the dynamic surface tension of the organic component is 60 mN / m or less.
[18] The resin composition according to the above aspect 16 or 17, wherein a solubility parameter (SP value) of the organic component is 7.25 or more.
[19] The resin composition according to any one of the above aspects 16 to 18, wherein a 50% cumulative volume particle size of the cellulose particles, measured by a laser diffraction particle size distribution meter, is 10 μm or less.
[20] The resin composition according to any one of the above aspects 16 to 19, wherein an average degree of polymerization of cellulose constituting the cellulose particles is 1000 or less.
[21] The resin composition according to any one of the above embodiments 16 to 20, wherein the cellulose constituting the cellulose particles contains crystalline cellulose.
[22] The resin composition according to aspect 21, wherein the average L / D of the crystalline cellulose is less than 30 and / or the average degree of polymerization is less than 500.
[23] The resin according to any one of the above aspects 16 to 22, wherein the resin composition further includes cellulose fibers, and the average L / D of the cellulose fibers is 30 or more and / or the average degree of polymerization is 300 or more. Composition.
[24] The resin composition according to any one of the above aspects 16 to 23, wherein the ratio of crystalline cellulose to the total mass of cellulose present in the resin composition is 50% by mass or more.
[25] The amount of the cellulose is 30 to 99% by mass and the amount of the organic component is 1 to 70% by mass with respect to the total of 100% by mass of the total amount of cellulose and the amount of the organic component in the resin composition. %, The resin composition according to any one of the above aspects 16 to 24.
[26] The aspect according to any one of the above aspects 16 to 25, wherein the organic component is selected from the group consisting of a rosin derivative, an alkylphenyl derivative, a bisphenol A derivative, a β-naphthyl derivative, a styrenated phenyl derivative, and a hardened castor oil derivative. Resin composition.

  The cellulose preparation according to the present invention has good dispersibility in the resin, and the resin composition obtained by dispersing the cellulose preparation in the resin has excellent flow characteristics at the time of melting and injection moldability. It is good. In addition, the resin composition has a low coefficient of linear expansion, and has an effect that strength and elongation are excellent at the time of pulling and bending deformation.

  Hereinafter, the present invention will be described in detail together with specific embodiments. The following embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist.

[Cellulose preparation]
The cellulose preparation according to the present invention includes cellulose particles and an organic component that covers at least a part of the surface of the cellulose particles. That is, the cellulose preparation includes cellulose particles in which at least a part of the surface is coated with an organic component. In one embodiment, the organic component has a static surface tension of 20 mN / m or more. In one embodiment, the organic component has a boiling point higher than that of water. The cellulose preparation according to the present invention is dispersed in a resin because at least a part of the surface of the contained cellulose particles (hereinafter sometimes referred to as “cellulose particles of the present invention”) is coated with a specific organic component. The resin composition in which the cellulose preparation is dispersed has characteristics that it has excellent fluidity at the time of melting and good elongation at the time of pulling.

  In a preferred embodiment, the organic component coats the particles by binding to at least part of the surface of the cellulose particles. The bond between the cellulose particle surface and the organic component is due to non-covalent bonds such as hydrogen bonds and intermolecular forces. In the following, the treatment for binding at least a part of the surface of the cellulose particle and the organic component may be referred to as “compositing treatment with organic component (compositing step)”.

<Cellulose raw material>
The cellulose raw material for preparing the cellulose particles of the present invention is preferably a natural cellulosic material (a natural material-derived fibrous material containing cellulose). The natural cellulosic material may be plant or animal and may be derived from microorganisms. Examples of natural cellulosic materials include fiber materials derived from natural products containing cellulose such as wood, bamboo, wheat straw, rice straw, cotton, ramie, squirts, bagasse, kenaf, beet, and bacterial cellulose. Examples of commonly available natural cellulosic materials include natural cellulosic materials (powdered cellulose) that are in powder form, such as cellulose floc and crystalline cellulose. As the cellulose raw material of the cellulose particles of the present invention, one kind of natural cellulosic substance may be used, or two or more kinds of natural cellulosic substances may be used in combination. The cellulose raw material is preferably used in the form of a refined pulp, but the method for purifying the pulp is not particularly limited, and any pulp such as dissolved pulp, kraft pulp, NBKP, LBKP, or fluff pulp may be used. Good.

<Average degree of polymerization of cellulose>
The average degree of polymerization of cellulose can be measured according to the reduced specific viscosity method using a copper ethylenediamine solution described in the confirmation test (3) of “15th revised Japanese Pharmacopoeia Manual (published by Yodogawa Shoten)”.

  The average degree of polymerization of cellulose constituting the cellulose particles of the present invention is preferably 1000 or less. If the average degree of polymerization is 1000 or less, in the step of compounding with the organic component, the cellulose is easily subjected to physical treatment such as stirring, pulverization, and grinding, and the compounding is easily promoted. As a result, the dispersibility in the resin increases. The average degree of polymerization of cellulose is more preferably 750 or less, further preferably 500 or less, still more preferably 350 or less, particularly preferably 300 or less, extremely preferably 250 or less, and most preferably 200 or less. The lower the average degree of polymerization of cellulose, the easier the control of complexing. Therefore, the lower limit is not particularly limited, but a preferred range is 10 or more.

<Hydrolysis of cellulose>
Examples of a method for controlling the average degree of polymerization of cellulose include hydrolysis treatment. By the hydrolysis treatment, the depolymerization of the amorphous cellulose inside the cellulose fiber proceeds, and the average degree of polymerization decreases. At the same time, the hydrolysis process removes impurities such as hemicellulose and lignin in addition to the above-described amorphous cellulose, so that the inside of the fiber becomes porous. Thereby, in the process of giving mechanical shearing force to cellulose and organic components such as in the kneading process described later, the cellulose is easily subjected to mechanical treatment, and the cellulose is easily refined. As a result, the surface area of cellulose becomes high, and the control of complexing with organic components becomes easy.

  The method for hydrolysis is not particularly limited, and examples thereof include acid hydrolysis, alkaline oxidation decomposition, hydrothermal decomposition, steam explosion, and microwave decomposition. These methods may be used alone or in combination of two or more. In the acid hydrolysis method, for example, α-cellulose obtained as a pulp from a fibrous plant is used as a cellulose raw material, and this is dispersed in an aqueous medium, and an appropriate amount of proton acid, carboxylic acid, Lewis acid, heteropoly acid, etc. In addition, the average degree of polymerization can be easily controlled by heating while stirring. The reaction conditions such as temperature, pressure, and time at this time vary depending on the cellulose species, cellulose concentration, acid species, and acid concentration, but are appropriately adjusted to achieve the desired average degree of polymerization. For example, the conditions of using 2 mass% or less mineral acid aqueous solution and processing a cellulose for 10 minutes or more under 100 degreeC or more and pressurization are mentioned. Under these conditions, a catalyst component such as an acid penetrates into the inside of the cellulose fiber, the hydrolysis is accelerated, the amount of the catalyst component to be used is reduced, and subsequent purification is facilitated. In addition, the dispersion liquid of the cellulose raw material at the time of hydrolysis may contain a small amount of an organic solvent in a range not impairing the effects of the present invention, in addition to water.

<Crystal form and crystallinity of cellulose>
The cellulose constituting the cellulose particles of the present invention preferably contains crystalline cellulose, more preferably crystalline cellulose. The crystallinity of the crystalline cellulose is preferably 10% or more. When the degree of crystallinity is 10% or more, the mechanical properties (strength and dimensional stability) of the cellulose particles themselves are increased. Therefore, when dispersed in a resin, the strength and dimensional stability of the resin composition tend to increase. . The crystallinity of the cellulose constituting the cellulose particles of the present invention is more preferably 30% or more, further preferably 50% or more, and still more preferably 70% or more. The upper limit of the crystallinity is not particularly limited, but is preferably 90% or less.

The degree of crystallinity is obtained by the following equation from the diffraction pattern (2θ / deg. Is 10 to 30) when cellulose is measured by wide-angle X-ray diffraction by the Segal method.
Crystallinity (%) = ([Diffraction intensity due to (200) plane of 2θ / deg. = 22.5] − [Diffraction intensity due to amorphous of 2θ / deg. = 18]) / [2θ / Deg. = Diffraction intensity due to (200) plane of 22.5] × 100

  As the crystal form of cellulose, type I, type II, type III, type IV, and the like are known. Among them, type I and type II are widely used, and type III and type IV are obtained on a laboratory scale. However, it is not widely used on an industrial scale. As the cellulose constituting the cellulose particles of the present invention, the structural mobility is relatively high, and by dispersing the cellulose particles in the resin, the linear expansion coefficient is lower, and the strength and elongation at the time of tensile and bending deformation are reduced. Since a more excellent resin composite can be obtained, it is preferably crystalline cellulose containing cellulose type I crystals, more preferably crystalline cellulose containing cellulose type I crystals and a crystallinity of 10% or more. preferable.

<Cellulose shape (length (L), diameter (D), and L / D ratio)>
In the present disclosure, the length, diameter, and L / D ratio of cellulose (specifically, cellulose particles and cellulose fibers) are pure cellulose (preferably wet cake after hydrolysis) at a concentration of 1% by mass. A water dispersion obtained by dispersing in an aqueous suspension and dispersing with a high shear homogenizer (for example, trade name “Excel Auto Homogenizer ED-7” manufactured by Nippon Seiki Co., Ltd.) at a rotational speed of 15,000 rpm × 5 minutes. , Diluted with pure water to 0.1-0.5% by mass, cast on mica and air-dried as a measurement sample, measured with a high-resolution scanning microscope (SEM) or atomic force microscope (AFM) Ask. Specifically, the length of the randomly selected cellulose image (specifically, cellulose) in an observation field whose magnification is adjusted so that at least 100, for example, 100 to 150 cellulose is observed. The long diameter of the particle or the fiber length of the cellulose fiber when present (L), the diameter (specifically, the short diameter of the cellulose particle or the fiber diameter of the cellulose fiber when present) (D), and a ratio thereof ( L / D). For example, when the cellulose particles are crystalline cellulose having a ratio (L / D) of less than 30, and the crystalline cellulose and cellulose fiber coexist in the measurement sample, those having a ratio (L / D) of less than 30 are crystallized. Cellulose, 30 or more can be classified as cellulose fiber. The number average value of the length (L), the number average value of the diameter (D), and the number average value of the ratio (L / D) are calculated as at least 100, for example, 100 to 150 number average values.
Or the length of a cellulose in a composition, a diameter, and L / D ratio can be confirmed by measuring with the above-mentioned measuring method by making the composition which is a solid into a measurement sample.
Or, the length, diameter, and L / D ratio of cellulose in the composition are obtained by dissolving the resin component in the composition in an organic or inorganic solvent capable of dissolving the resin component of the composition, separating the cellulose, After sufficiently washing with a solvent, an aqueous dispersion in which the solvent was replaced with pure water was prepared, and the cellulose concentration was diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried. It can be confirmed by measuring a sample as a measurement sample by the measurement method described above.

  When confirming the length, diameter, and L / D ratio of the cellulose particles in the cellulose preparation, the cellulose preparation is dispersed in water or an organic solvent (the dispersion method is a high shear with a concentration of 1% by weight of the cellulose preparation). After being treated with a homogenizer (for example, trade name “Excel Auto Homogenizer ED-7” manufactured by Nippon Seiki Co., Ltd.), the measurement is performed by AFM according to the method described above.

  The length (L) of the cellulose particles of the present invention is preferably 200 nm or more, more preferably 500 nm or more, and still more preferably 1000 nm or more, from the viewpoint of giving a resin composite having a low linear expansion coefficient. In addition, from the viewpoint of fluidity and injection moldability when the resin composition is melted, it is preferably 10,000 nm or less, more preferably 5000 nm or less, and still more preferably 3000 nm or less.

  The diameter (D) of the cellulose particles of the present invention is preferably 20 nm or more, more preferably 30 nm or more from the viewpoint of giving a resin composite having a low coefficient of linear expansion, and the dispersibility in the resin, as well as when the resin composition is melted From the viewpoints of fluidity and injection moldability, it is preferably 500 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less, still more preferably 350 nm or less, and most preferably 300 nm or less.

  The L / D of the cellulose particles of the present invention is preferably less than 30 and more preferably 20 or less from the viewpoints of dispersibility in the resin, fluidity when the resin composition is melted, and injection moldability. It is preferably 15 or less, more preferably 10 or less, even more preferably 5 or less, particularly preferably less than 5, and most preferably 4 or less. L / D may be 1 or more, but preferably 2 or more from the viewpoint of balancing the low linear expansion coefficient and good fluidity and injection moldability during melting while ensuring dispersibility in the resin. More preferably, it is 3 or more.

<Content of colloidal cellulose particles>
The cellulose preparation according to the present invention preferably contains colloidal cellulose particles as cellulose particles. The higher the ratio of colloidal cellulose particles occupying the whole cellulose particles, the more the dispersion progresses when the cellulose preparation using the cellulose particles is dispersed in the resin, so that a network with a high surface area can be formed. Dimensional stability tends to improve. The content of colloidal cellulose particles with respect to 100% by mass of cellulose particles is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and 80% by mass. The above is particularly preferable. The upper limit of the content of colloidal cellulose particles is not particularly limited, and the theoretical upper limit is 100% by mass.

The content of colloidal cellulose particles can be measured by the following method. In a planetary mixer (for example, manufactured by Shinagawa Kogyo Co., Ltd., 5DM-03-R, the stirring blade is a hook type), the cellulose is kneaded at 126 rpm at room temperature and normal pressure for 30 minutes, Using a high shear homogenizer (for example, trade name “Excel Auto Homogenizer ED-7” manufactured by Nippon Seiki Co., Ltd.) with a solid content of 0.5% by mass, treatment conditions: rotational speed Disperse at 15,000 rpm for 5 minutes, and use a centrifuge (for example, Kubota Corporation, trade name “6800 type centrifuge” rotor type RA-400 type), treatment condition: centrifugal force 39200 m ² / s in the centrifuged supernatant was collected for 10 minutes, further, the absolute dry this supernatant was centrifuged for 45 min at 116000m ² / s, the solids remaining in the supernatant after centrifugation In is measured to calculate the mass percentage.

<Volume average particle diameter of cellulose>
In the present disclosure, the volume average particle diameter of cellulose is measured by a laser diffraction particle size distribution meter. Further, according to the present disclosure, “integrated 50% particle diameter in volume frequency particle size distribution obtained by laser diffraction particle size distribution meter (spherical equivalent diameter of particle when integrated volume is 50% with respect to volume of whole particle)” "May be referred to as" volume average particle diameter "or" cumulative volume 50% particle diameter ".

The volume average particle diameter of cellulose can be measured by the following method. In a planetary mixer (for example, manufactured by Shinagawa Kogyo Co., Ltd., 5DM-03-R, the stirring blade is a hook type), the cellulose is kneaded at 126 rpm at room temperature and normal pressure for 30 minutes, Using a high shear homogenizer (for example, trade name “Excel Auto Homogenizer ED-7”, manufactured by Nippon Seiki Co., Ltd.) at a concentration of 0.5% by mass, a rotational speed of 15,000 rpm × 5 Disperse in minutes and centrifuge for 10 minutes at a processing condition: centrifugal force of 39200 m ² / s using a centrifuge (for example, Kubota Corporation, trade name “6800 type centrifuge”, rotor type RA-400 type). The supernatant obtained is collected, and the supernatant is further centrifuged at 116000 m ² / s for 45 minutes, and the supernatant after centrifugation is collected. Using this supernatant, a laser diffraction / scattering particle size distribution meter (for example, HORIBA, Ltd., trade name “LA-910” or trade name “LA-950”, ultrasonic treatment for 1 minute, refractive index of 1. 20) The integrated 50% particle diameter (volume average particle diameter) in the volume frequency particle size distribution obtained in 20) is measured.

  The cellulose particles of the present invention are more preferable as the particle diameter is smaller. As the particle size is smaller, when the cellulose preparation containing the cellulose particles is dispersed in the resin, the dispersion proceeds and a network with a high surface area can be formed, so that the strength and dimensional stability of the obtained resin composite are improved. There is a tendency. The volume average particle diameter of the cellulose particles of the present invention is preferably 10 μm or less, more preferably 8.0 μm, further preferably 5.0 μm or less, and more preferably 3.0 μm or less. More preferably, it is particularly preferably 1.0 μm or less, particularly preferably 0.7 μm or less, extremely preferably 0.5 μm or less, and most preferably 0.3 μm or less. The lower limit of the particle diameter is not particularly limited, but may actually be 0.05 μm or more.

<Zeta potential>
The zeta potential of cellulose constituting the cellulose particles of the present invention is preferably −40 mV or less. When the zeta potential is in this range, when the cellulose particles and the resin are compounded, it is possible to maintain good melt fluidity without causing excessive bonding between the cellulose particles and the resin. The zeta potential is more preferably −30 mV or less, further preferably −25 mV or less, particularly preferably −20 mV or less, and most preferably −15 mV or less. The lower the value, the better the physical properties of the compound, so the lower limit is not particularly limited, but -5 mV or more is preferred.

  The zeta potential here can be measured by the following method. Cellulose is made into a pure water suspension with a concentration of 1% by mass, and using a high shear homogenizer (for example, trade name “Excel Auto Homogenizer ED-7” manufactured by Nippon Seiki Co., Ltd.), treatment conditions: 15,000 rpm × A water dispersion obtained by dispersing in 5 minutes is diluted with pure water to 0.1 to 0.5% by mass, and a zeta electrometer (for example, Otsuka Electronics, apparatus name ELSZ-2000ZS type, standard cell unit) is used. Use and measure at 25 ° C.

<Crystalline cellulose>
The cellulose particles of the present invention preferably contain the aforementioned crystalline cellulose, and more preferably the aforementioned crystalline cellulose. Crystalline cellulose can be obtained through the above hydrolysis using the above cellulose as a raw material. In one embodiment, the crystalline cellulose has an average degree of polymerization of less than 500 and / or an average L / D of less than 30. By using crystalline cellulose, the combination of cellulose particles and organic components is promoted. When a cellulose preparation is blended with a resin to prepare a resin composition, the dispersibility of the cellulose is improved. Further, the resin composition Can have excellent flow properties and injection moldability when melted. As a result, a resin composition in which the cellulose preparation is dispersed in a resin has a low coefficient of linear expansion, and can exhibit the effect of excellent elongation during tensile and bending deformation.

  The average degree of polymerization of the crystalline cellulose is preferably less than 500, more preferably 400 or less, further preferably 250 or less, particularly preferably 230 or less, particularly preferably 200 or less, and most preferably 180 or less. The smaller the degree of polymerization, the greater the above-described effect of crystalline cellulose. Therefore, the lower limit is not particularly set, but it may be 50 or more in practice.

  The average L / D of crystalline cellulose is preferably less than 30, more preferably 20 or less, further preferably 15 or less, and particularly preferably 10 or less. The smaller the L / D, the greater the above-mentioned effect. Therefore, the lower limit is not particularly set, but in reality, it may be 2 or more.

<Cellulose fiber>
The cellulose preparation preferably further contains cellulose fibers. Cellulose fiber is treated by crushing methods such as high-pressure homogenizer, microfluidizer, ball mill and disk mill after treating cellulose raw materials such as pulp with hot water at 100 ° C or higher to hydrolyze the hemicellulose part. It refers to fine cellulose. In one embodiment, the cellulose fiber has an average degree of polymerization of 300 or more. In one embodiment, the cellulose fiber has an average L / D controlled within a range of 30 or more. By using the cellulose fiber, when the cellulose preparation is blended with the resin, the resin composition can further maintain good dispersibility of the cellulose, and the resin composition can have good flow characteristics and injection moldability when melted. . As a result, the resin composition in which the cellulose preparation is dispersed in the resin has a lower linear expansion coefficient, and can exhibit an effect that the strength is further improved during tensile and bending deformation.

  The average polymerization degree of the cellulose fiber is more preferably 350 or more, further preferably 400 or more, particularly preferably 500 or more, and particularly preferably 700 or more. From the viewpoint of complexing with an organic component, the average degree of polymerization is preferably 1500 or less, and more preferably 1000 or less.

  The fiber length (L) of the cellulose fiber is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 50 μm or more from the viewpoint of providing a resin composite having a low linear expansion coefficient. From the viewpoint of fluidity at the time of melting of the product and injection moldability, it is preferably 1000 μm or less, more preferably 500 μm or less, and still more preferably 100 μm or less.

  The fiber diameter (D) of the cellulose fiber is preferably a nanometer size (that is, less than 1 μm), and the fiber diameter is more preferably 500 nm or less. The fiber diameter of the cellulose fiber is preferably 450 nm or less, more preferably 400 nm or less, further preferably 350 nm or less, further preferably 300 nm or less, further preferably 200 nm or less, and further preferably 100 nm. Or less, more preferably 50 nm or less, and most preferably 30 nm or less. The fiber diameter of the cellulose fiber is preferably 1 nm or more, more preferably 2 nm or more.

  From the viewpoint of effectively expressing the mechanical properties of the resin composite, it is desirable that the fiber diameter of the cellulose fiber be within the above range.

  Moreover, the L / D lower limit of the cellulose fiber is preferably 50, more preferably 80, more preferably 100, still more preferably 120, and most preferably 150. The upper limit is not particularly limited, but is preferably 1000 or less from the viewpoint of handleability.

<Combination of crystalline cellulose and cellulose fiber>
The cellulose preparation of the present invention preferably contains cellulose particles (preferably, the above-described crystalline cellulose having an L / D of less than 30) and cellulose fibers having an L / D of 30 or more. In the case of a combination of cellulose particles (preferably crystalline cellulose having an L / D of less than 30) and cellulose fibers having an L / D of 30 or more, the cellulose particles and the organic component are favorably combined. This improves the dispersibility of the cellulose preparation in the resin when the cellulose preparation is mixed with the resin to produce a resin composition, and the resin composition has excellent flow characteristics and injection moldability when melted. Have. Therefore, the resin composition in which the cellulose preparation is dispersed in the resin has a low linear expansion coefficient, and can exhibit an effect of excellent elongation and strength at the time of pulling and bending deformation. In addition, by optimizing the blending ratio of the above cellulose particles (preferably crystalline cellulose) and cellulose fibers, the above effects in the resin composition can be expressed well even when the cellulose particles are added in a low amount. As a result, the resin composite Can be reduced in weight.

  The ratio of crystalline cellulose to the total mass of cellulose present in the cellulose preparation is preferably 50% by mass or more. The ratio is more preferably more than 50% by mass, still more preferably 60% by mass or more, still more preferably 70% by mass or more, and most preferably 80% by mass or more. The upper limit of the ratio is preferably 98% by mass, more preferably 96% by mass, and most preferably 95% by mass.

<Binding ratio between cellulose and organic components>
In the cellulose preparation according to the present invention, the organic component is preferably bonded to the surface of the cellulose particle with a weak force. The weak force is, for example, a non-covalent bond (hydrogen bond, coordination bond, ionic bond, intermolecular force, etc.), physical adsorption, electrostatic attractive force, or the like. When the organic component and cellulose are not covalently bonded but bonded with a weak force, the cellulose component is released and released from the resin in the process of mixing and dispersing the cellulose preparation in the molten resin, and cellulose. The original surface is exposed. When the exposed cellulose particle surfaces interact with each other, the cellulose network tends to become stronger. The stronger the cellulose network, the better the mechanical properties of the resin composition and the better the mechanical strength.

The degree of covalent bond between cellulose and the organic component is represented by the following bond rate.
The cellulose preparation powder is pulverized through a 250 μm sieve, and 1 g of it is collected. This sample is placed in 10 mL of an organic solvent (for example, ethanol) or water (a medium capable of dissolving organic components), and stirred at room temperature for 60 minutes under stirring with a stirrer. The organic solvent or water is filtered through a PTFE membrane filter having an opening of 0.4 μm, and the organic solvent or water is evaporated from the filtrate. The mass of the residue collected from the filtrate is obtained, and the binding rate is calculated from the following equation. Here, the amount of the organic component in the cellulose preparation may be a theoretical value obtained from the blending amount at the time of production, or may be obtained from chemical analysis such as NMR, IR, X-ray diffraction.
Binding rate (%) = [1-([Mass of residue (g)] / [Amount of organic component in cellulose preparation (g)]
])] × 100

  In the cellulose preparation according to the present invention, the binding rate is preferably 90% or less, more preferably 50% or less, further preferably 20% or less, and even more preferably 10% or less. Preferably, it is particularly preferably 5% or less. The lower the binding rate, the higher the dispersibility of the cellulose preparation in the resin and the mechanical properties after dispersion. Therefore, the lower limit is not particularly limited, but theoretically it is 0% or more.

<Organic component>
In the present disclosure, the “organic component” typically has a functional group composed of carbon, skeleton, hydrogen, oxygen, carbon, nitrogen, chlorine, sulfur, phosphorus and the like. As long as it has the above-described structure in the molecule, those in which the inorganic compound and the functional group are chemically bonded are also included in the organic component in the present invention.

<Boiling point of organic components>
The organic component covering the surface of the cellulose particle of the present invention (hereinafter sometimes referred to as “organic component of the present invention”) has a boiling point higher than that of water. In addition, the boiling point higher than water refers to a boiling point higher than the boiling point at each pressure in the water vapor pressure curve (for example, 100 ° C. under 1 atm). Since the boiling point of the organic component of the present invention is higher than that of water, when the cellulose preparation according to the present invention is mixed with the molten resin, the water contained in the cellulose preparation evaporates, and the water and the organic component are Since it is substituted, the dispersion of cellulose in the resin is promoted.

  The organic component of the present invention is preferably liquid at room temperature (25 ° C.). Organic components that are liquid at room temperature are easily compounded with cellulose, and are easily mixed uniformly with the resin. Moreover, it is easy to prevent organic components from aggregating and recrystallizing in the resin composition.

<Static surface tension of organic components>
The static surface tension of the organic component of the present invention is 20 mN / m or more. This static surface tension is a surface tension measured by the Wilhelmy method described later. When using a liquid organic component at room temperature, it is measured at 25 ° C., but when using a solid or semi-solid organic component at room temperature, the organic component is heated above its melting point and melted. Use the value measured and temperature corrected to 25 ° C. The organic component of the present invention can be used in any state as long as the static surface tension is satisfied when the cellulose preparation is used. For example, the organic component of the present invention may be a single organic component or a mixture of two or more organic components, and is used in the form of an organic component dissolved in an organic solvent or water. May be.

  When the static surface tension is in a specific range, the hydrophilic component of the organic component of the present invention can uniformly cover the surface by hydrogen bonding with the hydroxyl group on the cellulose surface. Moreover, since the hydrophobic group is exposed at the time of drying on the surface of the uniformly covered cellulose primary particles, the cellulose is easily dispersed in the resin at the time of preparing the resin composition. If the static surface tension of the organic component is too low, the hydrophobicity of the organic component is too strong, resulting in insufficient coating of the cellulose surface and insufficient dispersibility of the cellulose. On the other hand, if the static surface tension of the organic component is too high, the coating on the cellulose surface is sufficient, but the affinity between the cellulose and the resin is impaired, and as a result, the dispersibility of the cellulose decreases.

  When producing a resin composition by kneading cellulose particles and a resin to balance the affinity to the cellulose interface and the resin, good dispersibility, resin composition fluidity, strength and In order to express the improvement in elongation, it is preferable to control the static surface tension of the organic component of the present invention within a specific range. The static surface tension of the organic component of the present invention is preferably 23 mN / m or more, more preferably 25 mN / m or more, further preferably 30 mN / m or more, still more preferably 35 mN / m or more, and particularly preferably 39 mN / m or more. preferable. The static surface tension of the organic component of the present invention is preferably less than 72.8 mN / m, more preferably 60 mN / m or less, further preferably 50 mN / m or less, and even more preferably 45 mN / m or less.

  The static surface tension is measured by the Wilhelmy method using an automatic surface tension measuring device (for example, Kyowa Interface Science Co., Ltd., trade name “CBVP-Z type”, using the attached glass cell). Specifically, when the organic component is liquid at room temperature, the sample was prepared in an attached stainless steel petri dish so that the height from the bottom to the liquid surface was 7 mm to 9 mm, and the temperature was adjusted to 25 ° C. ± 1 ° C. It will be measured later and the static surface tension is obtained by the following formula. γ = (P−mg + shρg) / Lcosθ. Here, γ: Static surface tension, P: Balance force, m: Plate mass, g: Gravitational constant, L: Plate circumference, θ: Plate-liquid contact angle, s: Plate cross-sectional area, h: ( Depth of sinking from the liquid surface, ρ: density of the liquid. Note that the static surface tension measured at a temperature of the melting point + 5 ° C. is employed for convenience because the static surface tension of a solid at normal temperature cannot be measured by the above-described method. When the melting point is an unknown substance, the melting point is first measured by visual melting point measurement method (JIS K6220), heated to a temperature higher than the melting point, adjusted to a temperature of the melting point + 5 ° C., and the Wilhelmy method described above. The static surface tension will be measured.

<Dynamic surface tension of organic components>
The dynamic surface tension of the organic component of the present invention is preferably 60 mN / m or less. This dynamic surface tension is calculated using the maximum bubble pressure method (measures the maximum pressure (maximum bubble pressure) when air is passed through a thin tube (hereinafter referred to as a probe) inserted in the liquid and bubbles are generated, and the surface tension is calculated. This is the surface tension measured by the method. The dynamic surface tension of the present invention refers to a 5% by mass organic component dissolved or dispersed in ion-exchanged water to prepare a measurement solution, adjusted to a temperature of 25 ° C., and then subjected to a dynamic surface tension meter (eg, Hidehiro Seiki Co., Ltd.). Product name Theta Science t-60 type, probe (capillary TYPE I (peak resin), single mode) is used, and the value of the surface tension measured with a bubble generation period of 10 Hz. The tension is obtained by the following equation: σ = ΔP · r / 2, where σ: dynamic surface tension, ΔP: pressure difference (maximum pressure−minimum pressure), and r: capillary radius.

  The dynamic surface tension measured by the maximum bubble pressure method means the dynamic surface tension of the organic component in a fast moving field. Organic components usually form micelles in water. A low dynamic surface tension indicates that the diffusion rate of molecules of organic components from the micelle state is high, and a high dynamic surface tension means that the diffusion rate of molecules is low. When the cellulose preparation or resin composition according to the present invention is obtained, micelles are formed when water evaporates from the cellulose surface due to the small dynamic surface tension (that is, the diffusion rate of molecules is large). The organic component molecules are diffused on the cellulose surface, and the cellulose surface can be uniformly coated. Thereby, when a cellulose particle carries out secondary aggregation, the cellulose particle surface is hydrophobized moderately, The excessive hydrogen bond of cellulose particles and aggregation by it are inhibited. As a result, when the cellulose and the resin are compounded, the resin well enters the gap between the cellulose (particularly the gap between the cellulose particles), and the dispersibility of the cellulose is improved.

  On the other hand, when the dynamic surface tension is large, the diffusion rate of molecules is slower than the evaporation rate of water, and part of the organic component adheres to the cellulose surface in a lump (not diffusing). It attracts and aggregates. As a result, the dispersibility of cellulose at the time of compounding with the resin is deteriorated.

  The dynamic surface tension of the organic component of the present invention is more preferably 55 mN / m or less, more preferably 50 mN / m or less, further preferably 45 mN / m or less, and particularly preferably 40 mN / m or less. The dynamic surface tension of the organic component of the present invention is preferably 10 mN / m or more, more preferably 15 mN / m or more, further preferably 20 mN / m or more, particularly preferably 30 mN / m or more, and most preferably 35 mN / m or more. preferable.

<Solubility parameter of organic component (SP value)>
The organic component of the present invention preferably has a solubility parameter (SP value) of 7.25 or more. When the organic component has an SP value in this range, in addition to promoting the composite of cellulose and the organic component, the dispersion of cellulose in the resin is promoted.

According to the document of Fadders (R. F. Feders: Polymer Engineering & Science, vol. 12 (10), p. 2359-2370 (1974)), the SP value is determined as follows. It is thought that it depends on the type and number of substituents, and according to Ueda et al. (Paint Research, No. 152, Oct. 2010), SP values for existing main solvents shown in Examples described later. (Cal / cm ³ ) ^1/2 is published.

  The SP value of the organic component of the present invention can be experimentally determined from the boundary between solubility and insolubility when the organic component is dissolved in various solvents having known SP values. For example, when 1 mL of an organic component is dissolved at room temperature under stirring with a stirrer for 1 hour in various solvents (10 mL) having different SP values in the tables shown in the examples, it is determined whether or not the total amount is dissolved. For example, when the organic component is soluble in diethyl ether, the SP value of the organic component is 7.25 or more.

<Types of organic components>
It does not specifically limit as an organic component of this invention, For example, fats and oils, a fatty acid, surfactant, etc. can be used.

  Examples of the fat include esters of fatty acids and glycerin. Oils and fats usually take the form of triglycerides (tri-O-acylglycerin). Oils and fats are classified into dry oils, semi-dry oils and non-dry oils in the order in which they are easily oxidized and solidified by fatty oils, and those used in various applications such as edible and industrial can be used. These are used singly or in combination of two or more.

  Examples of animal and vegetable oils include terpin oil, tall oil, rosin, white squeezed oil, corn oil, soybean oil, sesame oil, rapeseed oil (canola oil), rice bran oil, coconut oil, coconut oil, safflower oil (safflower oil), coconut oil (Palm kernel oil), cottonseed oil, sunflower oil, sesame oil (pepper oil), flaxseed oil, olive oil, peanut oil, almond oil, avocado oil, hazelnut oil, walnut oil, grape seed oil, mustard oil, lettuce oil, Fish oil, whale oil, salmon oil, liver oil, cacao butter, peanut butter, palm oil, lard (pig fat), het (beef tallow), chicken oil, sebum, sheep fat, horse fat, smaltz, milk fat (butter, ghee, etc.) , Hardened oil (margarine, shortening, etc.), castor oil (vegetable oil) and the like. Examples of mineral oil include liquid paraffin, silicone oil, calcium soap base grease, calcium composite soap base grease, sodium soap base grease, aluminum soap base grease, lithium soap base grease, non-soap base grease, silicon grease, etc. Greases; naphthenic and paraffinic mineral oils; partially synthetic oils obtained by mixing PAO and esters (or hydrocracked oils) with mineral oils and highly hydrocracked oils; chemically synthesized oils such as PAO (polyalphaolefin) -Total synthetic oil, synthetic oil, etc. are mentioned.

  Fatty acid refers to a compound represented by the general formula CnHmCOOH (n and m are integers), and those used for various purposes such as food and industrial use can be used. For example, the following are used alone or in combination of two or more.

  Examples of saturated fatty acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid Acid, margaric acid, stearic acid, nonadecyl acid, arachidic acid, heicosyl acid, behenic acid, tricosyl acid, lignoceric acid, etc., and examples of unsaturated fatty acids include α-linolenic acid, stearidonic acid, eicosapentaenoic acid, Ω-3 fatty acids such as docosapentaenoic acid, docosahexaenoic acid; ω-6 fatty acids such as linoleic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, docosapentaenoic acid; palmitoleic acid, vaccenic acid, paulin Ω-7 fatty acids such as acids; oleic acid, elaidic acid, Elca Ω-9 fatty acids such as acid and nervonic acid.

  Examples of the surfactant include compounds having a chemical structure in which a hydrophilic substituent and a hydrophobic substituent are covalently bonded, and those used for various applications such as food and industrial use can be used. For example, the following are used alone or in combination of two or more.

  As the surfactant, any of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used, but in terms of affinity with cellulose. Anionic surfactants and nonionic surfactants are preferred, and nonionic surfactants are more preferred.

  Examples of the anionic surfactant include fatty acid sodium (fatty acid) such as fatty acid sodium, fatty acid potassium, and sodium alphasulfo fatty acid ester, and linear alkylbenzene series such as sodium linear alkylbenzene sulfonate. Examples of alcohol-based (anionic) systems include sodium alkyl sulfates and sodium alkyl ether sulfates. Examples of alpha olefins include sodium alpha olefin sulfonates. Examples of normal paraffins include sodium alkyl sulfonates. It is also possible to use 1 type or in mixture of 2 or more types.

  Examples of nonionic surfactants include fatty acids (nonionic), glycolipids such as sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkanolamides, and the like. Examples of the ion) include polyoxyethylene alkyl ethers and the like, and examples of the alkylphenol type include polyoxyethylene alkyl phenyl ethers. These may be used alone or in combination.

  Examples of the zwitterionic surfactant include alkylamino fatty acid sodium and the like as the amino acid type, alkyl betaine and the like as the betaine type, alkylamine oxide and the like as the amine oxide type, and one or two of them. It is also possible to mix and use seeds or more.

  Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts and dialkyldimethylammonium salts, which can be used alone or in combination of two or more. .

As the surfactant used as the organic component of the present invention, the following can be suitably used in addition to the above. For example, acyl amino acid salts such as acyl glutamate, higher alkyl sulfates such as sodium laurate, sodium palmitate, sodium lauryl sulfate, potassium lauryl sulfate, polyoxyethylene lauryl sulfate triethanolamine, polyoxyethylene sodium lauryl sulfate, etc. Anionic surfactants such as N-acyl sarcosine salts such as sodium alkyl ether sulfate, lauroyl sarcosine sodium; alkyl trimethyl ammonium salts such as stearyl trimethyl ammonium chloride and lauryl trimethyl ammonium chloride; distearyl dimethyl ammonium chloride dialkyl dimethyl ammonium chloride Alkylpyridinium such as salt, chloride (N, N'-dimethyl-3,5-methylenepiperidinium), cetylpitidinium chloride Cationic surfactants such as salts, alkyl quaternary ammonium salts, alkylamine salts such as polyoxyethylene alkylamine, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives; 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) ) Imidazoline-based amphoteric surfactants such as 2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazo betaine, lauryl dimethyl aminoacetic acid betaine, alkyl betaine, amide betaine, betaine such as sulfo betaine amphoteric surfactants such as amphoteric surfactants, sorbitan mono-oleate, Sorubitanmo Neu Sosuteareto, Sorubitanmo Sorbitan fatty acid esters such as laurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, monostearic acid Glycerin, α, α'-oleic acid pyroglutamate glycerin, glycerin polyglycerin fatty acid such as glyceryl monostearate malic acid, propylene glycol fatty acid esters such as propylene glycol monostearate, hydrogenated castor oil derivative, glycerin alkyl ether, poly Oxyethylene-sorbitan monostearate, polyoxyethylene-sorbitan monooleate, polyoxyethylene-sorbitan tetraoleate Polyoxyethylene-sorbitan fatty acid esters, polyoxyethylene-sorbitol monolaurate, polyoxyethylene-sorbitol monooleate, polyoxyethylene-sorbitol pentaoleate, polyoxyethylene-sorbitol monostearate, polyoxy Polyoxyethylene-glycerin fatty acid esters such as ethylene-glycerin monoisostearate, polyoxyethylene-glycerin triisostearate, polyoxyethylene monooleate, polyoxyethylene distearate, polyoxyethylene monodiolate, Polyoxyethylene fatty acid esters such as ethylene glycol stearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil Polyoxyethylene castor oil hardened castor oil derivatives such as noisostearate, polyoxyethylene hardened castor oil triisostearate, polyoxyethylene hardened castor oil monopyroglutamic acid monoisostearic acid diester, polyoxyethylene hardened castor oil maleic acid, etc. Nonionic surfactants and the like.

  Among the above, surfactants having a polyoxyethylene chain, a carboxylic acid, or a hydroxyl group as a hydrophilic group are preferred from the viewpoint of affinity with cellulose, and a polyoxyethylene surfactant having a polyoxyethylene chain as a hydrophilic group (Polyoxyethylene derivatives) are more preferable, and nonionic polyoxyethylene derivatives are more preferable. The polyoxyethylene chain length of the polyoxyethylene derivative is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 15 or more. The longer the chain length, the higher the affinity with cellulose. However, in balance with the coating property, 60 or less is preferable, 50 or less is more preferable, 40 or less is more preferable, 30 or less is particularly preferable, and 20 or less is Most preferred.

  When cellulose is blended in a hydrophobic resin (for example, polyolefin, polyphenylene ether, etc.), it is preferable to use a resin having a polyoxypropylene chain instead of a polyoxyethylene chain as a hydrophilic group. The polyoxypropylene chain length is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 15 or more. The longer the chain length, the higher the affinity with cellulose. However, in balance with the coating property, 60 or less is preferable, 50 or less is more preferable, 40 or less is more preferable, 30 or less is particularly preferable, and 20 or less is Most preferred.

  Among the surfactants mentioned above, in particular, as the hydrophobic group, the alkyl ether type, alkyl phenyl ether type, rosin ester type, bisphenol A type, β naphthyl type, styrenated phenyl type, and hardened castor oil type are compatible with the resin. Therefore, it can be preferably used. The preferred alkyl chain length (in the case of alkylphenyl, the number of carbon atoms excluding the phenyl group) is preferably 5 or more, more preferably 10 or more, still more preferably 12 or more, and particularly preferably 16 or more. When the resin is a polyolefin, the higher the number of carbons, the higher the affinity with the resin, so the upper limit is not set, but is preferably 30 or less, and more preferably 25 or less.

  Among these hydrophobic groups, those having a cyclic structure or those having a bulky polyfunctional structure are preferred, and those having a cyclic structure include alkylphenyl ether type, rosin ester type, bisphenol A type, β naphthyl type, The styrenated phenyl type is preferable, and the one having a polyfunctional structure is preferably a hardened castor oil type.

  Among these, rosin ester type and hardened castor oil type are particularly preferable.

  In particular, among the above-mentioned animal and plant oils, terpin oil, tall oil, rosin, and derivatives thereof are organic components that coat the surface of the cellulose particles of the present invention from the viewpoints of affinity for the cellulose surface and uniform coating properties. Is preferred.

  Terpin oil (also known as terbin oil) is an essential oil obtained by steam distillation of pine tree chips or pine oil obtained from these trees. Say. Examples of terpin oil include gum turpentine oil (obtained by steam distillation of pine resin), wood terpin oil (obtained by steam distillation or dry distillation of pine tree chips), turpentine sulfate Oil (obtained by distilling chips when heat-treated when manufacturing sulfate pulp) and sulfite turpentine oil (obtained by distilling chips when heat-treating when manufacturing sulfite pulp), almost colorless To light yellow liquid, except α-pinene and β-pinene, except turpentine oil. Unlike other turpentine oils, sulfite turpentine oil is mainly composed of p-cymene. If it contains the above-mentioned component, it will be contained in terpine oil, and all can be used as an organic component of this invention individually or in mixture.

  Tall oil is an oil mainly composed of resin and fatty acid, which is a by-product of making kraft pulp from pine wood. As tall oil, tall fat mainly composed of oleic acid and linoleic acid may be used, or tall rosin mainly composed of a diterpenoid compound having 20 carbon atoms such as abietic acid may be used.

  Rosin is a residue that remains after distilling turpentine essential oil by collecting balsams such as pine sap, which is the sap of pine family plants, and is a natural resin mainly composed of rosin acid (abietic acid, parastolic acid, isopimaric acid, etc.) It is. Also called colophony or colophony. Among these, tall rosin, wood rosin, and gum rosin can be preferably used. It is more preferable to use rosin derivatives obtained by subjecting these rosins to various stabilization treatments, esterification treatments, purification treatments and the like. The stabilization treatment refers to subjecting the rosins to hydrogenation, disproportionation, dehydrogenation, polymerization treatment or the like. The esterification treatment refers to a treatment in which the rosins or the rosins subjected to the stabilization treatment are reacted with various alcohols to form rosin esters. Various known alcohols or epoxy compounds can be used for the production of the rosin ester. Examples of the alcohol include monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, and lauryl alcohol; dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and neopentyl glycol; Examples include trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and cyclohexanedimethanol; and tetrahydric alcohols such as pentaerythritol and diglycerin. Also, isopentyldiol, ethylhexanediol, erythrulose, ozonated glycerin, caprylyl glycol, glycol, (C15-18) glycol, (C20-30) glycol, glycerin, diethylene glycol, diglycerin, dithiaoctanediol, DPG, Thioglycerin, 1,10-decanediol, decylene glycol, triethylene glycol, tilimethylgydroxymethylcyclohexanol, phytanetriol, phenoxypropanediol, 1,2-butanediol, 2,3-butanediol, butylethyl Multivalents such as propanediol, BG, PG, 1,2-hexanediol, hexylene glycol, pentylene glycol, methylpropanediol, menthanediol, lauryl glycol Alcohol may be used. In addition, those classified as sugar alcohols such as inositol, erythritol, xylitol, sorbitol, maltitol, mannitol, lactitol and the like are also included in the polyhydric alcohol.

Furthermore, alcoholic water-soluble polymers can also be used as the alcohol. Alcoholic water-soluble polymers include polysaccharides / mucopolysaccharides, those classified as starches, those classified as polysaccharide derivatives, those classified as natural resins, those classified as cellulose and derivatives, proteins -Those classified as peptides, those classified as peptide derivatives, those classified as synthetic homopolymers, those classified as acrylic (methacrylic acid) acid copolymers, those classified as urethane polymers, Examples include those classified as laminates, those classified as cationic polymers, and those classified as other synthetic polymers. Water-soluble ones can be used at room temperature. More specifically, sodium polyacrylate, cellulose ether, calcium alginate, carboxyvinyl polymer, ethylene / acrylic acid copolymer, vinyl pyrrolidone polymer, vinyl alcohol / vinyl pyrrolidone copolymer, nitrogen-substituted acrylamide polymer, poly Cationic polymers such as acrylamide and cationized gar gum, dimethylacrylammonium polymer, acrylic acid / methacrylic acid acrylic copolymer, POE / POP copolymer, polyvinyl alcohol, pullulan, agar, gelatin, tamarind seed polysaccharide, xanthan gum, carrageenan , High methoxyl pectin, low methoxyl pectin, gar gum, gum arabic, crystalline cellulose, arabinogalactan, karaya gum, tragacanth gum, alginic acid, alginate Bumin, casein, curdlan, gellan gum, dextran, cellulose, polyethylene imine, polyethylene glycol, cationized silicone polymer and the like.

  Among the above-mentioned various rosin esters, the coating properties on the surface of the cellulose particles and the dispersibility of the cellulose preparation in the resin tend to be further promoted, so that rosin and water-soluble polymer are preferably esterified, An esterified product with polyethylene glycol (also referred to as rosin ethylene oxide adduct, polyoxyethylene glycol resin acid ester, polyoxyethylene rosin acid ester) is particularly preferable.

  The organic component may be an alkylphenyl type compound, and examples thereof include alkylphenol ethoxylates, that is, nonionic surfactants obtained by ethoxylation of alkylphenol with ethylene oxide. Since the hydrophilic polyoxyethylene (POE) chain and the hydrophobic alkylphenol group are linked by an ether bond, it is also called poly (oxyethylene) alkylphenyl ether. In general, a series of products having different average chain lengths is commercially available as a mixture of many compounds having different alkyl chain lengths and POE chain lengths. The alkyl chain length is commercially available having 6 to 12 carbon atoms (excluding the phenyl group), and typical alkyl group structures include nonylphenol ethoxylate and octylphenol ethoxylate. Moreover, as a typical POE group structure, there are those having an ethylene oxide (EO) residue of 5 to 40, and typical ones are 15 to 30. The EO residue of nonylphenol ethoxylate is preferably 15-30, more preferably 15-25, and particularly preferably 15-20.

  The organic component may be a β-naphthyl type compound, for example, a β-mono-substituted product containing naphthalene as part of its chemical structure, and the carbon at the 2 or 3 or 6 or 7 position of the aromatic ring bonded to a hydroxyl group And a compound in which a hydrophilic group such as a PEO chain is covalently bonded. Moreover, as a typical POE group structure, there are those having 4 to 40 ethylene oxide (EO) residues, and typical ones include 15 to 30 ones. The EO residue is preferably 15 to 30, more preferably 15 to 25, and particularly preferably 15 to 20.

The organic component may be a bisphenol A type compound, for example, containing bisphenol A (chemical formula: (CH ₃ ) ₂ C (C ₆ H ₄ OH) ₂ ) as part of its chemical structure, And a compound in which a hydrophilic group such as a PEO chain is covalently bonded. Moreover, as a typical POE group structure, there are those having 4 to 40 ethylene oxide (EO) residues, and typical ones include 15 to 30 ones. The EO residue of nonylphenol ethoxylate is preferably 15-30, more preferably 15-25, and particularly preferably 15-20. When there are two ether bonds in one molecule, the EO residue indicates an average value obtained by adding the two ether bonds.

  The organic component may be a styrenated phenyl type compound. For example, a part of its chemical structure contains a styrenated phenyl group, and a phenol group in the structure and a hydrophilic group such as a PEO chain are covalently bonded. Compounds. The styrenated phenyl group has a structure in which 1 to 3 molecules of styrene are added to the benzene ring of the phenol residue. Moreover, as a typical POE group structure, there are those having 4 to 40 ethylene oxide (EO) residues, and typical ones include 15 to 30 ones. The EO residue of nonylphenol ethoxylate is preferably 15-30, more preferably 15-25, and particularly preferably 15-20. When there are two ether bonds in one molecule, the EO residue indicates an average value obtained by adding the two ether bonds.

  The organic component may be a hardened castor oil-type compound. For example, hydrogenated from castor oil (castor oil, castor oil, coconut oil), which is a kind of vegetable oil collected from the seeds of Euphorbiaceae As a hydrophobic group, a compound in which a hydroxyl group in the structure and a hydrophilic group such as a PEO chain are covalently bonded can be used. The components of castor oil are glycerides of unsaturated fatty acids (87% ricinoleic acid, 7% oleic acid, 3% linoleic acid) and a small amount of saturated fatty acids (3% palmitic acid, stearic acid, etc.). Moreover, as a typical POE group structure, there are those having 4 to 40 ethylene oxide (EO) residues, and typical ones include 15 to 30 ones. The EO residue of nonylphenol ethoxylate is preferably 15-30, more preferably 15-25, and particularly preferably 15-20.

  In a preferred embodiment, the organic component is selected from the group consisting of rosin derivatives, alkylphenyl derivatives, bisphenol A derivatives, β-naphthyl derivatives, styrenated phenyl derivatives, and hardened castor oil derivatives. In a preferred embodiment, the organic component is a polyoxyethylene derivative.

<Content ratio of cellulose and organic components>
The cellulose preparation according to the present invention preferably contains 30 to 99% by mass of cellulose and 1 to 70% by mass of organic components. By combining cellulose and an organic component, the organic component covers the surface of the cellulose particle with non-covalent chemical bonds such as hydrogen bonds and intermolecular forces, and as a result, the dispersion of cellulose in the resin is promoted. By making the content of the cellulose and the organic component in the above range, the composite is further promoted. The cellulose preparation according to the present invention preferably contains 50 to 99% by mass of cellulose and 1 to 50% by mass of organic components, and further contains 70 to 99% by mass of cellulose and 1 to 30% by mass of organic components. More preferably, it contains 80 to 99% by mass of cellulose and 1 to 20% by mass of organic components, and particularly preferably 90 to 99% by mass of cellulose and 1 to 10% by mass of organic components.

<Method for producing cellulose preparation>
Next, the manufacturing method of the cellulose formulation which concerns on this invention is demonstrated.
The method for producing a cellulose preparation according to the present invention is not particularly limited, and may be refined (particulate) after mixing raw material cellulose and organic components. Cellulose particles obtained by refining raw material cellulose may be used. By drying in a state where the organic component of the present invention is adhered, at least a part of the surface of the cellulose particles can be coated with the organic component. Moreover, you may perform refinement | miniaturization of raw material cellulose and the coating | cover with an organic component simultaneously.

  For example, the cellulose preparation according to the present invention can be produced by kneading raw material cellulose and the organic component of the present invention. Specifically, in the kneading step, it can be obtained by applying mechanical shearing force to cellulose and the organic component to make the cellulose fine (particulate) and to make the organic component complex on the cellulose surface. Moreover, in this kneading | mixing process, you may add hydrophilic substances other than an organic component, another additive, etc. You may dry as needed after a kneading | mixing process. The cellulose preparation according to the present invention may be undried after the kneading step or may be dried after that.

  In order to give a mechanical shearing force, for example, a kneading method using a kneader or the like can be applied. As a kneading machine, for example, a kneader, an extruder, a planetary mixer, a lycra machine, or the like can be used, which may be a continuous type or a batch type. The temperature at the time of kneading may be a result, and when heat is generated due to a compounding reaction, friction, or the like at the time of kneading, kneading may be performed while removing the heat. The above models may be used alone or in combination of two or more types.

  The kneading temperature is preferably lower from the viewpoint that the deterioration of the organic component is suppressed and the composite of cellulose and the organic component tends to be promoted. The kneading temperature is preferably 0 to 100 ° C, more preferably 90 ° C or less, further preferably 70 ° C or less, still more preferably 60 ° C or less, and 50 ° C or less. It is particularly preferred. In order to maintain the above kneading temperature under high energy, it is preferable to devise slow heating such as jacket cooling and heat dissipation.

  The solid content during kneading is preferably 20% by mass or more. By kneading in a semi-solid state where the viscosity of the kneaded material is high, the kneaded material does not become loose, and the kneading energy described below tends to be transmitted to the kneaded material and tends to promote compounding. The solid content at the time of kneading is more preferably 30% by mass or more, further preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit of the solid content is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, and 60% by mass from the viewpoint of obtaining a good kneading effect and a more uniform kneading state. More preferably, it is as follows. In order to make solid content into the said range, as a timing to add water, a required amount may be added before a kneading | mixing process, it may be added in the middle of a kneading | mixing process, and both may be implemented.

  Here, the kneading energy will be described. The kneading energy is defined as the amount of electric power per unit mass (Wh / kg) of the kneaded product. In the production of the cellulose preparation according to the present invention, the kneading energy is preferably 50 Wh / kg or more. When the kneading energy is 50 Wh / kg or more, the grindability imparted to the kneaded product is high, and the composite of cellulose and organic components tends to be further promoted. More preferably, the kneading energy is preferably 80 Wh / kg or more, more preferably 100 Wh / kg or more, further preferably 200 Wh / kg or more, still more preferably 300 Wh / kg or more, and particularly preferably 400 Wh / kg or more. It is considered that the higher the kneading energy is, the more the compounding is promoted. However, when the kneading energy is too high, the equipment becomes industrially excessive and an excessive load is applied to the equipment. Therefore, the upper limit of the kneading energy is preferably 1000 Wh / kg.

  The degree of conjugation is considered to be the proportion of bonds between cellulose and organic components due to hydrogen bonds, intermolecular forces, and the like. As the compounding progresses, when the resin and the cellulose preparation are kneaded, the dispersibility of cellulose in the resin composition tends to be improved in order to prevent aggregation between celluloses.

  The compounding in the kneading step is preferably performed under reduced pressure. When a wet cake containing water is used as a raw material for cellulose, it is carried out under reduced pressure to utilize hydrogen bonding of water between cellulose particles in the initial kneading stage, thereby further promoting particle refinement. Further, if the kneading is further carried out while discharging water out of the system under reduced pressure, it is efficient because the refinement of cellulose, dehydration, and coating of organic components proceed simultaneously.

  In obtaining the cellulose preparation according to the present invention, when drying the kneaded product obtained from the above kneading step, known methods such as shelf drying, spray drying, belt drying, fluidized bed drying, freeze drying, microwave drying, etc. The drying method can be used. When the kneaded product is subjected to a drying step, it is preferable that water is not added to the kneaded product, and the solid content concentration in the kneading step is maintained and the dried step is used.

  It is preferable that the moisture content of the cellulose preparation after drying is 1 to 20% by mass. By setting the moisture content to 20% by mass or less, problems such as adhesion to the container and rot, and cost problems in transportation and transportation are less likely to occur. Further, as the moisture content is lower, voids resulting from water evaporation are less likely to enter when mixed into the molten resin, and the physical properties (strength and dimensional stability) of the resin composite tend to increase. On the other hand, by setting the moisture content to 1% by mass or more, there is less possibility that the dispersibility deteriorates due to excessive drying. The water content of the cellulose preparation according to the present invention is more preferably 15% by mass or less, further preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Moreover, as a minimum of the moisture content of the cellulose formulation which concerns on this invention, 1.5 mass% or more is preferable.

  When the cellulose preparation is distributed in the market, it is preferable to pulverize the cellulose preparation into a powder form because the shape of the cellulose preparation is easier to handle. However, when spray drying is used as the drying method, drying and pulverization are performed at the same time, and therefore, it is not necessary to pulverize. When the cellulose preparation is pulverized, a known method such as a cutter mill, a hammer mill, a pin mill, or a jet mill can be used. The degree of pulverization is such that the pulverized product passes through a sieve having an opening of 1 mm. More preferably, it is preferable to grind so as to pass through a sieve having an opening of 425 μm and to have an average particle size (mass average particle size) of 10 to 250 μm. The obtained dry powder is obtained by agglomerating fine particles of the cellulose preparation to form secondary aggregates. This secondary aggregate is disintegrated when stirred in water and dispersed in the cellulose particles described above.

  The apparent mass average particle diameter of the secondary aggregate was determined by sieving 10 g of the sample for 10 minutes using a low-tap sieve shaker (for example, Sieve Shaker A type manufactured by Hira Kogyo Co., Ltd.) or JIS standard sieve (Z8801-1987) The cumulative mass 50% particle size in the particle size distribution obtained by doing.

<Dispersion aid>
The cellulose preparation according to the present invention may contain a polysaccharide as a dispersion aid in addition to the cellulose particles and the organic component. By containing a polysaccharide, the affinity of the organic component to the surface of the cellulose particles is increased, and the dispersion of the cellulose particles in the resin is promoted, which is preferable.

  The following are preferred as the polysaccharide. Examples thereof include water-soluble natural polysaccharides such as psyllium seed gum, karaya gum, carrageenan, alginic acid, sodium alginate, HM pectin, LM pectin, azotobacter vinelanzie gum, xanthan gum, gellan gum, and sodium carboxymethylcellulose. Among these anionic polysaccharides, sodium carboxymethylcellulose (hereinafter also referred to as “CMC-Na”) and xanthan gum are preferable. Moreover, these anionic polysaccharides may combine 2 or more types.

<Carboxymethylcellulose sodium>
Among the above anionic polysaccharides, CMC-Na is particularly preferable because it is easily complexed with cellulose. The CMC-Na here, but some or all of the hydrogen atoms on hydroxyl groups of cellulose consisting of anions polymer and Na cations substituted -CH ₂ COO group (carboxymethyl group), glucose D- are β It has a linear chemical structure with -1,4 bonds. CMC-Na is obtained, for example, by a production method in which pulp (cellulose) is dissolved with a sodium hydroxide solution and etherified with monochloroacetic acid (or a sodium salt thereof).

  In the cellulose preparation according to the present invention, it is particularly preferable from the viewpoint of complexing with cellulose that CMC-Na having a substitution degree and a viscosity prepared in the following specific ranges are included. The degree of substitution is the degree to which a carboxymethyl group is ether-bonded to a hydroxyl group (having three hydroxyl groups per glucose unit) in CMC-Na, and is preferably 0.6 to 2.0 per glucose unit. If the degree of substitution is in the above range, CMC-Na having a higher degree of substitution is more likely to be complexed with cellulose, and the storage elastic modulus of the cellulose composite is increased, and in a high salt concentration aqueous solution (for example, a 10% by mass sodium chloride aqueous solution). However, it is preferable because high suspension stability can be exhibited. More preferably, the substitution degree is 0.9 to 1.3.

The degree of substitution is measured by the following method. A sample (anhydrous) 0.5 g is accurately weighed, wrapped in filter paper and incinerated in a magnetic crucible. After cooling, transfer this to a 500 mL beaker, add about 250 mL of water and 35 mL of 0.05 M sulfuric acid and boil for 30 minutes. This is cooled, phenolphthalein indicator is added, excess acid is back titrated with 0.1 M potassium hydroxide, and calculated by the following formula.
A = [(af−bf1) / [sample anhydride (g)]] − [alkalinity (or + acidity)]
Degree of substitution = (162 × A) / (10000-80A)
here,
A: Amount of 0.05 M sulfuric acid consumed by alkali in 1 g of sample (mL)
a: Amount of 0.05 M sulfuric acid used (mL)
f: titer of 0.05M sulfuric acid b: titration volume of 0.1M potassium hydroxide (mL)
f1: titer of 0.1M potassium hydroxide 162: molecular weight of glucose 80: molecular weight of CH ₂ COONa-H

Measuring method of alkalinity (or acidity): 1 g of sample (anhydride) is accurately measured in a 300 mL flask, and about 200 mL of water is added and dissolved. To this is added 5 mL of 0.05 M sulfuric acid, boiled for 10 minutes, cooled, added with phenolphthalein indicator, and titrated with 0.1 M potassium hydroxide (SmL). At the same time, a blank test is performed (BmL), and the following formula is used.
Alkalinity = ((B−S) × f 2) / sample anhydride (g)
Here, f2 is the titer of 0.1M potassium hydroxide. When the value of (B−S) xf2 is (−), the acidity is set.

  The viscosity of CMC-Na is preferably 500 mPa · s or less in a 1% by mass pure aqueous solution. The viscosity here is measured by the following method. First, the CMC-Na powder is 1% by mass, and using a high shear homogenizer (for example, trade name “Excel Auto Homogenizer ED-7” manufactured by Nippon Seiki Co., Ltd.), treatment conditions: 15,000 rpm × 5 minutes Then, it is dispersed in pure water to prepare an aqueous solution. Next, about 3 hours after dispersion | distribution (25 degreeC preservation | save) about the obtained aqueous solution, it sets to a B-type viscosity meter (rotor rotation speed 60rpm), and after leaving still for 60 seconds, it is rotated for 30 seconds and measured. However, the rotor can be appropriately changed according to the viscosity.

  The lower the viscosity of CMC-Na, the easier the complexing with cellulose is promoted. Therefore, the viscosity of CMC-Na contained in the cellulose preparation according to the present invention is more preferably 200 mPa · s or less, and further preferably 100 mPa · s or less. The lower limit of the viscosity is not particularly set, but a preferable range is 1 mPa · s or more.

<Blending ratio of cellulose and dispersion aid>
The cellulose preparation according to the present invention preferably contains 30 to 99% by mass of cellulose particles whose surface is at least partially coated with the organic component of the present invention, and 1 to 70% by mass of a dispersion aid. Is more preferably 50 to 99% by mass, 1 to 50% by mass of a dispersion aid, more preferably 70 to 99% by mass of cellulose particles, and further preferably 1 to 30% by mass of dispersion aids. Is more preferably 80 to 99% by mass and 1 to 20% by mass of a dispersion aid, particularly preferably 90 to 99% by mass of cellulose particles and 1 to 10% by mass of a dispersion aid.

  The dispersion aid may be added when the cellulose preparation is obtained, or may be added before the cellulose preparation is added to the resin to obtain a composite. It is preferable to add the cellulose preparation when the cellulose preparation is obtained, since the addition amount of the organic component is suppressed and a desired effect is exhibited with a small amount. As an addition method, it may be added to the raw material cellulose or cellulose particles together with the organic component, may be added sequentially after adding the organic component, or the organic component is added sequentially after adding the dispersion aid. The addition method is free. In the case of sequential addition, drying may be performed after the addition of the first-stage organic component and the dispersion aid.

[Resin composition]
The resin composition according to the present invention can be a composition in which the cellulose preparation according to the present invention is dispersed in a resin.

<Type of resin>
The resin for dispersing the cellulose preparation according to the present invention is not particularly limited, and a wide variety of resins can be used. For example, by using a thermoplastic resin as a resin for dispersing the cellulose preparation according to the present invention, it is possible to obtain a thermoplastic resin composition using cellulose that does not inherently have thermoplasticity.

  The thermoplastic resin for dispersing the cellulose preparation according to the present invention is 250 from the viewpoint of preventing browning and aggregation due to decomposition of cellulose particles during the production of the resin composition and during the production of the molded product using the resin composition. Those that can be melt kneaded / extruded at a temperature of ℃ or lower are preferred. Examples of such thermoplastic resins include polyolefins such as polyethylene and polypropylene; elastomers such as ABS, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene rubber; And modified resins.

  As the polyolefin, polyolefin such as olefin resin and elastomer can be used. Further, a resin produced using a single site catalyst such as a metallocene catalyst can be used.

  As the olefin resin, excluding the following elastomer, low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, etc. Polypropylenes such as polypropylene (PP) and polypropylene-α-olefin copolymers; polypentenes such as poly-1-butene and poly-4-methyl-1-pentene, and mixtures thereof may be used. it can.

  Elastomers include natural rubber (NR), synthetic isoprene rubber (IR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), chloroprene (CR), halo. Rubber components such as butyl rubber (XIIR), butyl rubber (IIR), thermoplastic elastomer (TPO), and mixtures thereof can be used.

  These resin may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, polypropylene is preferable from the viewpoint of the strength of the resin.

<Resin content>
The resin content in the resin composition according to the present invention is preferably 70% by mass or more and 98% by mass or less with respect to the resin composition. When the resin content is 70% by mass or more, the obtained resin composition tends to have good moldability and thermoplasticity, and when it is 98% by mass or less, the dispersibility of the crystalline cellulose fine powder is high. It tends to be good. The resin content is more preferably 75% by mass or more and 90% by mass or less.

<Content of cellulose preparation>
The content of the cellulose preparation according to the present invention in the resin composition according to the present invention is preferably 1% by mass, and more preferably 1% by mass to 50% by mass with respect to the resin composition. When the content of the cellulose preparation is 1% by mass or more, the strength and impact resistance of the obtained molded product tend to be good. Moreover, when it is 50 mass% or less, it exists in the tendency for the intensity | strength and elastic modulus of the molded article obtained to become favorable. The content of the cellulose preparation according to the present invention is more preferably 30% by mass or less, further preferably 25% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

<Interface forming agent>
When the cellulose preparation according to the present invention is added to a resin, an interface forming agent that adheres the interface between the cellulose and the resin is added to achieve better mechanical properties (low linear expansion coefficient, strength, elongation). It is preferable. The interface forming agent may be a substance having both an affinity group for hydrophilic crystalline cellulose and an affinity group for a hydrophobic resin component in one molecule, and is a polymer such as a resin. Or a so-called low molecular weight compound. For example, the resin composition according to the present invention can contain a resin having a polar functional group in a partial structure as an interface forming agent. Examples of the resin having a polar functional group in a partial structure include modified polyolefin resin, polyamide, polyester, polyacetal, acrylic resin, and the like. When the interface forming agent is a resin, in the resin composition according to the present invention, the interface forming agent constitutes a part of the resin component.

  The modified polyolefin resin is preferably a polyolefin obtained by graft-modifying a carboxylic acid residue, a (meth) acrylic acid compound, or the like on a polyolefin. The unsaturated carboxylic acid used for graft modification is an unsaturated hydrocarbon having a carboxyl group. The derivatives include anhydrides. As the unsaturated carboxylic acid and derivatives thereof used in the present invention, fumaric acid, maleic acid, itaconic acid, citraconic acid, aconitic acid and their anhydrides, methyl fumarate, ethyl fumarate, propyl fumarate, Butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, maleic acid Dibutyl etc. are mentioned, More preferably, itaconic anhydride, maleic anhydride, etc. are illustrated. The (meth) acrylic acid compound is a compound containing at least one (meth) acryloyl group in the molecule. Examples of the (meth) acrylic acid compound include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, Examples include isobornyl (meth) acrylate, glycidyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and acrylamide. Here, the olefin can be preferably used as polyethylene or polypropylene, and the structure and molecular weight can be freely selected according to the base polymer of the composite.

  As the polyamide, both “n-nylon” synthesized by polycondensation reaction of ω amino acid and “n, m-nylon” synthesized by co-condensation polymerization reaction of diamine and dicarboxylic acid can be used (n Or, m is an index derived from the number of carbon atoms of the monomer component). For example, “n-nylon” (polycondensation reaction product) includes nylon 6, nylon 11, nylon 12 lauryl lactam (carbon number 12), and “n, m-nylon” (copolycondensation reaction product). Nylon 66, Nylon 610, Nylon 6T, Nylon 6I, Nylon 9T, Nylon M5T, Nylon 612, Kevlar (p-phenylenediamine + terephthalic acid copolycondensate), Nomex (m-phenylenediamine + isophthalic acid copolycondensate) Condensate) can be preferably used.

  As the polyester, a polycondensate of a polycarboxylic acid (dicarboxylic acid) and a polyalcohol (diol) can be used. For example, polyhydric carboxylic acid (dicarboxylic acid) components include terephthalic acid, 2,6-naphthalenedicarboxylic acid, polyhydric alcohol (diol) components such as ethylene glycol, 1,3-propanediol, 1,4 -Butanediol, 1,4-cyclohexanedimethanol and the like can be mentioned, and these polycondensates can be used.

  As the polyacetal, a homopolymer, a random copolymer (polyoxymethylene-oxymethylene random copolymer), or a block copolymer (polyoxymethylene-alkyl block copolymer) can be used.

  As the acrylic resin, a polymer of acrylic ester or methacrylic ester can be used.

  These interface forming agents may be used alone or in combination of two or more, and the mixing ratio can be freely set.

  For example, when the resin used as the base polymer is polyolefin, acid-modified polyolefin and / or polyamide can be suitably used as the interface forming agent. Here, as the acid-modified polyolefin, maleic acid-modified polyolefin, for example, maleic acid-modified polypropylene is preferable. When the base polymer is polypropylene, maleic acid-modified polypropylene can be preferably used. Since the maleic acid residue has a high affinity for the cellulose side interface and the polypropylene residue is compatible with the base polymer, the interface of the resin composition is brought into close contact, in addition to the dimensional stability and strength of the obtained resin composition, In particular, the elongation can be improved.

  Here, n-nylon can be suitably used as the polyamide. When the base polymer is polypropylene, nylon 6 can be preferably used. Nylon has a strong polymer molecular chain, and peptide residues have high affinity with the cellulose surface, so that it can impart dimensional stability and strength to the resin composition.

  The added amount of the interface forming agent may be an amount that molecularly covers the surface of cellulose, for example, 1 mass part or more with respect to 100 mass parts of cellulose. Preferably, 5 parts by mass or more is more preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is particularly preferable, and 20 parts by mass or more is most preferable. The upper limit of the addition amount of the interface forming agent is not necessarily set, but is preferably 50 parts by mass or less with respect to 100 parts by mass of cellulose in consideration of workability and durability of the resin composition.

  In order to improve the dimensional stability, the amount of the interface forming agent added is preferably 1 part by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of cellulose present in the cellulose preparation or resin composition. Preferably, 10 parts by mass or more is more preferable, 15 parts by mass or more is more preferable, and 20 parts by mass or more is particularly preferable. The upper limit of the addition amount of the interface forming agent is not necessarily set, but is preferably 50 parts by mass or less with respect to 100 parts by mass of cellulose in consideration of workability and durability of the resin composition.

  In order to increase the strength, for example, the addition amount of the interface forming agent is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of cellulose present in the cellulose preparation or resin composition. More preferred is at least 150 parts by mass, even more preferred is at least 150 parts by mass, and particularly preferred is at least 200 parts by mass. The upper limit of the addition amount of the interface forming agent is not necessarily set, but is preferably 500 parts by mass or less with respect to 100 parts by mass of cellulose in view of the workability and durability of the resin composition.

  The interface forming agent may be added during the production process of the cellulose preparation, or may be added when the cellulose preparation is added to the resin to obtain a resin composition. It is preferable to add the cellulose preparation when the cellulose preparation is obtained because the amount of the interface-forming agent is suppressed and a desired effect is exhibited with a small amount. The addition method is not particularly limited, and may be added together with other additives such as a dispersant, may be added sequentially after adding other additives, or an interface forming agent is added. Other additives may be added sequentially thereafter.

<Dispersant>
The resin composition according to the present invention may contain a dispersant such as a surfactant, a surface treatment agent, and an inorganic filler. The dispersing agent has a function of improving the compatibility between the cellulose preparation according to the present invention and the resin. That is, it has the function to disperse | distribute cellulose particle | grains favorably without aggregating in a resin composition, and to make the whole resin composition uniform. Therefore, as a dispersing agent to be contained in the resin composition according to the present invention, any dispersing agent can be used without any limitation as long as it can uniformly disperse cellulose particles in the resin composition. As such a dispersant, a known surfactant, surface treatment agent, inorganic filler, and the like that have affinity for at least both cellulose particles and resin can be appropriately used. The surfactant and the surface treatment agent may be organic components having a static surface tension of 20 mN / m or more and a boiling point higher than that of water, respectively.

  The content of the dispersant in the resin composition according to the present invention is preferably 1% by mass or more and 20% by mass or less. When the content of the dispersant is 1% by mass or more, the dispersibility of the cellulose particles in the resin composition tends to be good, and when it is 20% by mass or less, the strength of the molded product obtained from the resin composition. Tends to be maintained well. The content of the dispersant in the resin composition according to the present invention is more preferably 5% by mass or more and 15% by mass or less. In addition, since the organic component having a static surface tension of 20 mN / m or more and a boiling point higher than water also functions as a dispersant, the content of the dispersant includes an amount including the amount of the organic component. means.

  Examples of the surfactant include stearic acid, higher fatty acids such as calcium, magnesium and zinc salts of stearic acid and salts thereof; higher alcohols and higher polyhydric alcohols such as stearyl alcohol, glyceride stearate and polyethylene glycol; polyoxyethylene Examples include various fatty acid esters such as sorbitan monostearate. Among the above, stearic acid glyceride is preferable.

  Examples of the surface treatment agent include non-reactive silicone oils such as dimethyl silicone oil and higher fatty acid ester-modified silicone oil; reactive silicone oils such as epoxy-modified silicone oil, carbinol-modified silicone oil, and carboxyl-modified silicone oil; N- And lauryl-D, L-aspartic acid-β-lauryl ester.

  As the inorganic filler, metal elements in Groups I to VIII of the Periodic Table, for example, simple elements, oxides of Fe, Na, K, Cu, Mg, Ca, Zn, Ba, Al, Ti or Si elements , Hydroxides, carbon salts, sulfates, silicates, sulfites, and various viscosity minerals composed of these compounds. More specifically, for example, barium sulfate, calcium sulfate, magnesium sulfate, sodium sulfate. , Calcium sulfite, zinc oxide, silica, (heavy) calcium carbonate, aluminum borate, alumina, iron oxide, calcium titanate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium silicate, clay last Knight, glass beads, glass powder, silica sand, silica, quartz powder, diatomaceous earth, white carbon, etc.

  As the dispersant to be contained in the resin composition according to the present invention, one of these may be used alone, or two or more may be used in combination. Among the above, (heavy) calcium carbonate is preferable as the dispersant contained in the resin composition according to the present invention.

<Other additives>
In the resin composition according to the present invention, in addition to the cellulose preparation and resin according to the present invention, and in addition to the interface forming agent and the dispersant, other components may be added as necessary within the range not impairing the effects of the present invention. May be included. Examples of the other components include antioxidants, metal deactivators, flame retardants (organic phosphate ester compounds, inorganic phosphorus compounds, aromatic halogen flame retardants, silicone flame retardants, etc.), fluorine-based compounds, and the like. Polymers, plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather resistance (light) improvers, polyolefin nucleating agents, slips Agent, inorganic or organic filler or reinforcing material (glass fiber, carbon fiber, polyacrylonitrile fiber, whisker, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fiber, Conductive carbon black, etc.), various colorants, release agents and the like. The content of the other component is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less with respect to the entire resin composition.

  Although the resin composition according to the present invention can include a cellulose preparation as described above, in another embodiment of the present invention, the resin composition includes the above-described thermoplastic resin, the above-described cellulose particles, and the static. The organic component described above having a surface tension of 20 mN / m or more and a boiling point higher than water can be included. Further, in a preferred embodiment, the resin composition includes the above-described thermoplastic resin, the above-described cellulose particles, the above-described organic component having a static surface tension of 20 mN / m or more and a boiling point higher than water, and the resin composition. 1 part by mass or more of the above-described interface forming agent can be included with respect to 100 parts by mass of cellulose present. In these aspects, the cellulose content is 30 to 99 mass% and the organic component content is 1 to 70 mass% with respect to the total 100 mass% of the total cellulose content and the organic component content in the resin composition. preferable.

<Method for producing resin composition>
The method for producing the resin composition according to the present invention is not particularly limited, and can be appropriately selected from various methods used for dispersing inorganic particles and the like in the resin.

  The resin composition according to the present invention comprises, for example, heat-melting a resin or a mixture of a resin and an interface forming agent, and adding the cellulose preparation (or a combination of cellulose particles and organic components) and a dispersant according to the present invention thereto. In addition, it can be produced by a method of melt kneading together. Alternatively, the raw material of the resin and the raw material of the resin and the interface forming agent are supplied to the extruder and melted. On the other hand, the cellulose preparation (or a combination of cellulose particles and organic components) and the dispersant are supplied from the intermediate port of the extruder. By doing so, the resin composition according to the present invention can also be produced by a method of mixing and dispersing in an extruder. Examples of the extruder include a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, and a Banbury mixer. Among these, a melt kneading method using a twin screw extruder is preferable from the viewpoint of sufficient kneading.

  The melt-kneading temperature in the production of the resin composition is not particularly limited because it varies depending on the components used, but can usually be arbitrarily selected from 50 to 250 ° C, and in many cases 200 to 250 ° C. Range. Other manufacturing conditions may be appropriately selected from those usually used.

  The resin composition according to the present invention can be molded as a molded body of various parts by using various methods, for example, molding methods such as injection molding, extrusion molding, and hollow molding. When a thermoplastic resin is used as the resin, the obtained molded product has thermoplasticity and has strength, elastic modulus, and impact resistance that cannot be obtained with a molded product obtained solely from the thermoplastic resin. The surface properties such as roughness of the product and presence / absence of aggregation are also good.

  In particular, the resin composition according to the present invention is characterized by exhibiting excellent fluidity (melt flow rate: MFR) when the resin is melted by blending cellulose particles. Thereby, when the molten resin is injection-molded, even a complicated shape can be easily molded at a low pressure using a normal mold. This feature is achieved by the fine dispersion of cellulose particles in the resin. The cellulose particles (and cellulose fibers, if present) are finely dispersed in the resin matrix, so that the network structure of the cellulose particles (and further cellulose fibers if present) includes the resin, and the network structure is It exhibits thixotropic properties when the resin is melted. In the resin composition, the cellulose plays a role of a roller (pulley), thereby improving fluidity. In a preferred embodiment, the average degree of polymerization, average particle size (volume average particle size and mass average particle size), fiber length and fiber width, L / D, and / or zeta potential of cellulose dispersed in the resin are disclosed. When properly controlled within the range, the above characteristics are more easily exhibited.

  The invention is illustrated by the following examples. However, these do not limit the scope of the present invention. In addition, the measuring method of each physical property in an Example and a comparative example is as follows.

<Average degree of polymerization of cellulose>
It was measured by a reduced specific viscosity method using a copper ethylenediamine solution specified in the crystalline cellulose confirmation test (3) of “14th revised Japanese pharmacopoeia” (published by Yodogawa Shoten).

<Crystal form and crystallinity of cellulose>
Using an X-ray diffractometer (manufactured by Rigaku Corporation, multipurpose X-ray diffractometer), a diffraction image was measured by a powder method (at room temperature), and a crystallinity was calculated by a Segal method. The crystal form was also measured from the obtained X-ray diffraction image.

<L / D of cellulose particles>
Cellulose (wet cake after hydrolysis) is made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, treatment condition: rotational speed 15,000 rpm × 5 minutes) The aqueous dispersion was diluted with pure water to 0.1 to 0.5% by mass, cast on mica, and air-dried. An atomic force microscope (AFM) The ratio (L / D) when the length (L) and the diameter (D) of the particle image obtained at the time of measurement was obtained was calculated, and calculated as an average value of 100 to 150 particles.

<Colloidal cellulose content>
Each cellulose in a solid content of 40% by mass in a planetary mixer (trade name “5DM-03-R”, manufactured by Shinagawa Kogyo Co., Ltd., stirring blade hook type) at 126 rpm at room temperature and normal pressure for 30 minutes Kneaded. Subsequently, a pure water suspension having a solid content of 0.5% by mass was prepared, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, treatment condition: 15,000 rpm × 5 minutes), centrifuged (Kubota Shoji Co., Ltd., trade name “6800 type centrifuge”, rotor type RA-400 type, processing conditions: supernatant centrifuged at a centrifugal force of 39200 m ² / s for 10 minutes The supernatant was further centrifuged at 116000 m ² / s for 45 minutes.) The solid content remaining in the supernatant after centrifugation was measured by the absolutely dry method, and the mass percentage was calculated.

<Volume average particle diameter of cellulose>
In a planetary mixer (trade name “5DM-03-R”, manufactured by Shinagawa Kogyo Co., Ltd., stirring blade is a hook type) with a solid content of 40% by mass, kneading is performed at 126 rpm at room temperature and normal pressure for 30 minutes. did. Subsequently, a pure water suspension having a solid content of 0.5% by mass was prepared, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, treatment condition: 15,000 rpm × 5 minutes), centrifuged (Kubota Shoji Co., Ltd., trade name “6800 type centrifuge”, rotor type RA-400 type, processing conditions: supernatant centrifuged at a centrifugal force of 39200 m ² / s for 10 minutes The supernatant was further centrifuged at 116000 m ² / s for 45 minutes.) Volume obtained by laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., trade name “LA-910”, ultrasonic treatment for 1 minute, refractive index 1.20) using the supernatant after centrifugation. The 50% cumulative particle size (volume average particle size) in the frequency particle size distribution was measured.

<Zeta potential of cellulose>
Cellulose was made into a pure water suspension with a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, treatment condition: 15,000 rpm × 5 minutes) The aqueous dispersion obtained by dispersion was diluted with pure water to 0.1 to 0.5% by mass, and a zeta electrometer (manufactured by Otsuka Electronics, apparatus name ELSZ-2000ZS type, standard cell unit) was used. Measured at ° C.

<Static surface tension of organic components>
Using each organic component, static surface tension was measured by the Wilhelmy method using an automatic surface tension measuring device (manufactured by Kyowa Interface Science Co., Ltd., trade name “CBVP-Z type”, attached glass cell). Since each organic component used in Examples and Comparative Examples was liquid at room temperature, it was charged in a stainless steel petri dish attached to the apparatus so that the height from the bottom to the liquid level was 7 mm to 9 mm, and 25 ° C. ± 1 The temperature was measured after the temperature was adjusted to ° C., and was determined by the following formula. γ = (P−mg + shρg) / Lcosθ. Where P: balance force, m: mass of plate, g: gravitational constant, L: plate circumference, θ: contact angle between plate and liquid, s: plate cross-sectional area, h: liquid (to balance force) Depth sunk from the surface, ρ: density of the liquid (the organic component used in the examples and comparative examples was 1 ± 0.4 g / mL, so 1 was used).

  Those solid at room temperature were heated to the melting point or higher and melted, then the temperature was adjusted to the melting point + 5 ° C., and the surface tension was measured by the Wilhelmy method described above.

<Dynamic surface tension of organic components>
Using each organic component, bubbles are generated by the maximum bubble pressure method using a dynamic surface tension meter (product name: Theta Science t-60 type, manufactured by Eiko Seiki Co., Ltd., probe (capillary TYPE I (peak resin), single mode)). The dynamic surface tension was measured at a period of 10 Hz, and each organic component used in Examples and Comparative Examples was dissolved or dispersed in ion-exchanged water at 5% by mass to prepare a measurement solution, and 100 mL of the solution or dispersion was A glass beaker having a capacity of 100 mL was charged and the temperature was adjusted to 25 ° C. ± 1 ° C., and the measured value was used.The dynamic surface tension was obtained by the following equation: σ = ΔP · r / 2 Where σ: dynamic surface tension, ΔP: pressure difference (maximum pressure-minimum pressure), r: capillary radius.

<SP value of organic component>
The SP value of the organic component was determined from the range of the SP value of the solvent dissolved without phase separation after 1 mL of each was added dropwise to 10 mL of the solvent shown in the table below at room temperature and stirred with a stirrer for 1 hour.

<Binding ratio of organic components>
Cellulose preparation was added to 1 g of solid content in 10 mL of ethanol and stirred at room temperature for 60 minutes under stirring with a stirrer. The solvent was filtered through a PTFE membrane filter with an opening of 0.4 μm, and ethanol and other solvents were removed from the filtrate. Vaporized. The mass of the residue collected from the filtrate was determined, and the binding rate was calculated from the following equation.

  Bonding rate (%) = [1-([mass of residue (g)] / [amount of organic component in cellulose preparation (g)])] × 100

<Dispersibility>
The thin film obtained from the strand of the resin composition was observed with a transmission microscope using a microscope (manufactured by KEYENCE, trade name “VHX-1000”, magnification 200 ×), and the number of coarse particles having a short diameter of 100 μm or more was measured. . Based on the number of particles having a short diameter of 100 μm or more confirmed in a 2000 μm × 2000 μm field of view, the evaluation was performed according to the following criteria.
◎: 10 or less ○: Over 10 and 20 or less △: Over 20 and 50 or less ×: Over 50

<Colorability>
The thin film obtained from the strand of the resin composition was visually observed. Evaluation was performed according to the following criteria.
◎: Colorless and transparent ○: Light orange △: Dark orange ×: Dark orange to brown

<MFR (Melt Flow Rate)>
The pellet obtained from the strand of the resin composition was measured at 230 ° C. under a load of 2.16 kgf according to the method of ISO 1133 A method. The measured value of MFR of each resin composition was compared with the measured value of MFR of PP single pellet (manufactured by Sun Allomer Co., Ltd., product name “Sun Allomer PX600N”, hereinafter the same), and evaluated according to the following criteria. The unit was g / 10 minutes. In addition, MFR of the pellet of PP alone was 5.8 g / 10 min.
◎: 80% or more improvement over PP alone ○: 50% or more improvement over PP alone Δ: 20% or more improvement over PP alone ×: + 10% or less over PP alone (no effect)

<Linear expansion coefficient>
The pellets obtained from the strands of the resin composition were measured in the range of 0 to 60 ° C. according to the method of JIS K7197 (TMA method: thermomechanical analysis method), and evaluated based on the obtained measurement values according to the following criteria. (PP alone was 148 ppm / K).
(About Examples 1-28 and Comparative Examples)
A: Less than 120 ppm / K B: 120 ppm / K or more, less than 130 ppm / K Δ: 130 ppm / K or more, less than 140 ppm / K x: 140 to 150 ppm / K
(Examples 29 to 41)
A: Less than 40 ppm / K B: 40 ppm / K or more, less than 50 ppm / K Δ: 50 ppm / K or more, less than 60 ppm / K x: 60 to 70 ppm / K

<Tensile strength>
Tensile strength was measured using a universal material testing machine (Autograph AG-E type, manufactured by Shimadzu Corporation) using a JIS K7127 standard dumbbell-shaped test piece obtained in each Example and Comparative Example. The test temperature was room temperature, the crosshead speed was measured at 50 mm / min, and the yield value was determined as the tensile strength from the obtained stress-strain curve. The measured value of the tensile strength of each resin composition was compared with the measured value of the tensile strength of the PP pellet alone and evaluated according to the following criteria. The tensile strength of PP alone pellets was 33 MPa.
A: 130% or more improvement over PP alone B: 120% improvement over PP alone Δ: 110% improvement over PP alone X: Less than 110% over PP alone

<Tension stretch>
The breaking distance was determined as tensile elongation from the stress-strain curve obtained by the above-described measurement of tensile strength. The measured value of the tensile strength of each resin composition was compared with the measured value of the tensile elongation of the pellet of PP alone, and evaluated according to the following criteria. In addition, the tensile elongation of the pellet of PP alone was 20%.
◎: 200% or more improvement with respect to PP alone ○: 150% or more improvement with respect to PP alone △: 130% or more improvement with respect to PP alone ×: Less than 110% with respect to PP alone

Example 1
After shredding commercially available DP pulp (average polymerization degree 1600), it was hydrolyzed in 2.5 mol / L hydrochloric acid at 105 ° C. for 15 minutes, then washed with water and filtered to form a wet cake having a solid content of 50% by mass. Cellulose was prepared (average polymerization degree 220, crystal form I, crystallinity 78%, particle L / D1.6, colloidal cellulose content 55 mass%, particle diameter (accumulated volume 50% particle diameter, the same applies hereinafter). ) 0.2 μm, zeta potential −20 mV). Next, this wet cake-like cellulose is singly sealed in a closed planetary mixer (manufactured by Kodaira Manufacturing Co., Ltd., trade name “ACM-5LVT”, stirring blade is hook type) at 70 rpm for 20 minutes at room temperature and normal pressure. After crushed, rosin ethylene oxide adduct (rosin-polyethylene glycol ester, manufactured by Harima Chemicals Co., Ltd., trade name “REO-15”, static surface tension 39.7 mN / m, dynamic surface tension 48.1 mN / M, SP value of 7.25 or more, boiling point under atmospheric pressure of more than 100 ° C.) is added so that the cellulose / rosin ethylene oxide adduct becomes 80/20 (mass ratio), and milled at room temperature and atmospheric pressure at 70 rpm for 60 minutes. Process, and finally reduce the pressure (−0.1 MPa), set a 40 ° C. warm bath, perform coating and vacuum drying at 307 rpm for 2 hours, To obtain a cellulose formulation A (moisture content 2% by weight, less binding ratio of 5% of the organic component).

  12.5 parts by mass of the obtained cellulose preparation, 3 parts by mass of maleic acid-modified PP (manufactured by Sanyo Chemical Industries, Ltd., product name “Yumex 1001”), PP (manufactured by Sun Aroma Co., Ltd., product name “Sun Aroma PX600N”) 84.5 parts by mass, using a small kneader (manufactured by Xplore Instruments, product name “Xplore”) at 200 ° C. and 100 rpm (sialate 1570 (1 / s)) for 5 minutes, after passing through a die A strand of composite PP (resin composition) having a diameter of 1 mm was obtained. The strand was cut to a length of 1 cm at room temperature, 1 g was weighed, and a thin film having a thickness of 100 μm was obtained by hot pressing (200 ° C.). In addition, dumbbell-shaped test pieces of JIS K7127 standard were prepared from a resin obtained by melting pellets obtained from the strands (strands cut to 1 cm length) at 200 ° C. with an attached injection molding machine, and each evaluation. Used for. Each evaluation was performed using the obtained thin film, pellet, and dumbbell-shaped test piece. The results are shown in Table 2.

(Example 2)
Cellulose preparation B was obtained by the same method as in Example 1 except that the blending ratio of the cellulose / rosin ethylene oxide adduct was 95/5 (mass ratio) in the production method of the cellulose preparation of Example 1 (moisture content) 2% by mass, organic component binding rate of 5% or less). Using this cellulose preparation B, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

(Example 3)
Cellulose preparation C was obtained by the same method as in Example 1 except that the blending ratio of the cellulose / rosin ethylene oxide adduct was 50/50 (mass ratio) in the production method of the cellulose preparation of Example 1 (moisture content) 2% by mass, organic component binding rate of 5% or less). Using this cellulose preparation C, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

Example 4
Cellulose preparation D was obtained by the same method as in Example 1 except that the blending ratio of cellulose / rosin ethylene oxide adduct was 99/1 (mass ratio) in the production method of cellulose preparation of Example 1 (moisture content) 2% by mass, organic component binding rate of 5% or less). Using this cellulose preparation D, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

(Example 5)
In the production method of the cellulose preparation of Example 1, as an organic component, liquid paraffin (manufactured by Wako Pure Chemicals, special grade, static surface tension 26.4 mN / m (in addition, liquid paraffin was phase-separated from water, so dynamic surface tension The cellulose preparation E was obtained in the same manner as in Example 1 except that the boiling point under atmospheric pressure was over 100 ° C.) (2% by mass of water, organic component binding rate) 5% or less).
Using this cellulose preparation E, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

(Example 6)
In the production method of the cellulose preparation of Example 1, as an organic component, tall oil fatty acid (trade name “Hartol SR-30” manufactured by Harima Chemical Co., Ltd., static surface tension 30.2 mN / m (in addition, tall oil fatty acid is water and Because of the phase separation, the dynamic surface tension was the same as that of water.)) Cellulose preparation by the same method as in Example 1 except that SP value 7.25 or more and boiling point under atmospheric pressure was over 100 ° C.) F was obtained (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation F, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

(Example 7)
In the production method of the cellulose preparation of Example 1, as an organic component, terpine oil (trade name “Turpineol” manufactured by Yashara Chemical Co., Ltd., static surface tension 33.2 mN / m (in addition, since terpin oil was phase-separated with water, Surface tension became the same value as water.), Cellulose preparation G was obtained by the same method as in Example 1 except that SP value of 7.25 or more and boiling point under atmospheric pressure was over 100 ° C.) 2% by mass, organic component binding rate of 5% or less). Using this cellulose preparation G, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

(Example 8)
In the production method of the cellulose preparation of Example 1, rosin ethylene oxide adduct (rosin-polyethylene glycol ester, manufactured by Harima Chemicals Co., Ltd., trade name “REO-15”, static surface tension 39.7 mN / m as an organic component. , Dynamic surface tension of 48.1 mN / m, SP value of 7.25 or more, boiling point under atmospheric pressure of over 100 ° C., and tall oil fatty acid (trade name “Hartol SR-30” manufactured by Harima Chemical Co., Ltd.), static surface tension 20 parts by mass of 30.2 mN / m, SP value of 7.25 or more, boiling point under atmospheric pressure of more than 100 ° C.) mixed in an equal ratio (static surface tension 35 mN / m, dynamic surface tension 39 mN / m) The cellulose formulation H was obtained by the same method as Example 1 except having used as (water | moisture content 2 mass%, organic component binding rate 5% or less). Using this cellulose preparation H, a resin composition was prepared in the same manner as in Example 1, and evaluated. The results are shown in Table 3.

Example 9
In the production method of the cellulose preparation of Example 1, glycerin (static surface tension 63.4 mN / m, dynamic surface tension 71.9 mN / m, boiling point under normal pressure, higher than 100 ° C.) was used as an organic component. Cellulose preparation I was obtained in the same manner as in Example 1 (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation I, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

(Example 10)
After shredding commercially available DP pulp (average polymerization degree 1600), it was hydrolyzed in 2.5 mol / L hydrochloric acid at 70 ° C. for 15 minutes, then washed with water and filtered to form a wet cake with a solid content of 50% by mass. Cellulose (average polymerization degree 490, crystal form I, crystallinity 73%, particle L / D1.4, colloidal cellulose content 50 mass%, particle diameter 0.3 μm) was prepared. A cellulose preparation J was obtained in the same manner as in Example 1 except that the obtained wet cake-like cellulose was used as cellulose (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation J, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

(Example 11)
After shredding commercially available bagasse pulp (average degree of polymerization 1100), it was hydrolyzed in 1.5 mol / L hydrochloric acid at 70 ° C. for 15 minutes, filtered, and wet cake-like cellulose having a solid content of 50 mass% (average Polymerization degree 750, crystal form I type, crystallinity 69%, particle L / D1.3, colloidal cellulose content 40% by mass, particle diameter 0.5 μm) were prepared. A cellulose preparation K was obtained in the same manner as in Example 1 except that the obtained wet cake-like cellulose was used as cellulose (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation K, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

(Example 12)
After chopping commercially available KP pulp (average polymerization degree 1600), hydrolyzing in 2.5 mol / L hydrochloric acid at 120 ° C. for 50 minutes, followed by washing with water and filtration. Diluted, treated with a high shear homogenizer (manufactured by PRIMIX, trade name “TK homogenizer”, 8000 rpm, 15 minutes), further filtered, and wet cake-like cellulose having a solid content of 50 mass% (average polymerization degree 110, crystal form) Type I, 85% crystallinity, particle L / D 5.5, colloidal cellulose content 80% by mass, particle size 0.15 μm). A cellulose preparation L was obtained by the same method as in Example 1 except that the obtained wet cake-like cellulose was used as cellulose (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation L, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 4.

(Example 13)
Commercially available DP pulp (average polymerization degree 1620) was dissolved at −5 ° C. in a 60 mass% sulfuric acid aqueous solution so that the cellulose concentration was 4% by weight to obtain a cellulose dope. The cellulose dope was poured into 2.5 times by weight of water (5 ° C.) with stirring, and the cellulose was aggregated in a floc form to obtain a suspension. This suspension is hydrolyzed for 10 minutes after reaching a temperature of 80 ° C., and repeatedly washed with water and dehydrated until the pH of the supernatant reaches 4 or more, and a translucent white of paste-like cellulose particles having a cellulose concentration of 6% by weight. A paste was obtained. Further, the paste was diluted with water to a cellulose concentration of 5% by weight, and mixed with a high shear homogenizer (Excel Auto homogenizer) at a rotation speed of 15000 rpm or more for 5 minutes. Next, the paste was treated four times with an ultrahigh pressure homogenizer (Microfluidizer M-110EH type, manufactured by Mizuho Kogyo Co., Ltd., operating pressure 1750 kg / cm ² ) to obtain a transparent gel (transparent paste). . This transparent paste was washed / desolved three times with ion-exchanged water / ethanol = 50/50 (weight ratio) to obtain a gel-like product having a cellulose concentration of 5.2% by weight. This gel was mixed with a blender at a rotational speed of 10,000 rpm for 5 minutes. This dispersion was concentrated under reduced pressure with stirring to give a cellulose floc having a solid content of 50% by mass (average polymerization degree 80, crystal form II, crystallinity 28%, particle L / D0.1, colloidal cellulose content). 80% by mass and a particle diameter of 0.1 μm) were obtained. A cellulose preparation M was obtained in the same manner as in Example 1 except that this cellulose was used (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation M, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 4.

(Comparative Example 1)
In the manufacturing method of the cellulose preparation of Example 1, an organic component was not added, and a PP resin composition was prepared in the same manner as in Example 1 using wet cake-like cellulose (cellulose preparation N) having a cellulose concentration of 50% by mass. ,evaluated. The results are shown in Table 4.

(Comparative Example 2)
In the method for producing the cellulose preparation of Example 1, as an organic component, ethanol (manufactured by Wako Pure Chemicals, special grade, static surface tension 22.3 mN / m, dynamic surface tension 54.9 mN / m, SP value 12.58, Cellulose preparation O was obtained using a normal pressure boiling point of 78.4 ° C. so that the cellulose / organic component blending ratio was 80/20. Using this cellulose preparation O, a PP resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 3)
To 94 g of commercially available softwood bleached kraft pulp (refiner-treated, degree of polymerization 1050, solid content 25% by mass), 19.94 kg of ion-exchanged water was added to prepare an aqueous suspension (cellulose concentration 0.75% by mass). ). Using the obtained slurry in a bead mill (manufactured by Kotobuki Giken Kogyo Co., Ltd., trade name “Apex Mill AM-1”), zirconia beads having a diameter of 1 mm (filling rate: 70% by volume) as a medium, the rotating speed of the stirring blade is 2500 rpm, The cellulose dispersion was obtained by pulverizing twice by passing the cellulose aqueous dispersion at a feed rate of 0.4 L / min. This dispersion was concentrated under reduced pressure with stirring, and a cellulose floc having an average solid content of 50% by mass (average polymerization degree 1050, crystal form I, crystallinity 69%, particle L / D15000, colloidal cellulose content was measured. And a particle diameter of 550 μm) was obtained.

  This cellulose floc and rosin ethylene oxide adduct (rosin-polyethylene glycol ester, manufactured by Harima Kasei Co., Ltd., trade name “REO-15”, static surface tension 39.7 mN / m, dynamic surface tension 48.1 mN / m , SP value of 7.25 or more, boiling point under atmospheric pressure of more than 100 ° C.) was added to water so that the cellulose / rosin ethylene oxide adduct was 80/20 (mass ratio), and the dispersion was adjusted (cellulose concentration of 0.2%). 5% by mass). This was designated as Cellulose Dispersion P. Using this cellulose dispersion P, a PP resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 4)
In the method of Example 1, when preparing a resin composition, cellulose is not added, but rosin ethylene oxide adduct (rosin-polyethylene glycol ester, manufactured by Harima Chemicals Co., Ltd., trade name “REO-15” as an organic component) 2.5 parts by mass of a static surface tension of 39.7 mN / m, a dynamic surface tension of 48.1 mN / m, an SP value of 7.25 or more, and a boiling point of over 100 ° C. under normal pressure) 3 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., product name “Yumex 1001”) and 84.5 parts by mass of PP (manufactured by Sun Aroma Co., Ltd., product name “Sun Aroma PX600N”) are added, and a small kneader (manufactured by Xplore instruments) is added. , Product name “Xplore”), a resin composition was prepared in the same manner as in Example 1, and the resulting thin film, pellet, Each evaluation was performed using a test piece. The results are shown in Table 4.

  The resin composition of Comparative Example 1 in which the cellulose preparation N composed of cellulose particles not coated with an organic component was blended, and the Comparative Example 1 in which the cellulose preparation M composed of cellulose particles coated with ethanol having a boiling point lower than that of water was blended. In the resin composition, the dispersion of cellulose particles in PP was poor, the MFR was small, and there was only fluidity comparable to that of PP alone. Shaped articles such as thin films formed from these resin compositions all had small coefficients of expansion, tensile strength, and tensile elongation, and no improvement from those using PP alone was observed. Further, in the resin composition of Comparative Example 3 in which a rosin ethylene oxide adduct having a static surface tension of 20 mN / m or more and a boiling point higher than that of water and an aqueous dispersion of cellulose particles are blended, fluidity and tensile elongation are , Worse than PP alone.

  In addition, the resin composition of Comparative Example 4 was obtained by the same operation as in Example 1 except that the cellulose was not blended and the organic component was blended alone. No significant blending effects of stability, strength and elongation were observed.

  On the other hand, cellulose preparations A to C composed of cellulose particles kneaded with an organic component having a static surface tension of 20 mN / m or more and a boiling point higher than that of water and covering at least a part of the particle surface with the organic component. In the resin compositions of Examples 1 to 13 containing M, the dispersibility of the cellulose particles in the resin is good, and both the MFR and tensile elongation of the obtained resin composition are improved compared to those of PP alone. It had been. In particular, the resin compositions of Examples 1 to 12 in which cellulose preparations A to L in which type I crystalline cellulose particles were coated with an organic component were blended were improved in linear expansion coefficient and tensile strength from those of PP alone.

  In addition, from the results of the resin compositions of Examples 1, 10, 11, and 12 in which cellulose preparations A, J, K, and L composed of cellulose particles coated with rosin ethylene oxide adduct were blended, the average polymerization of cellulose particles The resin composition containing cellulose preparations A, J, and L having a degree of less than 500 is higher in MFR and linear expansion coefficient than the resin composition containing cellulose preparation K having an average degree of polymerization of cellulose particles of 750. The tensile strength and tensile elongation were both good. Moreover, compared with the cellulose formulation E (Example 5) coat | covered with the liquid paraffin which does not have a hydrophilic group, and the cellulose formulation I (Example 9) coat | covered with the glycerin which does not have a hydrophobic group, a hydrophobic group and a hydrophilic group are included. Cellulose preparations A, F, G and H (Examples 1 and 6 to 8) coated with organic components having both have better dispersibility in the resin, and in particular, linear expansion coefficient, tensile strength and tensile strength. The elongation was better.

(Example 14)
The cellulose preparation A of Example 1 was used, and the resin composition was changed to 12.5 parts by weight of the cellulose preparation, 0.1 parts by weight of maleic acid-modified PP, and the remainder was changed to 100 parts by weight of polypropylene. Using a small kneader, resin compositions were similarly prepared and evaluated. The results are shown in Table 5.

In evaluation of the resin composition of an Example, the evaluation criteria of Examples 14-28 were as follows.
<Linear expansion coefficient>
◎◎: Less than 80 ppm / K ◎: 80 ppm / K or more, less than 100 ppm / K ◎: 100 ppm / K or more, less than 120 ppm / K ○: 120 ppm / K or more, less than 130 ppm / K Δ: 130 ppm / K or more, 140 ppm / K <Tensile strength>
◎: Improved by 140% or more compared to PP alone ◎: Improved by 130% or more compared to PP alone ○: Improved by 120% or more compared to PP alone Δ: Improved by 110% or more compared to PP alone <Tensile elongation>
◎: 200% or more improvement over PP alone ○: 150% or more improvement over PP alone △: 130% or more improvement over PP alone

(Example 15)
Using cellulose preparation A of Example 1, as a resin composition, 12.5 parts by weight of the cellulose preparation, 0.5 parts by weight of maleic acid-modified PP, and PP as the rest are added. The resin composition was similarly prepared and evaluated using a small kneader with the mass ratio of / maleic acid-modified PP changed to 95/5. The results are shown in Table 5.

(Example 16)
Using the cellulose preparation A of Example 1 and changing the resin composition to 12.5 parts by weight of the cellulose preparation, 1.1 parts by weight of the maleic acid-modified PP, and adding PP as the rest to 100 parts by weight, A resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 5.

(Example 17)
Using the cellulose preparation A of Example 1, as a resin composition, 12.5 parts by weight of the cellulose preparation, 1.8 parts by weight of the maleic acid-modified PP, and the remainder is changed to 100 parts by weight of PP, A resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 5.

(Example 18)
Using the cellulose preparation A of Example 1, the resin composition was changed to 12.5 parts by weight of the cellulose preparation, 2.5 parts by weight of the maleic acid-modified PP, and the remaining PP was added to 100 parts by weight. A resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 5.

(Example 19)
Using the cellulose preparation A of Example 1, the resin composition was changed to 12.5 parts by weight of the cellulose preparation, 8.5 parts by weight of maleic acid-modified PP, and the remaining PP was added to 100 parts by weight. A resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 6.

(Example 20)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3 parts by mass, and a part of PP was replaced with polyamide 6 (Toray 0.1 parts by mass of Amilan CM1007) manufactured by Co., Ltd. was blended, and a resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 6.

(Example 21)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 In a similar manner, a resin composition was prepared and evaluated using a small kneader. The results are shown in Table 6.

(Example 22)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 The resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 6.

(Example 23)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 The resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 6.

(Example 24)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 The resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 7.

(Example 25)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 The resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 7.

(Example 26)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 20.0 parts by mass, and a resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 7.

(Example 27)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 30.0 parts by mass of this was blended, and a resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 7.

(Example 28)
In the resin composition composition of Example 1, the amount of cellulose preparation A was fixed at 12.5 parts by mass, the amount of maleic acid-modified PP was fixed at 3.0 parts by mass, and a part of PP was replaced to obtain polyamide 6 75.0 parts by mass of the resin composition was similarly prepared and evaluated using a small kneader. The results are shown in Table 7.

  As a result, the resin compositions of Examples 14 to 28, in which maleic acid-modified PP as an interface forming agent was blended in an amount of 1% by mass or more in terms of the mass ratio of cellulose, the linear expansion coefficient, tensile strength, and tensile elongation were all PP. It was better than alone.

(Example 29)
In the production method of the cellulose preparation of Example 2, as an organic component, polyoxyethylene alkylphenyl ether (Aoki Yushi Kogyo Co., Ltd. Braunon N-515 static surface tension 34.8 mN / m, dynamic surface tension 40.9 mN / m The cellulose preparation Q was obtained in the same manner as in Example 2 except that the boiling point under atmospheric pressure was over 100 ° C. (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation Q, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 30)
In the production method of the cellulose preparation of Example 2, as an organic component, polyoxyethylene styrenated phenyl ether (Aoki Yushi Kogyo Co., Ltd., Braunon KTSP-16, static surface tension 39.0 mN / m, dynamic surface tension 55.8 mN / m, a cellulose preparation R was obtained by the same method as in Example 2 except that the boiling point was over 100 ° C. under normal pressure (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation R, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 31)
In the method for producing the cellulose preparation of Example 2, polyoxyethylene β naphthyl ether (Brownon BN-10, static surface tension 48.2 mN / m, dynamic surface tension 51.7 mN / m, manufactured by Aoki Yushi Kogyo Co., Ltd.) as an organic component. Cellulose preparation S was obtained in the same manner as in Example 2 except that the boiling point under atmospheric pressure was over 100 ° C. (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation S, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 32)
In the production method of the cellulose preparation of Example 2, as an organic component, polyoxyethylene bisphenol A ether (Aoki Yushi Kogyo Co., Ltd., Braunon BEO-17.5 static surface tension 49.5 mN / m, dynamic surface tension 53.1 mN Cellulose preparation T was obtained by the same method as in Example 2 except that (/ m, boiling point under atmospheric pressure> 100 ° C.) was used (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation T, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 33)
In the method for producing the cellulose preparation of Example 2, as an organic component, polyoxyethylene hydrogenated castor oil ether (Aoki Yushi Kogyo Co., Ltd., BRAUnon RCW-20, static surface tension 42.4 mN / m, dynamic surface tension 52.9 mN / m Cellulose preparation U was obtained by the same method as in Example 2 except that the boiling point under atmospheric pressure was over 100 ° C. (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation U, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 34)
In the production method of the cellulose preparation of Example 2, as an organic component, polyoxyethylene linear alkyl ether (Aoki Yushi Kogyo Co., Ltd. Braunon CH-315L static surface tension 36.7 mN / m, dynamic surface tension 62.6 mN / m, a boiling point of 100 ° C. under normal pressure) was used to obtain a cellulose preparation V in the same manner as in Example 2 (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation V, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 35)
In the method for producing the cellulose preparation of Example 2, as an organic component, polyoxyethylene phytosterol ether (Nikko Chemicals Corporation NIKKOL BPS-20, static surface tension 51.3 mN / m, dynamic surface tension 65.7 mN / m, ordinary A cellulose preparation Q was obtained in the same manner as in Example 2 except that the rolling boiling point was higher than 100 ° C. (water content 2% by mass, organic component binding rate 5% or less). Using this cellulose preparation W, a resin composition was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 8.

(Example 36)
After obtaining the cellulose preparation A by the method of Example 1, the obtained cellulose preparation was 12.5 parts by mass, polyamide 6 (PA6) (trade name UBE nylon 1013B, manufactured by Ube Industries, Ltd., and the carboxyl end group ratio was ([ COOH] / [all end groups]) = 0.6) was added at 87.5 parts by mass, and the mixture was used at 240 ° C. and 100 rpm (sialate 1570 (1) using a small kneader (product name “Xplore”) manufactured by Xplore Instruments). / S)) for 5 minutes after circulation and kneading, a strand of φ1 mm resin composition was obtained through a die. The strand was cut to a length of 1 cm at room temperature, 1 g was weighed, and a thin film having a thickness of 100 μm was obtained by hot pressing (240 ° C.). In addition, dumbbell-shaped test pieces of JIS K7127 standard were prepared from a resin obtained by melting pellets obtained from the strands (strands cut into 1 cm length) at 260 ° C. with an attached injection molding machine, and evaluated each. Used for. Each evaluation was performed using the obtained thin film, pellet, and dumbbell-shaped test piece. The results are shown in Table 8.

(Example 37)
In the production method of the cellulose preparation of Example 1, as an organic component, polyoxyethylene alkylphenyl ether (Aoki Yushi Kogyo Co., Ltd. Braunon N-515 static surface tension 34.8 mN / m, dynamic surface tension 40.9 mN / m Cellulose preparation X was obtained in the same manner as in Example 1 except that the boiling point under atmospheric pressure was over 100 ° C.). Using the obtained cellulose preparation X, a resin composition was prepared in the same manner as in Example 38 and evaluated. The results are shown in Table 8.

(Example 38)
In the production method of the cellulose preparation of Example 1, as an organic component, polyoxyethylene styrenated phenyl ether (Aoki Yushi Kogyo Co., Ltd. Braunon KTSP-16 static surface tension 39.0 mN / m, dynamic surface tension 55.8 mN / m, a cellulose preparation Y was obtained in the same manner as in Example 1 except that the boiling point under atmospheric pressure was more than 100 ° C. Using the obtained cellulose preparation X, a resin composition was prepared in the same manner as in Example 38 and evaluated. The results are shown in Table 8.

(Example 39)
In the method for producing the cellulose preparation of Example 1, polyoxyethylene β naphthyl ether (Brownon BN-10, static surface tension 48.2 mN / m, dynamic surface tension 51.7 mN / m, manufactured by Aoki Oil & Fat Co., Ltd.) as an organic component. Cellulose preparation Z was obtained in the same manner as in Example 1 except that the boiling point under atmospheric pressure was over 100 ° C.). Using the obtained cellulose preparation X, a resin composition was prepared in the same manner as in Example 38 and evaluated. The results are shown in Table 8.

(Example 40)
In the production method of the cellulose preparation of Example 1, as an organic component, polyoxyethylene bisphenol A ether (Aoki Yushi Kogyo Co., Ltd. Braunon BEO-17.5 static surface tension 49.5 mN / m, dynamic surface tension 53.1 mN Cellulose preparation α was obtained in the same manner as in Example 1, except that / m, boiling point under atmospheric pressure was higher than 100 ° C.). Using the obtained cellulose preparation X, a resin composition was prepared in the same manner as in Example 38 and evaluated. The results are shown in Table 8.

(Example 41)
In the production method of the cellulose preparation of Example 1, polyoxyethylene hydrogenated castor oil ether (Brownon RCW-20 manufactured by Aoki Oil & Fat Co., Ltd., static surface tension 42.4 mN / m, dynamic surface tension 52.9 mN / m as an organic component) Cellulose preparation β was obtained in the same manner as in Example 1 except that the boiling point under atmospheric pressure was over 100 ° C.). Using the obtained cellulose preparation X, a resin composition was prepared in the same manner as in Example 38 and evaluated. The results are shown in Table 8.

  The cellulose preparation and the resin composition of the present disclosure can be suitably applied to resin composites for various uses that have a low coefficient of linear expansion and are advantageous in performance of excellent strength and elongation at the time of tensile and bending deformation.

Claims (22)

A cellulose preparation comprising cellulose particles and a surfactant that covers at least a part of the surface of the cellulose particles,
The cellulose particles have a diameter of 500 nm or less and a major axis / minor axis ratio (L / D) of 15 or less,
The surfactant has a static surface tension of 20 mN / m or more, a dynamic surface tension of 60 mN / m or less, a solubility parameter (SP value) of 7.25 or more, and a boiling point higher than water;
The cellulose preparation which has coat | covered the said cellulose particle by the said surfactant non-covalently bonding with at least one part of the surface of the said cellulose particle . The cellulose preparation according to claim 1, wherein the 50% cumulative volume particle diameter measured by a laser diffraction particle size distribution meter is 10 μm or less. The cellulose preparation according to claim 1 or 2 , wherein an average polymerization degree of cellulose constituting the cellulose particles is 1000 or less. The cellulose formulation as described in any one of Claims 1-3 in which the cellulose which comprises the said cellulose particle contains a crystalline cellulose. The cellulose preparation according to claim 4 , wherein the average degree of polymerization of the crystalline cellulose is less than 500. The cellulose preparation according to any one of claims 1 to 5 , wherein the cellulose preparation further comprises cellulose fibers, and the average L / D of the cellulose fibers is 30 and / or the average degree of polymerization is 300 or more. The cellulose formulation as described in any one of Claims 1-6 whose ratio of the crystalline cellulose with respect to the total mass of the cellulose which exists in the said cellulose formulation is 50 mass% or more. The cellulose preparation according to any one of claims 1 to 7 , comprising 30 to 99% by mass of cellulose and 1 to 70% by mass of the surfactant. Wherein the surfactant is a rosin derivative, alkylphenyl derivatives, bisphenol A derivatives, beta-naphthyl derivatives, styrenated phenyl derivatives, and is selected from the group consisting of castor oil derivatives, according to any one of claims 1-8 Cellulose preparation. The cellulose preparation according to any one of claims 1 to 9 , wherein the surfactant is a polyoxyethylene derivative. Resin composition comprising at least 1 wt% of cellulose formulation according to any one of claims 1-10. The resin composition of Claim 11 which further contains the interface formation agent of the quantity of 1 mass part or more with respect to 100 mass parts of cellulose which exists in the said cellulose formulation. The resin composition according to claim 11 or 12 , comprising a thermoplastic resin. A resin composition comprising a thermoplastic resin, cellulose particles, a surfactant, and an interface forming agent,
The cellulose particles have a diameter of 500 nm or less and a major axis / minor axis ratio (L / D) of 15 or less,
The surfactant has a static surface tension of 20 mN / m or more, a dynamic surface tension of 60 mN / m or less, a solubility parameter (SP value) of 7.25 or more, and a boiling point higher than water;
The surfactant coats the cellulose particles by non-covalently bonding to at least a part of the surface of the cellulose particles,
The resin composition whose quantity of the said interface formation agent is 1 mass part or more with respect to 100 mass parts of cellulose which exists in a resin composition. The resin composition according to claim 14 , wherein the cellulose particles have a 50% cumulative volume particle diameter of 10 μm or less as measured by a laser diffraction particle size distribution meter. The resin composition according to claim 14 or 15 , wherein an average degree of polymerization of cellulose constituting the cellulose particles is 1000 or less. Comprising said cellulose crystalline cellulose constituting the cellulose particles, the resin composition according to any one of claims 14-16. The resin composition according to claim 17 , wherein the average degree of polymerization of the crystalline cellulose is less than 500. The resin composition according to any one of claims 14 to 18 , wherein the resin composition further comprises cellulose fibers, and the average L / D of the cellulose fibers is 30 or more and / or the average degree of polymerization is 300 or more. object. The resin composition according to any one of claims 14 to 19 , wherein the ratio of crystalline cellulose to the total mass of cellulose present in the resin composition is 50 mass% or more. The total amount of cellulose in the resin composition and the total amount of the surfactant is 100% by mass, the amount of the cellulose is 30 to 99% by mass, and the amount of the surfactant is 1 to 70% by mass. The resin composition according to any one of claims 14 to 20 , which is 22. The surfactant according to any one of claims 14 to 21 , wherein the surfactant is selected from the group consisting of rosin derivatives, alkylphenyl derivatives, bisphenol A derivatives, β-naphthyl derivatives, styrenated phenyl derivatives, and hardened castor oil derivatives. Resin composition.