Granules, resin composition, and production methods and uses for these

Abstract

Provided are granules which are excellent in terms of handleability and feedability to kneaders and of the dispersability of a plant-derived fibrous filler in resins or rubbers. The granules comprise a plant-derived fibrous filler (A) having an average fiber diameter of 0.5-100 μm and an organic material (B) which is solid at normal temperature and normal pressure and has a molecular weight of 100-1,000, and have a bulk density of 0.1-0.5 g / cm3. The organic material (B) may be a non-fibrous material having a melting point of 100°C or higher. The organic material (B) may be a compound having a polar group and a hydrophobic skeleton such as a polycyclic aromatic ring. The fibrous filler (A) may be cellulose fibers. The granules may be kneaded together with a resin or a rubber to produce a composition.

Description

Granules and resin compositions, and methods for producing them and uses

[0001] The present disclosure relates to a granule and a resin composition containing a plant-derived filler, as well as methods for producing the same and uses thereof.

[0002] Cellulose, a plant-derived fiber, has a low environmental impact, is a sustainable resource, and has excellent properties such as a high modulus of elasticity, high strength, and a low coefficient of linear expansion. Therefore, it is used in a wide range of applications, such as materials for paper, films, and sheets, and resin composite materials (e.g., as a reinforcing agent for resins). Furthermore, cellulose is added to rubber compositions as a reinforcing agent to improve the mechanical properties of the rubber. Therefore, various methods have been proposed for uniformly dispersing cellulose in resins and rubbers.

[0003] Japanese Patent Laid-Open Publication No. 2019-178266 (Patent Document 1) discloses a composite to be blended into a resin, which comprises cellulose and a coating layer that covers at least a portion of the surface of the cellulose and contains a fluorene compound having multiple hydroxyl groups. In this document, a resin composition is produced by melt-kneading a wet composite containing cellulose nanofibers and a fluorene compound with polypropylene.

[0004] Japanese Patent Laid-Open Publication No. 2020-128475 (Patent Document 2) discloses a hybrid filler for resin mixing containing a composite of cellulose fibers and fine particles, including inorganic particles such as silica, triiron tetroxide, and graphene.

[0005] Japanese Patent Laid-Open Publication No. 2022-001631 (Patent Document 3) discloses a method for producing a dry powder of cellulose fibers to be mixed with a resin, which includes a slurry preparation step of preparing a slurry containing cellulose fibers and water, and a granulation step of stirring the slurry under reduced pressure to form a dry powder of the cellulose fibers, and in the granulation step, chopper-pulverizing the cellulose fiber particles formed by the stirring.

[0006] Japanese Patent Laid-Open No. 2022-169489 (Patent Document 4) and Japanese Patent Laid-Open No. 2022-169490 (Patent Document 5) disclose a method for producing a dried body to be mixed with a thermoplastic resin, which includes a drying and granulation step of removing the liquid from a dispersion containing fine cellulose fibers, a dispersant, and a liquid to obtain a dried body.

[0007] Japanese Patent Laid-Open Publication No. 2022-184494 (Patent Document 6) discloses a method for producing a cellulose fiber composite resin raw material used in the production of a cellulose fiber composite resin molding, in which undefibrated hydrophobically modified cellulose, a solvent, and a particulate thermoplastic resin are shear-mixed to defibrate the cellulose and compound it with the particulate thermoplastic resin to obtain the cellulose fiber composite resin raw material.

[0008] JP 2019-178266 A JP 2020-128475 A JP 2022-001631 A JP 2022-169489 A JP 2022-169490 A JP 2022-184494 A

[0009] However, even when the composites of Patent Documents 1 and 2 are blended with a resin or rubber, it is difficult to uniformly disperse cellulose in the resin or rubber. Moreover, even when thermoplastic resin compositions are prepared by the manufacturing methods of Patent Documents 3 to 6, the handling properties are poor for uniformly dispersing cellulose, and it is difficult to prepare a composition in which cellulose is highly dispersed in the thermoplastic resin.

[0010] Therefore, an object of the present invention is to provide a granule and a resin composition which are excellent in handleability and feedability to a kneader, and which exhibit excellent dispersibility of a plant-derived fibrous filler in a resin or rubber, as well as methods for producing the same and uses thereof.

[0011] As a result of intensive research into achieving the above object, the present inventors have combined a plant-derived fibrous filler (A) having an average fiber diameter of 0.5 to 100 μm with an organic material (B) that is solid at room temperature and normal pressure and has a molecular weight of 100 to 1000, and have achieved a bulk density of 0.1 to 0.5 g / cm ３The present inventors have found that by adjusting the composition to the above range, it is possible to provide granules that are easy to handle and feed into a kneader, and that exhibit excellent dispersibility of the plant-derived filler in resin or rubber, and have completed the present invention.

[0012] That is, the granules according to embodiment [1] of the present disclosure (or the present invention) contain a plant-derived fibrous filler (A) and an organic material (B), and have a bulk density of 0.1 to 0.5 g / cm ３ The granules are as follows: wherein the fibrous filler (A) has an average fiber diameter of 0.5 to 100 μm; the organic material (B) is solid at room temperature and normal pressure; and the molecular weight of the organic material (B) is 100 to 1,000.

[0013] Aspect [2] of the present disclosure is an aspect of the aspect [1], in which the proportion of the organic material (B) is 1 to 70 parts by mass per 100 parts by mass of the fibrous filler (A).

[0014] Aspect [3] of the present disclosure is an aspect of the above-described aspect [1] or [2], wherein the granules are used for kneading with a resin or rubber.

[0015] Aspect [4] of the present disclosure is any one of aspects [1] to [3], wherein the organic material (B) is a non-fibrous organic material having a melting point of 100° C. or higher.

[0016] Aspect [5] of the present disclosure is an aspect of any one of aspects [1] to [4], in which the organic material (B) is a compound having a hydrophobic skeleton and a polar group.

[0017] Aspect [6] of the present disclosure is an aspect of the above aspect [5], in which the hydrophobic skeleton is a polycyclic aromatic ring.

[0018] Aspect [7] of the present disclosure is any one of aspects [1] to [6], wherein the organic material (B) is a compound represented by the following formula (1):

[0019]

[0020] (wherein ring Z is an arene ring, R １ and R ２ is a substituent, X １represents a heteroatom-containing functional group, k represents an integer of 0 to 4, n represents an integer of 1 or more, and p represents an integer of 0 or more.

[0021] Aspect [8] of the present disclosure is directed to the above-described aspect [7], wherein in the formula (1), X １ But the group -(OA) ｍ１ In this embodiment, the group is —OH (wherein A represents an alkylene group, and m1 represents an integer of 0 or more).

[0022] Aspect [9] of the present disclosure is any one of aspects [1] to [8], in which the fibrous filler (A) is a cellulose fiber.

[0023] The present disclosure also includes, as aspect

[10] , a method for producing a granule of any of aspects [1] to [9], comprising: a mixing step of mixing a precursor of the plant-derived fibrous filler (A), a precursor of the organic material (B), and water to obtain a mixture; and a granulation step of granulating the obtained mixture to obtain a granule.

[0024] An embodiment

[11] of the present disclosure is an embodiment in which the mixture is extrusion-granulated in the granulation step of the embodiment

[10] .

[0025] The present disclosure also includes, as aspect

[12] , a resin composition comprising the granules of any one of aspects [1] to [9] and a resin.

[0026] Aspect

[13] of the present disclosure is an aspect of the aspect

[12] , in which the resin is a thermoplastic resin.

[0027] The present disclosure also includes, as aspect

[14] , a method for producing a resin composition, comprising a resin kneading step of kneading the granules of any one of aspects [1] to [9] with a resin.

[0028] The present disclosure also includes, as an aspect

[15] , a molded article of the resin composition of the aspect

[12] or

[13] , which is a part or material selected from automobile parts, electric / electronic parts, building materials, civil engineering materials, agricultural materials, packaging materials, household materials, and optical components.

[0029] The present disclosure also includes, as an aspect

[16] , a rubber composition comprising the granules of any one of the aspects [1] to [9] and rubber.

[0030] The present disclosure also includes, as an aspect

[17] , a method for producing a rubber composition, including a rubber kneading step of kneading the granules of any one of the aspects [1] to [9] with rubber.

[0031] The present disclosure also includes, as an aspect

[18] , a molded article of a vulcanizate of the rubber composition of the aspect

[16] , which is a belt, a roll, a gasket, an oil seal, a packing, a hose, a window frame rubber, a vibration damping material, a carpetbagging material, an automotive part, a tire, or an electric wire coating.

[0032] In this specification and claims, the number of carbon atoms in a substituent is represented by C １ , C ６ , C １０ For example, "C １ "Alkyl group" means an alkyl group having one carbon atom, ６－１０ The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms.

[0033] Furthermore, in this specification and claims, when a numerical range is indicated using "to", it is intended to include both ends of the range.

[0034] The present disclosure can provide granules that are easy to handle and feed into a kneader, and that have excellent dispersibility of plant-derived fibrous fillers in resins and rubbers.

[0035] The granules (or granulated matter) of the present disclosure are obtained by combining a plant-derived fibrous filler (A) having an average fiber diameter of 0.5 to 100 μm with an organic material (B) that is solid at room temperature and normal pressure and has a molecular weight of 100 to 1000, and have a bulk density of 0.1 to 0.5 g / cm ３ Since the granules of the present disclosure are adjusted to the above range, they have excellent handleability and feedability to a kneader, and the plant-derived fibrous filler (A) can be uniformly dispersed in resins and rubbers. Furthermore, by using the granules of the present disclosure, the fibrous filler (A) can be uniformly dispersed in various resins and rubbers without preparing a masterbatch.

[0036] [Plant-derived fibrous filler (A)] The plant-derived fibrous filler (A) is a filler (a bulking agent or a reinforcing agent) made from a plant, and is not particularly limited as long as it is fibrous.

[0037] Plant raw materials are not particularly limited and include wood, herbs, seed hairs, bamboo, sugarcane, etc. Wood includes conifers such as pine, fir, spruce, hemlock, and cedar; and broad-leaved trees such as beech, birch, poplar, and maple. Herbs include hemp, flax, Manila hemp, ramie, and other hemp species; straw; bagasse; Mitsumata, etc. Seed hairs include cotton linter, bombax cotton, and kapok.

[0038] The plant raw material may be waste paper, straw, food residue, etc. Examples of food residue include tea extract residue, coffee bean extract residue, grain husks, citrus peels, sugarcane residue, and bean skins.

[0039] These plant materials can be used alone or in combination of two or more. The plant material is preferably pulp with a low content of non-cellulose components such as lignin and hemicellulose. Commonly used pulps include wood pulps such as softwood pulp and hardwood pulp, and seed fiber pulps such as cotton linter pulp.

[0040] The fibrous filler (A) of the present disclosure is preferably formed from these plant materials, with cellulose fibers (fibrous cellulose) being particularly preferred.

[0041] The cellulose fibers may be highly crystalline, and the degree of crystallinity of the cellulose fibers is, for example, 40 to 100% (e.g., 50 to 100%), preferably 60 to 100%, more preferably 70 to 100%, and most preferably 75 to 99%. Typically, the degree of crystallinity is 60% or more (e.g., 60 to 98%). Examples of the crystalline structure of the cellulose fibers include type I, type II, type III, and type IV, with type I crystalline structure being preferred due to its excellent linear expansion properties and elastic modulus. The degree of crystallinity can be measured using a powder X-ray diffractometer (e.g., "Ultima IV" manufactured by Rigaku Corporation).

[0042] The cellulose fibers may contain non-cellulose components such as hemicellulose and lignin, and the proportion of the non-cellulose components in the fibrous cellulose is 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. The cellulose fibers may be cellulose fibers that are substantially free of non-cellulose components (particularly, cellulose fibers that do not contain non-cellulose components).

[0043] The degree of polymerization of the cellulose fibers may be 500 or more, preferably 600 or more (for example, 600 to 100,000) in terms of the mechanical properties of the composition.

[0044] The average fiber diameter of the fibrous filler (A) (particularly cellulose fibers) may be 0.5 to 100 μm, but is preferably on the order of microns, for example, 1 to 80 μm, preferably 5 to 70 μm, more preferably 10 to 50 μm, and most preferably 30 to 45 μm. If the average fiber diameter is too small, when the granules are blended with a resin or rubber and kneaded, the fibrous filler (A) may aggregate, making it difficult to uniformly disperse the fibrous filler (A). Conversely, if the average fiber diameter is too large, when the granules are blended with a resin or rubber and kneaded, the fibrous filler (A) may rise to the surface of the kneaded product, deteriorating the appearance.

[0045] The average fiber length of the fibrous filler (A) (particularly cellulose fibers) can be selected from a range of about 1 μm or more (e.g., 1 μm to 100 mm), for example, 10 μm or more (e.g., 0.01 to 50 mm), preferably 100 μm or more (e.g., 0.1 to 30 mm), even more preferably 300 μm or more (e.g., 0.3 to 20 mm), more preferably 500 μm or more (e.g., 0.5 to 10 mm), and most preferably 1 mm or more (e.g., 1 to 5 mm). If the average fiber length is too short, there is a risk that the mechanical properties will not be sufficiently improved even if the granules are blended with a resin or rubber. Conversely, if the average fiber length is too long, there is a risk that it will be difficult to uniformly disperse the fibrous filler (A) even if the granules are blended with a resin or rubber.

[0046] The ratio (aspect ratio) of the average fiber length to the average fiber diameter of the fibrous filler (A) (particularly cellulose fibers) is, for example, 5 or more (e.g., 5 to 10,000), preferably 10 or more (e.g., 10 to 5,000), further preferably 15 or more (e.g., 15 to 3,000), more preferably 20 or more (e.g., 20 to 100), and most preferably 25 or more (e.g., 25 to 50). If the aspect ratio is too small, the reinforcing effect may be reduced even when the granules are blended with a resin or rubber, whereas if the aspect ratio is too large, uniform dispersion of the fibrous filler (A) may be difficult even when the granules are blended with a resin or rubber.

[0047] In this specification and claims, the average fiber diameter, average fiber length, and aspect ratio of the fibrous filler (A) (particularly, cellulose fibers) may be calculated by averaging 50 fibers randomly selected from a scanning electron microscope image. The average fiber diameter, average fiber length, and aspect ratio of the fibrous filler (A) (particularly, cellulose fibers) are the average fiber diameter, average fiber length, and aspect ratio of the fibrous filler (A) in the granules obtained by extrusion granulation.

[0048] The proportion of the fibrous filler (A) (particularly cellulose fiber) in the granules may be 10% by mass or more, for example, 10 to 99% by mass, preferably 30 to 95% by mass, further preferably 50 to 90% by mass, more preferably 60 to 85% by mass, and most preferably 70 to 80% by mass. If the proportion of the fibrous filler (A) is too low, even if the granules are blended with a resin or rubber, the reinforcing effect of the fibrous filler (A) may be weakened, and the mechanical properties of the resin or rubber composition may not be improved. If the proportion is too high, it may be difficult to prepare the granules or the dispersibility of the fibrous filler (A) may be reduced.

[0049] [Organic Material (B)] The granules of the present disclosure can ensure granulation properties by blending an organic material (B) with the fibrous filler (A).

[0050] Since the organic material (B) is solid at room temperature and normal pressure, it is easy to handle, granules can be easily prepared, and when the granules are blended with a resin or rubber, the dispersibility of the fibrous filler (A) can be improved, eliminating the need to prepare a masterbatch for each resin or rubber. Note that the room temperature may be 20°C, and the normal pressure may be atmospheric pressure (101.3 kPa).

[0051] The molecular weight of the organic material (B) is 100 to 1,000, preferably 150 to 700, further preferably 200 to 500, even more preferably 300 to 500, and most preferably 400 to 500. If the molecular weight is too small, when the granules are blended with a resin or rubber and kneaded, the organic material (B) may volatilize, making it difficult to uniformly disperse the fibrous filler (A). Conversely, if the molecular weight is too large, there is a risk that the compatibility of the granules with the resin or rubber may decrease.

[0052] The shape of the organic material (B) is not particularly limited, but may be non-fibrous, and is preferably granular (or powdery). The granular shape may be spherical, approximately spherical, ellipsoidal, polygonal or polyhedral, flat, rod-like or columnar, or irregular. Of these, isotropic shapes such as spherical, and approximately isotropic shapes such as approximately spherical are preferred. Therefore, in the granular organic material, the ratio of the major axis to the minor axis (aspect ratio) is preferably close to 1, for example, 1 to 3, preferably 1 to 2, more preferably 1 to 1.5, more preferably 1 to 1.3, and most preferably 1 to 1.2.

[0053] The average particle size (D50) of the organic material (B) is, for example, 0.01 to 50 μm, preferably 0.1 to 30 μm, further preferably 0.5 to 20 μm, even more preferably 1 to 10 μm, and most preferably 2 to 5 μm. If the average particle size of the organic material (B) is too small, it may be difficult to mix it uniformly with the fibrous filler (A), whereas if it is too large, it may be difficult to prepare granules.

[0054] In this specification and claims, the average particle size of the organic material (B) can be measured by a conventional method, and means, for example, the median particle size (D50) measured on a volume basis using a laser diffraction particle size distribution analyzer.

[0055] The organic material (B) is preferably a compound having a polar group because it can improve affinity with the fibrous filler (A), and is particularly preferably a compound having a hydrophobic skeleton and a polar group because it is easy to handle.

[0056] Examples of the polar group include a hydroxyl group, a carboxyl group, an acyl group, an alkoxy group, a glycidyloxy group, an amino group, an N-substituted amino group, an amide group, a mercapto group, a halogen atom, and a cyano group. Examples of the acyl group include C groups such as an acetyl group and a propionyl group. １－４ Examples of the alkoxy group include a C alkoxy group such as a methoxy group and an ethoxy group. １－４ Examples of the N-substituted amino group include N-mono C groups such as methylamino and ethylamino groups. １－４ Examples of the polar groups include alkylamino groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. These polar groups may be derivatives such as salts or esters. These polar groups may be used alone or in combination of two or more. Of these, hydroxyl groups, carboxyl groups, amino groups, and amide groups are preferred, with hydroxyl groups being particularly preferred. The number of polar groups in one molecule of the organic material (B) may be one or more, and is, for example, 1 to 6, preferably 1 to 4, more preferably 1 to 3, and even more preferably 2.

[0057] Examples of the hydrophobic skeleton include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.

[0058] Examples of aliphatic hydrocarbons include C hexane, heptane, octane, decane, undecane, dodecane, pentadecane, and octadecane. ６－２４ Alkanes: C such as hexene, octene, decene, undecene, dodecene, pentadecene, and octadecene ６－２４ These aliphatic hydrocarbons can be used alone or in combination of two or more. Among these, C alkene such as octadecane is preferred. １２－２４ Alkanes are preferred.

[0059] Examples of aromatic hydrocarbons include monocyclic arene rings such as benzene rings; fused bicyclic C rings such as naphthalene rings; １０－１６ Arene ring; fused tricyclic ring such as anthracene ring, phenanthrene ring, etc. １２－１６ arene rings; biphenyl rings, binaphthyl rings, phenylnaphthalene rings (1-phenylnaphthalene rings, 2-phenylnaphthalene rings, etc.) and other bi-C rings ６－１２ arene ring; terphenylene ring, etc. ６－１２ These aromatic hydrocarbons can be used alone or in combination of two or more. Among these, fused bicyclic C rings such as benzene rings and naphthalene rings are preferred. １０－１６ arene ring; biphenyl ring, etc. ６－１０ An arene ring or a fluorene ring is preferred.

[0060] Examples of alicyclic hydrocarbons include hydrogenated aromatic hydrocarbons, as well as cyclopentane rings, cycloheptane rings, tetralin rings, etc. These alicyclic hydrocarbons can be used alone or in combination of two or more. Among these, C cyclohexane and other C cyclohexanes are preferred. ６－１０ A cycloalkane ring is preferred.

[0061] The hydrophobic skeleton may be at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, or may be a combination of two or more selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.

[0062] When the hydrophobic skeleton is a combination of two or more hydrocarbons selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, the hydrocarbons may be linked to each other by a direct bond or via a linking group. Examples of the linking group include an alkylene group, an ether group (ether bond), a thioether group (sulfide group), and a sulfonyl group. Examples of the alkylene group of the linking group include C groups such as a methylene group, an ethylidene group, an ethylene group, and an isopropylidene group. １－４The combination of these hydrocarbons is not particularly limited as long as the molecular weight does not exceed 1,000, but a combination of aromatic hydrocarbons is preferred, and a combination of a fluorene ring and at least one arene ring selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring is particularly preferred.

[0063] Commonly used compounds having a hydrophobic skeleton and a polar group include fatty acids or derivatives thereof, bisphenols, and fluorene compounds.

[0064] Fatty acids include palmitic acid, stearic acid, hydroxystearic acid, arachidic acid, behenic acid, montanic acid, and other C ８－２６ Saturated fatty acids: C, such as oleic acid and erucic acid ８－２６ Examples of fatty acid derivatives include fatty acid amides and fatty acid alkyl esters corresponding to these fatty acids. Examples of fatty acid alkyl esters include C methyl esters, ethyl esters, and the like. １－４ Alkyl esters and the like.

[0065] Examples of bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 2,2-bis(3-methyl-4-hydroxyphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol AD), bis(4-hydroxyphenyl)methane (bisphenol F), 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane (bisphenol G), bis(4-hydroxyphenyl)sulfone (bisphenol S), and 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z). Bisphenols include C ２－４ The alkylene oxide may be an alkylene oxide adduct in which alkylene oxide is added. The number of moles of alkylene oxide added is, for example, 1 to 10 moles, preferably 1 to 5 moles, and more preferably 1 to 3 moles.

[0066] (Organic material containing a polycyclic aromatic ring) In the granules of the present disclosure, when the granules are compounded with a resin or rubber and kneaded, the fibrous filler (A) can be uniformly dispersed, and the mechanical properties such as the strength and elastic modulus of the kneaded resin composition or rubber composition can be improved. From these points of view, the organic material (B) is preferably an organic material containing a polycyclic aromatic ring (an organic material whose hydrophobic skeleton is a polycyclic aromatic ring), more preferably an organic material containing a fluorene ring, even more preferably a fluorene compound having aryl groups at the 9,9-positions, and most preferably a compound represented by formula (1).

[0067] In the formula (1), examples of the arene ring represented by ring Z include monocyclic arene rings such as a benzene ring, and polycyclic arene rings. Examples of polycyclic arene rings include fused polycyclic arene rings (fused polycyclic hydrocarbon rings) and ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings).

[0068] The fused polycyclic arene ring includes, for example, a fused bicyclic arene ring (e.g., a fused bicyclic C ring such as a naphthalene ring). １０－１６ and fused bicyclic to tetracyclic arene rings such as fused tricyclic arenes (e.g., anthracene ring, phenanthrene ring, etc.). Preferred fused polycyclic arene rings include a naphthalene ring and an anthracene ring, with a naphthalene ring being particularly preferred.

[0069] Examples of the ring-assembled arene ring include biarene rings [for example, biphenyl rings, binaphthyl rings, phenylnaphthalene rings (for example, 1-phenylnaphthalene rings, 2-phenylnaphthalene rings, etc.)] ６－１２ arene ring, etc.], terarene ring (e.g., ter C such as terphenylene ring) ６－１２ Examples of preferred ring-assembly arene rings include biC ６－１０ Examples include an arene ring, particularly a biphenyl ring.

[0070] The two rings Z substituted at the 9-position of fluorene may be different or the same, but are usually the same ring in many cases. Among the rings Z, a benzene ring, a naphthalene ring, a biphenyl ring (particularly a benzene ring), etc. are preferred.

[0071] The substitution position of ring Z at the 9-position of fluorene is not particularly limited. For example, when ring Z is a naphthalene ring, the group corresponding to ring Z at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like.

[0072] X １ Examples of heteroatom-containing functional groups represented by the formula (1) include functional groups having at least one heteroatom selected from oxygen, sulfur, and nitrogen atoms. The number of heteroatoms contained in such functional groups is not particularly limited, but may generally be 1 to 3, and preferably 1 or 2.

[0073] The functional group may be, for example, a group -[(OA) ｍ１ -Y １ ] (In the formula, Y １ is a hydroxyl group, a glycidyloxy group, an amino group, an N-substituted amino group, or a mercapto group, A is an alkylene group, and m1 is an integer of 0 or more), a group -(CH ２ ) ｍ２ -COOR ３ (In the formula, R ３ represents a hydrogen atom or an alkyl group, and m2 represents an integer of 0 or more.

[0074] Group - [(OA) ｍ１ -Y １ ], where Y １ Examples of the N-substituted amino group include N-monoalkylamino groups (N-monoC groups) such as methylamino and ethylamino groups. １－４ N-monohydroxyalkylamino groups (N-monohydroxy C alkylamino groups, etc.), hydroxyethylamino groups, etc. １－４ alkylamino groups, etc.).

[0075] The alkylene group A includes a linear or branched alkylene group, and examples of the linear alkylene group include C alkylene groups such as an ethylene group, a trimethylene group, and a tetramethylene group. ２－６ Alkylene group (preferably linear C ２－４ Alkylene group, more preferably linear C ２－３Examples of the branched alkylene group include a branched C alkylene group such as a propylene group, a 1,2-butanediyl group, and a 1,3-butanediyl group. ３－６ Alkylene group (preferably branched C ３－４ alkylene groups, particularly propylene groups).

[0076] m1, which indicates the number of repetitions of the oxyalkylene group (OA) (average number of moles added), can be selected from the range of 0 or more (e.g., 0 to 15, preferably 0 to 10), and may be, for example, 0 to 8 (e.g., 1 to 8), preferably 0 to 5 (e.g., 1 to 5), more preferably 0 to 4 (e.g., 1 to 4), particularly 0 to 3 (e.g., 1 to 3), and may usually be 0 to 2 (e.g., 0 to 1). When m1 is 2 or more, the types of alkylene groups A may be the same or different. Furthermore, the types of alkylene groups A in the same or different rings Z may be the same or different.

[0077] Group -(CH ２ ) ｍ２ -COOR ３ In this case, R ３ Examples of the alkyl group represented by the formula (I) include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group. １－６ Examples of the alkyl group include C １－４ Alkyl groups, especially C １－２ It is an alkyl group. m2, which indicates the number of repeating methylene groups (average number of moles added), is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. m2 may usually be 0 or 1 or 2.

[0078] Among these, the group X is preferred because it can greatly improve the dispersibility of the fibrous filler (A). １ Is Y １ is a hydroxyl group -[(OA) ｍ１ —OH] [wherein A is a C group such as an ethylene group] ２－６ Alkylene groups (e.g., C ２－４ Alkylene groups, especially C ２－３ alkylene group), and m1 is an integer of 0 to 5 (for example, 0 or 1).

[0079] In the formula (1), the group X substituted on the ring Z １ The number n is 1 or more, preferably 1 to 3, and more preferably 1 or 2 (particularly 1). The number n of substitutions in each ring Z may be the same or different.

[0080] Group X １ can be substituted at an appropriate position on ring Z. For example, when ring Z is a benzene ring, it is often substituted at at least one selected from the group consisting of the 2-, 3- and 4-positions of the phenyl group (particularly the 3- and / or 4-positions, especially the 4-position). When ring Z is a naphthalene ring, it is often substituted at any one of the 5- to 8-positions of the naphthyl group. For example, the 9-position of the fluorene is substituted at the 1- or 2-position of the naphthalene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and the group X can be substituted at the 1,5-position, 2,6-position, etc. (particularly when n is 1, 2,6-position relationship) with respect to this substitution position. １ In addition, when n is 2 or more, the substitution position is not particularly limited. In addition, in the ring assembly arene ring Z, the group X １ The substitution position of is not particularly limited, and may be substituted on the arene ring bonded to the 9-position of the fluorene and / or on the arene ring adjacent to this arene ring. For example, the 3- or 4-position of the biphenyl ring Z may be bonded to the 9-position of the fluorene, and when the 3-position of the biphenyl ring Z is bonded to the 9-position of the fluorene, the group X １ The substitution position may be any of the 2-, 4-, 5-, 6-, 2'-, 3'-, and 4'-positions, and preferably the 6-position.

[0081] In the formula (1), the substituent R ２ Examples of the alkyl group include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (a linear or branched C group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, or a t-butyl group), １－１０ an alkyl group, preferably a linear or branched C １－６ alkyl group, more preferably a linear or branched C １－４alkyl group, cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.) ５－１０ cycloalkyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl (tolyl) group, dimethylphenyl (xylyl) group, etc.), biphenyl group, naphthyl group, etc. ６－１２ aryl group], aralkyl group (C such as benzyl group, phenethyl group) ６－１０ Aryl-C １－４ alkyl groups, alkoxy groups (e.g., methoxy groups, ethoxy groups, propoxy groups, n-butoxy groups, isobutoxy groups, t-butoxy groups, and other linear or branched C １－１０ alkoxy groups, cycloalkoxy groups (e.g., cyclohexyloxy groups, etc.) ５－１０ cycloalkoxy groups, etc.), aryloxy groups (e.g., phenoxy groups, etc.) ６－１０ aryloxy group, aralkyloxy group (e.g., benzyloxy group, etc.) ６－１０ Aryl-C １－４ alkyloxy group, alkylthio group (e.g., methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc.) １－１０ alkylthio groups, cycloalkylthio groups (e.g., cyclohexylthio groups, etc.) ５－１０ cycloalkylthio groups, arylthio groups (e.g., thiophenoxy groups, etc.) ６－１０ arylthio group, aralkylthio group (e.g., benzylthio group, etc.) ６－１０ Aryl-C １－４ alkylthio groups, acyl groups (e.g., acetyl groups, etc.) １－６ acyl group, a nitro group, a cyano group, etc.

[0082] These substituents R ２ Representative examples of the substituent R include a halogen atom, a hydrocarbon group (an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group), an alkoxy group, an acyl group, a nitro group, a cyano group, and a substituted amino group. ２ Examples of the alkyl group include linear or branched C alkyl groups, alkoxy groups (e.g., methoxy groups), and the like. １－４Alkoxy groups, etc.), in particular alkyl groups (especially straight-chain or branched C groups such as methyl groups, １－４ The substituent R is preferably an alkyl group. ２ is an aryl group, the substituent R ２ may form the ring assembly arene ring together with the ring Z. ２ The types of may be the same or different in the same or different rings Z.

[0083] Substituent R ２ The coefficient p can be appropriately selected depending on the type of ring Z, and may be, for example, an integer of about 0 to 8, an integer of 0 to 4, preferably an integer of 0 to 3 (e.g., 0 to 2), and more preferably 0 or 1. In particular, when p is 1, the ring Z is a benzene ring, a naphthalene ring, or a biphenyl ring, and the substituent R ２ may be a methyl group.

[0084] Substituent R １ Examples of the alkyl group include a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, or a bromine atom), a carboxyl group, and an alkoxycarbonyl group (such as a methoxycarbonyl group). １－４ alkoxy-carbonyl group, etc.), alkyl group (C such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, etc. １－６ alkyl group), aryl group (phenyl group, etc. ６－１０ aryl groups).

[0085] These substituents R １ Among these, linear or branched C １－４ Alkyl groups (especially C groups such as methyl groups) １－３ alkyl group), carboxyl group or C １－２ An alkoxy-carbonyl group, a cyano group, or a halogen atom is preferred. The number of substitutions k is an integer of 0 to 4 (e.g., 0 to 3), preferably an integer of 0 to 2 (e.g., 0 or 1), and particularly 0. The numbers of substitutions k may be the same or different, and when k is 2 or more, the number of substituents R １ The types of substituents R substituted on the two benzene rings of the fluorene ring may be the same or different. １The types of the substituents R may be the same or different. １ The substitution position of is not particularly limited, and may be, for example, the 2- to 7-positions (such as the 2-, 3-, and / or 7-positions) of the fluorene ring.

[0086] Among these, preferred fluorene compounds include 9,9-bis(hydroxyphenyl)fluorene, 9,9-bis(5-hydroxy-1-naphthyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, and other 9,9-bis(hydroxyphenyl)fluorene compounds. ６－１２ 9,9-bis(di- or trihydroxy C aryl)fluorene, such as 9,9-bis(3,4-dihydroxyphenyl)fluorene; ６－１２ 9,9-bis(mono or di C aryl)fluorene such as 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene and 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)fluorene; １－４ Alkyl-hydroxy C ６－１２ 9,9-bis(aryl)fluorene such as 9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene and 9,9-bis(4-phenyl-3-hydroxyphenyl)fluorene; ６－１２ Aryl-hydroxy C ６－１２ 9,9-bis(hydroxy(poly)C such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene; ２－４ Alkoxy-C ６－１２ 9,9-bis(mono or di C aryl)fluorene such as 9,9-bis[3-methyl-4-(2-hydroxyethoxy)phenyl]fluorene; １－４ Alkyl-hydroxy(poly)C ２－４ Alkoxy-C ６－１２ aryl)fluorene; 9,9-bis(C aryl)fluorene such as 9,9-bis[3-phenyl-4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-phenyl-3-(2-hydroxyethoxy)phenyl]fluorene; ６－１２ Aryl-hydroxy(poly)C ２－４ Alkoxy-C６－１２ Particularly preferred fluorene compounds include 9,9-bis(hydroxy(poly)C) such as 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF). ２－４ 9,9-bis(hydroxy(poly)C such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF), ２－４ 9,9-bis(phenyl-hydroxy(poly)C such as 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPPEF) ２－４ alkoxy-phenyl)fluorene, most preferably 9,9-bis(hydroxy(poly)C such as BPEF ２－４ alkoxy-phenyl)fluorene.

[0087] These fluorene compounds can be used alone or in combination of two or more. The term "(poly)alkoxy" is used to mean both an alkoxy group and a polyalkoxy group.

[0088] The proportion of the fluorene compound represented by the formula (1) in the organic material (B) may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass.

[0089] (Characteristics of Organic Material (B)) The organic material (B) may be crystalline or amorphous. When the organic material (B) is crystalline, the melting point of the organic material (B) may be any melting point that allows melt-kneading, and may be 100°C or higher (e.g., 100 to 250°C), for example, 120 to 230°C, preferably 130 to 200°C, particularly preferably 135 to 180°C, even more preferably 140 to 170°C, more preferably 145 to 165°C, and most preferably 150 to 163°C. When the organic material (B) is amorphous, it may be meltable (or flowable) within the above melting point range. If the melting point of the organic material (B) is too low, it may not be able to maintain a solid state, making it difficult to produce granules. Conversely, if the melting point is too high, it may be difficult to handle.

[0090] In this specification and claims, the melting point of the organic material (B) means the peak top temperature in a DSC curve obtained by differential scanning calorimetry (DSC).

[0091] In order to facilitate uniform dispersion of the fibrous filler (A) in the resin or rubber during the kneading process of the granules with the resin or rubber, the organic material (B) is preferably in a state where it is not complexed (chemically modified) with the fibrous filler (A) by forming a covalent bond such as an ether bond or an ester bond. When the organic material (B) and the fibrous filler (A) are complexed, it is preferable that they are complexed by relatively loose bonding or affinity such as by hydrogen bonding. When complexed by loose bonding, it can be estimated that the degree of freedom of the fibrous filler (A) in the resin or rubber composition is high, and the mechanical properties (such as flexural fatigue resistance) of the resin or rubber composition can be improved.

[0092] The proportion of the organic material (B) [particularly the fluorene compound represented by the formula (1)] is, for example, 1 to 70 parts by mass, preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, even more preferably 20 to 40 parts by mass, and most preferably 30 to 35 parts by mass, relative to 100 parts by mass of the fibrous filler (A). If the proportion of the organic material (B) is too low, it may be difficult to prepare granules or the dispersibility of the fibrous filler (A) may decrease. Conversely, if the proportion is too high, the reinforcing effect of the fibrous filler (A) may be weakened, and the mechanical properties of the resin or rubber composition may not be improved.

[0093] (Other Components) The granules of the present disclosure may further contain conventional additives. Examples of conventional additives include adhesives, pressure-sensitive adhesives, adhesion improvers, tackifiers, silane coupling agents, softeners, crosslinking agents, crosslinking aids, reinforcing agents, plasticizers, anti-aging or antioxidants, colorants, stabilizers, release agents, lubricants, flame retardants, vibration-damping agents, flame retardant aids, antistatic agents, conductive agents, flow adjusters, leveling agents, antifoaming agents, surface modifiers, stress-reducing agents, nucleating agents, crystallization accelerators, antibacterial agents, and preservatives.

[0094] These additives can be used alone or in combination of two or more. The total amount of these additives may be 50 parts by mass or less, for example, 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the fibrous filler (A).

[0095] [Granule Properties] The shape of the granules of the present disclosure is not particularly limited, but granular (or powder) form is preferred. The granules may be spherical, approximately spherical, ellipsoidal, polygonal or polyhedral, flat, rod-like or columnar, irregular, or the like. Of these, the granules are preferably isotropic, such as spherical, or approximately isotropic, such as approximately spherical or cylindrical. Therefore, in granular granules, the ratio of the major axis to the minor axis (aspect ratio) is preferably close to 1, for example, 1 to 3, preferably 1 to 2, more preferably 1 to 1.5, more preferably 1 to 1.3, and most preferably 1 to 1.2. When the granules are cylindrical, the major axis corresponds to the larger of the height of the cylinder and the diameter of the circular base, and the minor axis corresponds to the smaller of the height of the cylinder and the diameter of the circular base.

[0096] The average particle size (D50) of the granules is, for example, 0.1 to 20 mm, preferably 1 to 10 mm, further preferably 1.5 to 5 mm, more preferably 2 to 4 mm, and most preferably 2.5 to 3.5 mm. If the average particle size of the granules is too small, it may be difficult to mix them uniformly with the fibrous filler (A), whereas if it is too large, it may be difficult to prepare the granules.

[0097] In this specification and claims, the average particle size of the granules can be measured by a conventional method, for example, by randomly selecting 50 particles from an image of a scanning electron microscope photograph and calculating the average particle size.

[0098] The bulk density of the granules of the present disclosure is 0.1 to 0.5 g / cm ３ and preferably 0.13 to 0.4 g / cm ３ , more preferably 0.15 to 0.3 g / cm ３ , more preferably 0.18 to 0.25 g / cm ３ , most preferably 0.19 to 0.23 g / cm３ If the bulk density is too small, when the granules are mixed with resin or rubber, there is a risk that the granules will not be meshed well with the kneader screw, making stable feeding impossible, whereas if the bulk density is too large, the granules will be too compacted, making dispersion in the kneader less likely.

[0099] In this specification and claims, the bulk density of the granules can be determined by measuring the volume and mass using a measuring cylinder, and in detail, can be measured by the method described in the examples below.

[0100] [Method for producing granules] The granules of the present disclosure are obtained through a mixing step in which a precursor of the plant-derived fibrous filler (A), a precursor of the organic material (B), and water are mixed to obtain a mixture, and a granulation step in which the obtained mixture is granulated to obtain granules. In the present disclosure, the use of water in the mixing step makes it easy to mix the precursors uniformly and is also highly safe.

[0101] In the mixing step, the proportion of water is, for example, 10 to 500 parts by mass, preferably 50 to 300 parts by mass, more preferably 100 to 250 parts by mass, even more preferably 130 to 200 parts by mass, and most preferably 150 to 180 parts by mass, relative to 100 parts by mass of the precursor of the plant-derived fibrous filler (A). If the proportion of water is too low, it may be difficult to uniformly mix the precursor of the plant-derived fibrous filler (A) and the precursor of the organic material (B). Conversely, if the proportion of water is too high, the productivity of the granules may decrease.

[0102] The precursors may be mixed (or stirred) by conventional mixing or stirring means, for example, at a rotation speed of about 100 to 10,000 rpm, preferably 500 to 5,000 rpm, more preferably 1,000 to 3,000 rpm, and particularly preferably 1,500 to 2,500 rpm.

[0103] Conventional mixing or stirring methods include methods using a ball mill, tumble mixer, ribbon blender, Henschel mixer, mixing roller, kneader, Banbury mixer, extruder (single-screw or twin-screw extruder, etc.), and the like.

[0104] The mixing time is, for example, 1 to 100 minutes, preferably 3 to 60 minutes, and more preferably 5 to 30 minutes.

[0105] In the granulation step, the granulation method can be selected from conventional granulation methods, such as tumbling granulation, fluidized bed granulation, stirring granulation, crushing granulation, compression granulation, extrusion granulation, and dissolution granulation. Among these, compression granulation and extrusion granulation are preferred, and extrusion granulation is particularly preferred because it is easy to produce granules having the desired bulk density. Extrusion granulation can be performed using a conventional extrusion granulator such as a disc pelletizer.

[0106] The granulation temperature can be selected within the range of room temperature to about 200°C, preferably room temperature to 100°C, and more preferably room temperature to 50°C. Since the temperature may rise due to kneading, for convenience, granulation may be carried out usually at room temperature in an unheated state.

[0107] The obtained granules may be subjected to a drying step. In the drying step, the drying method may be natural drying, but from the viewpoint of productivity, it is preferable to dry by heating. The heating temperature is, for example, 50 to 200°C, preferably 60 to 150°C, and more preferably 80 to 120°C. The drying time is, for example, 1 to 24 hours, preferably 3 to 15 hours, and more preferably 5 to 10 hours.

[0108] [Resin Composition] The resin composition of the present disclosure contains the granules and a resin. The granules are granular and have a specific bulk density, making them easy to handle. For example, when preparing a resin composition by kneading the granules with a resin, the granules can be smoothly fed into a kneader via a feeder or the like, and even when kneaded with a resin, aggregation of the fibrous filler (A) contained in the granules can be suppressed. Therefore, the fibrous filler (A) can be uniformly dispersed in the resin composition, improving the mechanical properties of the resin composition.

[0109] (Resin) The resin may be a curable resin (thermo- or photo-curable resin) or a thermoplastic resin.

[0110] Examples of the curable resin include phenolic resins such as resol-type phenolic resins and novolac-type phenolic resins; amino resins such as urea resins, melamine resins and guanamine resins; furan resins; unsaturated polyester resins; diallyl phthalate resins; vinyl ester resins (or epoxy (meth)acrylate resins); polyfunctional (meth)acrylate resins; epoxy resins; urethane resins; polyimide resins such as bismaleimide resins; and silicone resins.

[0111] Examples of thermoplastic resins include polyolefin resins such as linear olefin resins and cyclic olefin resins; styrene resins such as polystyrene, styrene-methyl methacrylate copolymer (MS resin), styrene-acrylonitrile copolymer (AS resin), high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-butadiene-styrene copolymer (MBS resin); and (meth)acrylic acid copolymers such as polymethyl methacrylate (PMMA) and (meth)acrylic acid-(meth)acrylic acid ester copolymers. ) acrylic resins; vinyl acetate resins such as polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), and polyvinyl acetal (polyvinyl formal (PVF), polyvinyl butyral (PVB), etc.); vinyl chloride homopolymers (PVC); vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers; vinylidene chloride resins such as vinylidene chloride-vinyl chloride copolymers and vinylidene chloride-acrylonitrile copolymers; fluororesins such as polytetrafluoroethylene (PTFE); polyalkylene arylate resins, polyarylate resins polyester-based resins such as bisphenol A polycarbonate-based resins; polyamide-based resins such as aliphatic polyamide resins, aromatic polyamide resins, and aramid resins; polyacetal-based resins such as polyacetal resin (POM); polyphenylene ether-based resins such as polyphenylene ether (PPE); polyether ketone-based resins such as polyether ketone (PEK), polyether ether ketone (PEEK), and polyether ketone ether ketone ketone (PEKEKK) Resins; phenoxy resins; polyketone resins such as aliphatic polyketone resins; polyphenylene sulfide resins such as polyphenylene sulfide (PPS); polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES); cellulose esters such as nitrocellulose, cellulose acetate, and cellulose acetate propionate; cellulose ethers such as ethyl cellulose and carboxymethyl cellulose; thermoplastic polyimide resins such as polyetherimide (PEI) and polyamideimide; polyethernitrile resins;Examples of thermoplastic elastomers include polystyrene-based thermoplastic elastomers (TPE), polyolefin-based TPE (TPO), polydiene-based TPE, chlorine-based TPE, fluorine-based TPE, polyurethane-based TPE (TPU), polyester-based TPE (TPEE), and polyamide-based TPE (TPA).

[0112] These resins can be used alone or in combination of two or more. Among these, thermoplastic resins are preferred.

[0113] The density of the thermoplastic resin is, for example, 0.85 to 3 g / cm ３ The density may be selected from a range of about 0.9 to 2.7 g / cm ３ , preferably 0.95 to 2 g / cm ３ , more preferably 0.95 to 1.5 g / cm ３ may be.

[0114] The weight average molecular weight Mw of the thermoplastic resin may be selected, for example, from the range of about 10,000 to 10,000,000. The number average molecular weight Mn may be selected, for example, from the range of about 10,000 to 1,000,000, preferably 50,000 to 800,000, preferably 100,000 to 500,000, and more preferably 200,000 to 400,000. The molecular weight distribution (Mw / Mn) may be selected, for example, from the range of about 1 to 50, for example, 2 to 25.

[0115] In the present specification and claims, the weight average molecular weight, number average molecular weight and molecular weight distribution can be measured by GPC in terms of standard polystyrene.

[0116] Among the thermoplastic resins, it is preferable to include at least one selected from polyolefin-based resins, polyacetal-based resins, polyester-based resins and polyamide resins, and polyolefin-based resins are particularly preferable.

[0117] (Polyolefin Resin) Examples of polyolefin resins include linear olefin resins containing an α-olefin as a main polymerization component, and cyclic olefin resins containing cyclic olefins as polymerization components (cyclic olefin copolymers (COC) such as ethylene-norbornene copolymers, addition or ring-opening polymers of cyclic olefins such as polynorbornene, polydicyclopentadiene, polycyclopentadiene, or hydrogenated products thereof, or hydrogenated products thereof). Of these, linear olefin resins are preferred.

[0118] Examples of the α-olefins that are polymerization components of chain olefin resins include α-C olefins such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. ２－２０ Olefins and the like.

[0119] These α-olefins can be used alone or in combination of two or more. ２－１０ Olefins are preferred, and α-C olefins such as ethylene and propylene are preferred. ２－６ Olefins are particularly preferred.

[0120] The chain olefin resin may be a homopolymer or copolymer of the α-olefin. The polymerization components in the copolymer may contain two or more types of α-olefins, or may contain a copolymerizable monomer different from the α-olefin. The copolymer may be a random copolymer, a block copolymer, or the like.

[0121] Examples of the copolymerizable monomer include (meth)acrylic acid C such as (meth)acrylic acid, methyl (meth)acrylate, and ethyl (meth)acrylate. １－１０Examples of suitable vinyl esters include (meth)acrylic monomers such as alkyl esters, glycidyl (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile; unsaturated carboxylic acids or acid anhydrides thereof such as maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, and anhydrides thereof; vinyl carboxylic acid esters such as vinyl acetate and vinyl propionate; non-conjugated alkadienes such as 1,4-hexadiene, 1,7-octadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene; and conjugated alkadienes such as butadiene and isoprene.

[0122] These copolymerizable monomers can be used alone or in combination of two or more. When a chain olefin resin such as a polyethylene resin contains a copolymerizable monomer, the proportion of the copolymerizable monomer relative to all structural units may be about 70 mol% or less, and is usually 50 mol% or less, for example, 30 mol% or less (e.g., 0.01 to 30 mol%), preferably 20 mol% or less (e.g., 0.1 to 20 mol%), and more preferably 10 mol% or less (e.g., 1 to 10 mol%).

[0123] Representative chain olefin resins include poly-α-C resins such as polyethylene resins, polypropylene resins, poly-1-butene resins, and poly-4-methyl-1-pentene resins. ２－６ Examples include olefin-based resins, and polyethylene-based resins and polypropylene-based resins are preferred, with polyethylene-based resins being particularly preferred.

[0124] Examples of polyethylene resins include polyethylenes such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene (UHMWPE); ethylene-(α-C) copolymers such as ethylene-propylene copolymers, ethylene-(1-butene) copolymers, ethylene-propylene-(1-butene) copolymers, and ethylene-(4-methyl-1-pentene) copolymers; ３－１０ olefin copolymers; modified polyethylene such as maleic anhydride modified polyethylene; chlorinated polyethylene; ionomers, and the like.

[0125] These polyethylene resins can be used alone or in combination of two or more. Among these polyethylene resins, linear polyethylenes with almost no branched structure, such as HDPE, LLDPE, and UHMWPE, are preferred, and from the viewpoint of the mechanical properties of the resin composition, HDPE and UHMWPE, among which HDPE, are particularly preferred.

[0126] The density of the polyethylene resin is 0.910 to 0.980 kg / m according to JIS K 6922-1. ３ In view of the excellent mechanical properties of the resin composition, for example, 0.930 to 0.970 kg / m ３ , preferably 0.940 to 0.965 kg / m ３ , more preferably 0.950 to 0.962 kg / m ３ , more preferably 0.955 to 0.960 kg / m ３ is.

[0127] The melt mass flow rate (MFR) of the polyethylene resin is, in accordance with JIS K 6922-2, for example, 3 to 80 g / 10 min, preferably 5 to 50 g / 10 min, more preferably 10 to 30 g / 10 min, and even more preferably 15 to 25 g / 10 min. If the MFR is too small, the melt moldability of the resin composition may be reduced, whereas if the MFR is too large, the mechanical properties of the resin composition may be reduced.

[0128] The melting point (DSC method) of the polyethylene resin is, in accordance with ISO 11357-3, for example, 80 to 150° C., preferably 100 to 145° C., further preferably 120 to 140° C., and even more preferably 130 to 135° C. If the melting point is too low, the heat resistance of the resin composition may be reduced, and if the melting point is too high, the melt moldability of the resin composition may be reduced.

[0129] (Polyacetal Resin) Polyacetal resins essentially contain oxymethylene units (-CH ２Polyacetal resins include polyacetal homopolymers (homopolymers) consisting only of repeating oxymethylene units, and polyacetal copolymers (copolymers) containing oxymethylene units and at least one copolymerizable monomer (comonomer) unit. Polyacetal resins may be homopolymers (homopolymers), but are often copolymers in view of their excellent thermal stability and wide range of applications.

[0130] The polyacetal copolymer (copolymer) may be a copolymer composed of two components, a terpolymer composed of three components, etc. The polyacetal copolymer (copolymer) may be a random copolymer, a block copolymer, a graft copolymer, etc.

[0131] The comonomer units of the copolymer include oxy C ２－６ Alkylene units (e.g., oxyethylene groups (—OCH ２ CH ２ -), oxy C such as oxypropylene group, oxytetramethylene group ２－４ alkylene units, etc.).

[0132] These comonomer units can be used alone or in combination of two or more kinds. The proportion of the comonomer unit is, for example, 0.01 to 30 mol %, preferably 0.03 to 20 mol %, and more preferably 0.03 to 15 mol %, based on the total polyacetal resin.

[0133] Specifically, the polyacetal resin may be a homopolymer or copolymer containing, as a main polymerization component, an aldehyde such as formaldehyde, paraformaldehyde, or acetaldehyde, or a cyclic ether or cyclic formal such as trioxane, ethylene oxide, propylene oxide, 1,3-dioxolane, 1,3-dioxane, diethylene glycol formal, or 1,4-butanediol formal.

[0134] The polyacetal resin may contain other copolymerization components, such as alkyl or aryl glycidyl ethers, such as methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidyl ether, and naphthyl glycidyl ether; alkylene or polyalkylene glycol diglycidyl ethers, such as ethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and butanediol diglycidyl ether; alkyl or aryl glycidyl alcohols; cyclic esters, such as β-propiolactone; and vinyl compounds, such as vinyl ethers.

[0135] The polyacetal resin may have a linear or branched structure or may be crosslinked. The terminals of the polyacetal resin may be stabilized by, for example, esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof, urethanization with an isocyanate compound, or etherification.

[0136] These polyacetal resins may be used alone or in combination of two or more.

[0137] The density of polyacetal resin is 0.95 to 1.8 g / cm according to ISO 1183. ３ In terms of excellent mechanical properties of the resin composition, for example, 1 to 1.75 g / cm ３ , preferably 1.1 to 1.73 g / cm ３ , more preferably 1.2 to 1.7 g / cm ３ , more preferably 1.3 to 1.5 g / cm ３ is.

[0138] The melt mass flow rate (MFR) of the polyacetal resin is, in accordance with ISO 1133 (190°C, 2.16 kg load), for example, 5 to 100 g / 10 min, preferably 10 to 80 g / 10 min, further preferably 30 to 60 g / 10 min, and even more preferably 40 to 50 g / 10 min. If the MFR is too small, the melt moldability of the resin composition may be reduced, whereas if the MFR is too large, the mechanical properties of the resin composition may be reduced.

[0139] The deflection temperature under load of the polyacetal resin, in accordance with ISO 75-1, 2, is, for example, 60 to 200° C., preferably 70 to 150° C., further preferably 80 to 130° C., and even more preferably 90 to 110° C. If the deflection temperature under load is too low, the heat resistance of the resin composition may be reduced, whereas if it is too high, the melt moldability of the resin composition may be reduced.

[0140] (Polyester Resin) Examples of polyester resins include polyesters obtained by reacting (condensation reaction) a diol component with a dicarboxylic acid component.

[0141] Examples of the diol component include aliphatic diols such as alkanediols and polyalkanediols; alicyclic diols such as cycloalkanediols and di(hydroxyalkyl)cycloalkanes; and aromatic diols such as dihydroxyarenes, aromatic aliphatic diols, and bisphenols.

[0142] Examples of alkanediols include C alkanediols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-pentanediol, and neopentyl glycol. ２－１０ Alkanediols and the like.

[0143] Examples of polyalkanediols include di- or tri-C diethylene glycol, dipropylene glycol, and triethylene glycol. ２－４ Alkanediols and the like.

[0144] Examples of cycloalkanediols include C cyclohexanediols and the like. ５－８ Cycloalkanediols and the like.

[0145] Examples of the di(hydroxyalkyl)cycloalkane include di(hydroxy C) such as cyclopentane dimethanol and cyclohexane dimethanol. １－４ alkyl) C ５－８ Cycloalkanes and the like.

[0146] Dihydroxyarenes include hydroquinone, resorcinol, and biphenol.

[0147] Examples of aromatic aliphatic diols include di(hydroxy C) such as 1,4-benzenedimethanol and 1,3-benzenedimethanol. １－４ alkyl) C ６－１０ arenes, etc.

[0148] Bisphenols include bis(hydroxyphenyl) C such as bisphenol A. １－１０ Alkanes and the like.

[0149] These diol components can be used alone or in combination of two or more. Among these diol components, C olefins such as ethylene glycol and 1,4-butanediol are preferred. ２－６ Alkanediols are preferred, C ２－５ Alkanediols are more preferred, C ３－５ Alkanediols are more preferred.

[0150] Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic carboxylic acids, and derivatives of these dicarboxylic acids.

[0151] Examples of aliphatic carboxylic acids include alkanecarboxylic acids. Examples of alkanecarboxylic acids include C carboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. ２－２０ Alkane-dicarboxylic acids and the like.

[0152] Examples of the alicyclic dicarboxylic acid include cycloalkane dicarboxylic acids, di- or tricycloalkane dicarboxylic acids, etc. Examples of the cycloalkane dicarboxylic acid include C cyclohexane dicarboxylic acids, etc. ５－１０ Examples of di- or tricycloalkanedicarboxylic acids include decalindicarboxylic acid, norbornanedicarboxylic acid, and adamantanedicarboxylic acid.

[0153] Examples of aromatic dicarboxylic acids include arene dicarboxylic acids, biphenyl dicarboxylic acids, diphenyl alkane dicarboxylic acids, diphenyl ketone dicarboxylic acids, diphenyl ether dicarboxylic acids, etc. Examples of arene dicarboxylic acids include C carboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, and phenanthrene dicarboxylic acid. ６－１４ Examples of the diphenyl dicarboxylic acids include 2,2'-biphenyl dicarboxylic acid, and examples of the diphenyl alkane dicarboxylic acids include 4,4'-diphenylmethane dicarboxylic acid and 2,2-di(4-carboxyphenyl)hexafluoropropane dicarboxylic acid. １－１０ Examples of diphenyl ketone dicarboxylic acids include 4,4'-diphenyl ketone dicarboxylic acid, etc. Examples of diphenyl ether dicarboxylic acids include 4,4'-diphenyl ether dicarboxylic acid, etc.

[0154] Examples of the derivatives of dicarboxylic acids include dicarboxylic acid halides such as dicarboxylic acid chlorides; dicarboxylic acid anhydrides; and lower alkyl esters such as methyl esters and ethyl esters. １－４ Alkyl esters are preferred, C １－２ Alkyl esters are particularly preferred.

[0155] These dicarboxylic acid components can be used alone or in combination of two or more. Among these dicarboxylic acid components, cycloalkane-dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; arene dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenecarboxylic acid are preferred, and C ６－１０ Arene-dicarboxylic acids are particularly preferred.

[0156] Among these polyester resins, polyalkylene arylate resins such as polyalkylene terephthalate resins and polyalkylene naphthalate resins are preferred in terms of mechanical properties and heat resistance.

[0157] The polyalkylene arylate resin may be a polyalkylene arylate resin having an alkylene arylate unit (particularly, C such as ethylene terephthalate, butylene terephthalate, or ethylene-2,6-naphthalate). ２－６ Examples of the copolymerizable monomers constituting the copolyester include homopolyesters of alkylene arylate units (alkylene arylate units), and copolyesters having an alkylene arylate unit content of 80 mol % or more (particularly 90 mol % or more). In addition to the dicarboxylic acid component and diol component mentioned above, examples of the copolymerizable monomers constituting the copolyester include hydroxycarboxylic acids such as hydroxybenzoic acid and lactones such as caprolactone. Among these copolymerizable monomers, dicarboxylic acid components such as isophthalic acid are commonly used. Examples of the polyalkylene arylate resin include polyC such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin. ２－４ Alkylene naphthalate resins are preferred.

[0158] Representative polyalkylene arylate resins include polyC such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. ２－１０ Alkylene C ８－１６ Arylate; poly-C such as poly-1,4-cyclohexanedimethylene terephthalate ５－１０ Cycloalkane-di C １－４ Alkylene C ８－１６ Examples include arylates.

[0159] These polyalkylene arylate resins can be used alone or in combination of two or more. Among these, polyC such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are preferred. ２－６ Alkylene C ８－１６ Arylate is preferred, and poly(C) such as polybutylene terephthalate is preferred. ３－５ Alkylene C ８－１２ The arylates are particularly preferred.

[0160] These polyester resins may be crystalline like polyalkylene arylate resins, amorphous like polyarylate resins, or transparent polyester resins (amorphous transparent polyester resins). The crystallinity of the polyester resin can also be adjusted by the copolymerization components described above. For example, the crystallinity may be adjusted by using an asymmetric aliphatic diol component such as propylene glycol or 1,3-butanediol; or an asymmetric aromatic dicarboxylic acid component such as phthalic acid or isophthalic acid.

[0161] The density of the polyester resin is 0.95 to 1.8 g / cm according to ISO 1183. ３ In terms of excellent mechanical properties of the resin composition, for example, 1 to 1.75 g / cm ３ , preferably 1 to 1.7 g / cm ３ , more preferably 1.1 to 1.5 g / cm ３ , more preferably 1.2 to 1.4 g / cm ３ is.

[0162] The melt volume flow rate (MVR) of polyester resins is, for example, 5 to 100 cm in accordance with ISO 1133 (250°C, 2.16 kg load). ３ / 10 min, preferably 10 to 50 cm ３ / 10 minutes, more preferably 15 to 40 cm ３ / 10 minutes, more preferably 20 to 30 cm ３ If the MVR is too small, the melt moldability of the resin composition may be reduced, whereas if the MVR is too large, the mechanical properties of the resin composition may be reduced.

[0163] The weight average molecular weight of the polyester resin can be selected from a range of about 3,000 to 1,000,000, based on an evaluation method using gel permeation chromatography with polystyrene as the standard, and is, for example, 5,000 to 800,000, preferably 8,000 to 600,000, more preferably 10,000 to 500,000, and even more preferably 30,000 to 500,000.

[0164] The glass transition temperature (Tg) of the polyester resin is, for example, 30 to 350°C, preferably 40 to 300°C, more preferably 50 to 250°C, and even more preferably 60 to 200°C.

[0165] (Polyamide-based resin) The polyamide-based resin may be formed from at least one selected from the group consisting of an aliphatic monomer component, an alicyclic monomer component, and an aromatic monomer component. Among these, it is preferable to contain an aliphatic monomer component, and an aliphatic monomer component is particularly preferable.

[0166] In the present specification and claims, the monomer component having a carboxyl group such as a dicarboxylic acid described later may be an acid halide such as an acid chloride, or an amide-forming derivative such as an acid anhydride.

[0167] Examples of the aliphatic monomer component include an aliphatic diamine component, an aliphatic dicarboxylic acid component, an aliphatic aminocarboxylic acid component, and a lactam component.

[0168] Examples of the aliphatic diamine component include linear or branched C diamines such as tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, 2-methyloctamethylenediamine, trimethylhexamethylenediamine, decamethylenediamine, and dodecamethylenediamine. ２－２０ Among these, linear or branched C alkylene diamines are preferred. ４－１６ Alkylenediamines are preferred, and linear or branched C ６－１２ Alkylenediamines are particularly preferred.

[0169] Examples of the aliphatic dicarboxylic acid component include saturated aliphatic dicarboxylic acids (straight-chain or branched-chain alkanedicarboxylic acids) and unsaturated aliphatic dicarboxylic acids.

[0170] Examples of the linear or branched alkanedicarboxylic acid include linear or branched C alkanedicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,10-decanedicarboxylic acid. １－２０Among these, linear or branched C ２－１６ Alkane-dicarboxylic acids are preferred, and linear or branched C alkane-dicarboxylic acids such as adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, etc. ４－１２ Alkane-dicarboxylic acids are particularly preferred.

[0171] Examples of unsaturated aliphatic dicarboxylic acids include C carboxylic acids such as maleic acid, fumaric acid, and itaconic acid. ２－１０ Alkene-dicarboxylic acids and the like.

[0172] The aliphatic aminocarboxylic acid component includes amino C such as 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. ２－２０ Among these, amino C ３－１６ Alkyl-carboxylic acids are preferred, amino C ５－１１ Alkyl-carboxylic acids are particularly preferred.

[0173] The lactam component may be a lactam corresponding to the aliphatic aminocarboxylic acid, such as ε-caprolactam, ω-laurolactam, etc., having a 4- to 13-membered ring. Of these, lactams having a 7- to 13-membered ring are preferred.

[0174] The alicyclic monomer component may have an alicyclic skeleton (or an aliphatic hydrocarbon ring skeleton), and examples thereof include an alicyclic diamine component, an alicyclic dicarboxylic acid component, and an alicyclic aminocarboxylic acid component.

[0175] Examples of the alicyclic diamine component include diaminocycloalkanes, bis(aminoalkyl)cycloalkanes, and bis(aminocyclohexyl)alkanes.

[0176] Examples of diaminocycloalkanes include diamino C such as diaminocyclohexane. ５－１０ Cycloalkanes and the like.

[0177] Examples of the bis(aminoalkyl)cycloalkane include bis(amino C) such as bis(aminomethyl)cyclohexane. １－４ alkyl) C ５－１０Cycloalkanes and the like.

[0178] Examples of the bis(aminocyclohexyl)alkane include bis(aminocyclohexyl) C such as bis(4-aminocyclohexyl)methane and 2,2-bis(4-aminocyclohexyl)propane. １－６ Alkanes; bis(amino-mono to tri C) such as bis(4-amino-3-methylcyclohexyl)methane, bis(4-amino-3,5-dimethylcyclohexyl)methane, and 2,2-bis(4-amino-3-methylcyclohexyl)propane; １－６ Alkyl-C ５－１０ Cycloalkyl)C １－６ Alkanes and the like.

[0179] Examples of the alicyclic dicarboxylic acid component include cycloalkane dicarboxylic acids, crosslinked cyclic cycloalkane dicarboxylic acids, cycloalkene dicarboxylic acids, and crosslinked cyclic cycloalkene dicarboxylic acids.

[0180] Examples of cycloalkanedicarboxylic acids include C cycloalkanedicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. ５－１０ Cycloalkane-dicarboxylic acids and the like are included.

[0181] Examples of the bridged cyclic cycloalkanedicarboxylic acid include bi- or tricycloalkanedicarboxylic acids such as decalindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, and tricyclodecanedicarboxylic acid.

[0182] Examples of cycloalkene dicarboxylic acids include C cyclohexene dicarboxylic acids. ５－１０ Cycloalkene-dicarboxylic acids and the like.

[0183] Examples of the bridged cyclic cycloalkene dicarboxylic acid include bi- or tricycloalkene dicarboxylic acids such as norbornene dicarboxylic acid.

[0184] Examples of the alicyclic aminocarboxylic acid component include aminocycloalkanecarboxylic acids, and specifically, amino C such as aminocyclohexanecarboxylic acids. ５－１０ Cycloalkane-carboxylic acid and the like.

[0185] The aromatic monomer component may be any component as long as it has an aromatic ring skeleton, and examples thereof include aromatic (or aromatic aliphatic) diamine components, aromatic (or aromatic aliphatic) dicarboxylic acid components, and aromatic (or aromatic aliphatic) aminocarboxylic acid components.

[0186] Examples of the aromatic (or aromatic aliphatic) diamine component include diaminoarenes, bis(aminoalkyl)arenes, etc. Examples of the diaminoarenes include diamino C arenes such as m-phenylenediamine, p-phenylenediamine, and m-xylylenediamine. ６－１４ Examples of bis(aminoalkyl)arenes include bis(amino C １－４ alkyl arenes and the like.

[0187] Examples of the aromatic (or araliphatic) dicarboxylic acid component include benzene dicarboxylic acids, alkylbenzene dicarboxylic acids, polycyclic arene dicarboxylic acids, diarylalkane dicarboxylic acids, diaryl ketone dicarboxylic acids, diaryl ether dicarboxylic acids, diaryl sulfide dicarboxylic acids, and diaryl sulfone dicarboxylic acids.

[0188] Examples of benzenedicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Examples of alkylbenzenedicarboxylic acids include C alkyl benzenedicarboxylic acids such as 4-methylisophthalic acid and 5-methylisophthalic acid. １－４ alkyl-benzenedicarboxylic acids and the like.

[0189] Examples of polycyclic arene dicarboxylic acids include condensed polycyclic arene dicarboxylic acids and ring-assembled arene dicarboxylic acids.

[0190] Examples of the condensed polycyclic arene dicarboxylic acids include naphthalenedicarboxylic acids such as 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; anthracene dicarboxylic acid; and condensed polycyclic C such as phenanthrene dicarboxylic acid. １０－２４ arene-dicarboxylic acids, preferably fused polycyclic C １０－１４ arene-dicarboxylic acids.

[0191] Examples of ring-assembled arene dicarboxylic acids include bi-C such as 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. ６－１０ arene-dicarboxylic acids and the like.

[0192] Diarylalkanedicarboxylic acids include di-C such as 4,4'-diphenylmethanedicarboxylic acid. ６－１０ Aryl C １－６ Alkane-dicarboxylic acids and the like.

[0193] Examples of diaryl ketone dicarboxylic acids include di(C) ketone dicarboxylic acids such as 4,4′-diphenyl ketone dicarboxylic acid. ６－１０ aryl) ketone-dicarboxylic acid and the like.

[0194] Diaryl ether dicarboxylic acids include di(C) such as 4,4′-diphenyl ether dicarboxylic acid. ６－１０ aryl) ether-dicarboxylic acid and the like.

[0195] Diaryl sulfide dicarboxylic acids include di(C) such as 4,4'-diphenyl sulfide dicarboxylic acid. ６－１０ aryl) sulfide-dicarboxylic acid, and the like.

[0196] Diarylsulfonedicarboxylic acids include di(C) such as 4,4'-diphenylsulfonedicarboxylic acid. ６－１０ aryl) sulfone-dicarboxylic acid and the like.

[0197] Examples of aromatic aminocarboxylic acid components include aminoarenecarboxylic acids. Examples of aminoarenecarboxylic acids include amino C such as aminobenzoic acid. ６－１２ arene-carboxylic acid and the like.

[0198] The polyamide resin can be formed by using these monomer components alone or in combination of two or more. For example, it may be formed by polymerization of a diamine component and a dicarboxylic acid component, polymerization of an aminocarboxylic acid component and / or a lactam component, or polymerization of a diamine component and a dicarboxylic acid component with an aminocarboxylic acid component and / or a lactam component. Furthermore, the polyamide resin may be a homopolyamide formed from a single monomer component (a single diamine component and a dicarboxylic acid component, a single aminocarboxylic acid component, or a single lactam component), or a copolyamide formed by copolymerizing multiple monomer components. Representative polyamide resins include aliphatic polyamide resins, alicyclic polyamide resins, and aromatic polyamide resins. Of these, aliphatic polyamide resins are preferred.

[0199] The aliphatic polyamide resin may be formed from aliphatic monomer units derived from aliphatic monomer components. Examples of the aliphatic polyamide resin include homopolyamides of aliphatic diamine components and aliphatic dicarboxylic acid components, such as polyamide 46, polyamide 66, polyamide 610, and polyamide 612; homopolyamides of aliphatic aminocarboxylic acid components and / or corresponding lactam components, such as polyamide 6, polyamide 11, and polyamide 12; and copolymers (copolyamides) of multiple aliphatic monomer components, such as copolyamide 6 / 66, copolyamide 6 / 11, and copolyamide 66 / 12.

[0200] In this specification and claims, the " / " in the copolyamide indicates that the copolyamide is formed from the monomers (units) before and after it as copolymerization components (copolymerization units). In other words, copolyamide 6 / 66 means a copolymer having units that form polyamide 6 and units that form polyamide 66.

[0201] The aliphatic polyamide resin is preferably an aliphatic polyamide resin containing an aliphatic monomer component having an alkylene group with a carbon number of, for example, 4 to 12, preferably 6 to 11, and more preferably 6 to 9. Typical preferred aliphatic polyamide resins include homopolyamides of an aliphatic diamine component and an aliphatic dicarboxylic acid component, such as polyamide 46, polyamide 66, polyamide 610, and polyamide 612; and homopolyamides of an aliphatic aminocarboxylic acid component and / or the corresponding lactam component, such as polyamide 6.

[0202] The density of the polyamide resin is 0.95 to 1.8 g / cm according to ISO 1183. ３ In view of the excellent mechanical properties of the resin composition, for example, 1 to 1.7 g / cm ３ , preferably 1 to 1.5 g / cm ３ , more preferably 1.05 to 1.3 g / cm ３ , more preferably 1.1 to 1.2 g / cm ３ is.

[0203] The melt volume flow rate (MVR) of polyamide resins is, for example, 10 to 400 cm in accordance with ISO 1133 (275°C, 5 kg load). ３ / 10 min, preferably 50 to 350 cm ３ / 10 min, more preferably 100 to 300 cm ３ / 10 min, more preferably 150 to 250 cm ３ If the MVR is too small, the melt moldability of the resin composition may be reduced, whereas if the MVR is too large, the mechanical properties of the resin composition may be reduced.

[0204] The number average molecular weight Mn of the polyamide resin can be selected from the range of about 7,000 to 1,000,000, for example, 10,000 to 750,000, preferably 20,000 to 500,000, further preferably 30,000 to 500,000, and even more preferably 50,000 to 500,000, based on an evaluation method using gel permeation chromatography with polystyrene as the standard.

[0205] (Ratio of Granules) The ratio of the granules can be selected from a range of about 1 to 100 parts by mass relative to 100 parts by mass of the resin, and is preferably 3 to 50 parts by mass, 5 to 30 parts by mass, 10 to 20 parts by mass, 13 to 18 parts by mass, 14 to 17 parts by mass, and most preferably 15 to 16 parts by mass in the following stepwise manner. If the ratio of the granules is too low, it may be difficult to uniformly disperse the plant-derived fibrous filler (A) in the resin, and conversely, if it is too high, the moldability of the resin composition may be reduced.

[0206] (Plant-derived fibrous filler) The resin composition of the present disclosure may further contain a second plant-derived fibrous filler in addition to the plant-derived fibrous filler (A) (first plant-derived fibrous filler) contained in the granules. The second fibrous filler, including preferred embodiments, can be selected from the fibrous fillers exemplified as the plant-derived fibrous filler (A) contained in the granules.

[0207] The proportion of the second plant-derived fibrous filler relative to 100 parts by mass of the resin may be 100 parts by mass or less, for example, 50 parts by mass or less, preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and more preferably 2 parts by mass or less, for example, 0.1 to 3 parts by mass.

[0208] In the resin composition of the present disclosure, the granules preferably contain a plant-derived fibrous filler because the plant-derived fibrous filler can be easily dispersed uniformly in the resin composition. Therefore, the resin composition of the present disclosure is preferably substantially free of, and particularly preferably completely free of, a second plant-derived fibrous filler.

[0209] (Additives) The resin composition of the present disclosure may further contain conventional additives that are blended into resins such as thermoplastic resins. Examples of such additives include coupling agents such as silane coupling agents, softeners, crosslinking agents, crosslinking aids, fillers or reinforcing agents, plasticizers, anti-aging or antioxidants (e.g., aromatic amine-based and benzimidazole-based anti-aging agents), colorants such as dyes and pigments, stabilizers (e.g., ultraviolet absorbers, light stabilizers, and heat stabilizers), release agents, lubricants, flame retardants (e.g., phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants), vibration-damping agents, flame retardant aids, antistatic agents, conductive agents, dispersants, flow control agents, leveling agents, lubricants, antifoaming agents, surface modifiers, stress reducers, adhesives, pressure-sensitive adhesives, adhesion improvers, tackifiers, nucleating agents, crystallization accelerators, antibacterial agents, and preservatives. These additives can be used alone or in combination of two or more.

[0210] The total proportion of the additives may be 1000 parts by mass or less relative to 100 parts by mass of the resin, for example, 0.01 to 100 parts by mass, preferably 0.1 to 50 parts by mass, further preferably 0.5 to 30 parts by mass, and further preferably 1 to 20 parts by mass.

[0211] (Characteristics of Resin Composition) The resin composition of the present disclosure has excellent mechanical properties because the fibrous filler (A) such as cellulose fiber is uniformly dispersed in the resin composition.

[0212] The flexural strength of the resin composition of the present disclosure may be, for example, 10 MPa or more, for example, 10 to 300 MPa, preferably 20 to 200 MPa, and more preferably 30 to 150 MPa.

[0213] When the resin is a polyolefin-based resin, the flexural strength of the resin composition of the present disclosure may be, for example, 10 to 100 MPa, preferably 20 to 80 MPa, more preferably 22 to 50 MPa, more preferably 25 to 40 MPa, and most preferably 30 to 35 MPa.

[0214] When the resin is a polyacetal resin, the flexural strength of the resin composition of the present disclosure may be, for example, 30 to 300 MPa, preferably 50 to 200 MPa, further preferably 70 to 150 MPa, more preferably 80 to 100 MPa, and most preferably 85 to 95 MPa.

[0215] When the resin is a polyester-based resin, the flexural strength of the resin composition of the present disclosure may be, for example, 30 to 300 MPa, preferably 50 to 200 MPa, more preferably 70 to 150 MPa, more preferably 80 to 120 MPa, and most preferably 90 to 100 MPa.

[0216] When the resin is a polyamide-based resin, the flexural strength of the resin composition of the present disclosure may be, for example, 30 to 300 MPa, preferably 50 to 250 MPa, more preferably 70 to 200 MPa, more preferably 100 to 150 MPa, and most preferably 120 to 130 MPa.

[0217] The flexural modulus of the resin composition of the present disclosure may be 1000 MPa or more, for example, 1000 to 10000 MPa, preferably 1300 to 8000 MPa, and more preferably 1500 to 5000 MPa.

[0218] When the resin is a polyolefin-based resin, the flexural modulus of the resin composition of the present disclosure is, for example, 1000 to 3000 MPa, preferably 1200 to 2500 MPa, more preferably 1300 to 2000 MPa, more preferably 1400 to 1800 MPa, and most preferably 1500 to 1700 MPa.

[0219] When the resin is a polyacetal resin, the flexural modulus of the resin composition of the present disclosure is, for example, 2000 to 8000 MPa, preferably 2500 to 5000 MPa, further preferably 3000 to 4500 MPa, more preferably 3500 to 4000 MPa, and most preferably 3700 to 3900 MPa.

[0220] When the resin is a polyester resin, the flexural modulus of the resin composition of the present disclosure is, for example, 1500 to 8000 MPa, preferably 2000 to 5000 MPa, more preferably 2500 to 4000 MPa, more preferably 3000 to 3800 MPa, and most preferably 3400 to 3600 MPa.

[0221] When the resin is a polyamide-based resin, the flexural modulus of the resin composition of the present disclosure is, for example, 2000 to 8000 MPa, preferably 3000 to 5000 MPa, more preferably 3500 to 4500 MPa, more preferably 3800 to 4200 MPa, and most preferably 3900 to 4100 MPa.

[0222] In this specification and claims, the flexural strength and flexural modulus of a resin composition can be measured in accordance with ISO 178. The flexural strength and flexural modulus are measured for a resin composition that does not contain a reinforcing agent or a filler.

[0223] The shape of the resin composition of the present disclosure is not particularly limited, and may be in the form of pellets or the like.

[0224] (Method for Producing Resin Composition) The resin composition of the present disclosure can be produced by a method including a resin kneading step of kneading granules with a resin. In the resin kneading step, the method for kneading the granules with the resin may be a conventional kneading method depending on the type of resin. Examples of the kneading method include a method in which a thermoplastic resin, granules, and other components, as necessary, are kneaded by a conventional method such as dry mixing or melt kneading. Of these kneading methods, melt kneading is preferred.

[0225] In the case of melt-kneading, the kneading temperature may be equal to or higher than the melting point (or melting temperature) of the organic material (B), for example, 150 to 300°C, preferably 170 to 280°C, and more preferably 180 to 250°C.

[0226] When the thermoplastic resin is a polyolefin resin, the kneading temperature is, for example, 170 to 250°C, preferably 180 to 230°C, and more preferably 190 to 210°C.

[0227] When the thermoplastic resin is a polyacetal resin, the kneading temperature is, for example, 170 to 250°C, preferably 180 to 230°C, and more preferably 190 to 210°C.

[0228] When the thermoplastic resin is a polyester resin, the kneading temperature is, for example, 180 to 280°C, preferably 200 to 250°C, and more preferably 220 to 240°C.

[0229] When the thermoplastic resin is a polyamide resin, the kneading temperature is, for example, 180 to 280°C, preferably 200 to 250°C, and more preferably 220 to 240°C.

[0230] As a method for melt-kneading, a conventional method can be used, and it may be a method using an extrusion kneader such as a twin-screw extrusion kneader. The screw rotation speed is, for example, 10 to 1000 rpm, preferably 50 to 300 rpm, and more preferably 100 to 200 rpm.

[0231] (Molded Article) The molded article of the present disclosure can be produced by molding the resin composition using a conventional molding method. Conventional molding methods include compression molding, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting molding. When the resin is a thermoplastic resin, the resin composition of the present disclosure has excellent melt fluidity, so among these molding methods, molding methods that require high melt fluidity, such as injection molding, injection compression molding, and extrusion molding, are preferred, and injection molding is particularly preferred.

[0232] In the injection molding method, the cylinder temperature is, for example, 150 to 300° C., preferably 180 to 280° C., and more preferably 180 to 260° C. If the cylinder temperature is too low, moldability may be reduced, and conversely, if it is too high, the mechanical properties of the molded article may be reduced.

[0233] When the thermoplastic resin is a polyolefin resin, the cylinder temperature is, for example, 150 to 250°C, preferably 180 to 230°C, and more preferably 190 to 210°C.

[0234] When the thermoplastic resin is a polyacetal resin, the cylinder temperature is, for example, 150 to 250°C, preferably 180 to 230°C, and more preferably 200 to 220°C.

[0235] When the thermoplastic resin is a polyester resin, the cylinder temperature is, for example, 150 to 300°C, preferably 220 to 280°C, and more preferably 240 to 260°C.

[0236] When the thermoplastic resin is a polyamide resin, the cylinder temperature is, for example, 150 to 300°C, preferably 220 to 280°C, and more preferably 240 to 260°C.

[0237] The injection pressure is, for example, 10 to 100 MPa, preferably 20 to 80 MPa, and more preferably 40 to 60 MPa.

[0238] The mold temperature is, for example, 10 to 130° C., preferably 15 to 120° C., and more preferably 20 to 100° C. If the mold temperature is too low, the productivity of the molded article may decrease, whereas if the mold temperature is too high, the mechanical properties of the molded article may decrease.

[0239] When the thermoplastic resin is a polyolefin resin, the mold temperature is, for example, 10 to 100°C, preferably 15 to 50°C, and more preferably 20 to 40°C.

[0240] When the thermoplastic resin is a polyacetal resin, the mold temperature is, for example, 10 to 100°C, preferably 20 to 70°C, and more preferably 30 to 50°C.

[0241] When the thermoplastic resin is a polyester resin, the mold temperature is, for example, 30 to 120°C, preferably 50 to 90°C, and more preferably 60 to 80°C.

[0242] When the thermoplastic resin is a polyamide resin, the mold temperature is, for example, 30 to 130°C, preferably 60 to 100°C, and more preferably 70 to 90°C.

[0243] The shape of the molded article of the present disclosure is not particularly limited and can be selected depending on the application, and examples thereof include one-dimensional structures such as linear or thread-like structures, two-dimensional structures such as film-like, sheet-like, and plate-like structures, and three-dimensional structures such as block-like, rod-like, tubular, hollow, etc. In particular, the resin composition of the present disclosure allows molded articles to be produced with high productivity by injection molding, so that even three-dimensional structures can be produced with high productivity.

[0244] [Rubber Composition] The rubber composition of the present disclosure includes the granules and rubber. The granules are granular and have a specific bulk density, making them easy to handle. For example, when preparing a rubber composition by kneading the granules with rubber, the granules can be smoothly fed into a kneader, and even when kneaded with rubber, aggregation of the fibrous filler (A) contained in the granules can be suppressed. Therefore, the fibrous filler (A) can be uniformly dispersed in the rubber composition, improving the mechanical properties of the rubber composition.

[0245] (Rubber) The rubber contained in the resin composition is an unvulcanized rubber component. The rubber is not particularly limited, and conventional rubbers can be used. Examples of conventional rubbers include diene rubbers, olefin rubbers, acrylic rubbers (ACM, ANM), butyl rubbers (IIR), epichlorohydrin rubbers (CO), polysulfide rubbers (OT, EOT), urethane rubbers (U), silicone rubbers (Q), fluororubbers (FFKM, FKM), and sulfur-containing rubbers. These rubbers can be used alone or in combination of two or more. Of these rubbers, diene rubbers and / or olefin rubbers are preferred because they have a significant effect of improving the dispersibility of the fibrous filler (A).

[0246] Examples of diene rubbers include natural rubber (NR), epoxidized natural rubber, polybutadiene [e.g., butadiene rubber (BR), 1,2-polybutadiene (VBR)], isoprene rubber (IR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and styrene-butadiene rubber (SBR). These diene rubbers may be hydrogenated rubbers (e.g., hydrogenated BR, hydrogenated NBR, hydrogenated SBR, etc.). These diene rubbers may be used alone or in combination of two or more.

[0247] Examples of olefin-based rubbers include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-butene rubber, ethylene-1-butene-diene rubber, propylene-1-butene-diene rubber, polyisobutylene rubber, ethylene-vinyl acetate rubber, maleic acid-modified ethylene-propylene rubber (M-EPM), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), and maleic acid-modified chlorinated polyethylene (M-CM). Examples of diene units (non-conjugated diene units) contained in olefin-based rubbers include units derived from dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene. These olefin-based rubbers can be used alone or in combination of two or more.

[0248] The copolymer rubber may be a random or block copolymer, and block copolymers include copolymers having an AB type, ABA type, tapered type, or radial teleblock type structure.

[0249] Of these, diene rubbers and / or olefin rubbers are preferred, and at least one selected from the group consisting of SBR, EPM and EPDM is particularly preferred.

[0250] Among these, diene rubbers are preferred because they can highly improve the hardness and tear strength of the vulcanizate of the rubber composition.Furthermore, among diene rubbers, diene rubbers having an aromatic skeleton or aromatic ring, such as SBR, are particularly preferred because they have a significant effect of improving the dispersibility of the fibrous filler (A).

[0251] The proportion of the diene rubber in the rubber may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass.

[0252] (Ratio of Granules) The ratio of granules can be selected from a range of about 1 to 100 parts by mass per 100 parts by mass of rubber, preferably 3 to 50 parts by mass, 5 to 40 parts by mass, 5.5 to 30 parts by mass, 6 to 20 parts by mass, 6 to 15 parts by mass, 6.5 to 12 parts by mass, and most preferably 7 to 10 parts by mass. If the ratio of granules is too low, it may be difficult to uniformly disperse the plant-derived fibrous filler (A) in the rubber, and conversely, if it is too high, the moldability of the rubber composition may be reduced.

[0253] (Plant-derived fibrous filler) The rubber composition of the present disclosure may further contain a third plant-derived fibrous filler in addition to the plant-derived fibrous filler (A) (first plant-derived fibrous filler) contained in the granules. The third fibrous filler, including preferred embodiments, can be selected from the fibrous fillers exemplified as the plant-derived fibrous filler (A) contained in the granules.

[0254] The proportion of the third plant-derived fibrous filler relative to 100 parts by mass of rubber may be 100 parts by mass or less, for example, 10 parts by mass or less, preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and most preferably 1 part by mass or less, for example, 0.1 to 2 parts by mass.

[0255] In the rubber composition of the present disclosure, the granules preferably contain a plant-derived fibrous filler because the plant-derived fibrous filler can be easily dispersed uniformly in the rubber composition. Therefore, the rubber composition of the present disclosure is preferably substantially free of, and particularly preferably completely free of, a third plant-derived fibrous filler.

[0256] (Additives) The rubber composition of the present disclosure may further contain conventional additives compounded into rubber. Examples of such additives include vulcanizing agents (sulfur-based vulcanizing agents such as sulfur, organic peroxides, etc.), vulcanization aids, fillers or reinforcing agents (carbon black, silica, short fibers, etc.), coupling agents such as silane coupling agents, softeners, plasticizers, anti-aging or antioxidant agents (aromatic amine-based or benzimidazole-based antioxidants, etc.), colorants such as dyes and pigments, stabilizers (ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), release agents, lubricants, flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.), vibration-damping agents, flame retardant aids, antistatic agents, conductive agents, dispersants, flow adjusters, leveling agents, lubricants, antifoaming agents, surface modifiers, stress reducers, adhesives, pressure-sensitive adhesives, adhesion improvers, tackifiers, nucleating agents, crystallization accelerators, antibacterial agents, and preservatives. These additives can be used alone or in combination of two or more.

[0257] The total proportion of the additives may be 1000 parts by mass or less, for example, 0.01 to 100 parts by mass, preferably 0.1 to 50 parts by mass, further preferably 0.5 to 30 parts by mass, and further preferably 1 to 20 parts by mass, per 100 parts by mass of rubber.

[0258] (Characteristics of Rubber Composition) The rubber composition of the present disclosure has excellent mechanical properties because the fibrous filler (A) such as cellulose fiber is uniformly dispersed in the rubber composition.

[0259] The vulcanizate (crosslinked product) of the rubber composition of the present disclosure has high hardness. The hardness (Type A durometer) of the vulcanizate of the rubber composition of the present disclosure may be 30 or more, for example, 35 to 50, preferably 37 to 45, further preferably 38 to 43, and even more preferably 39 to 41.

[0260] In this specification and claims, hardness (type A durometer) can be measured using a durometer (type A) in accordance with ISO 7619-1.

[0261] (Method for Producing Rubber Composition) The rubber composition of the present disclosure can be produced by a method including a rubber kneading step of kneading granules with rubber. In the rubber kneading step, the granules and rubber may be kneaded by a conventional kneading method depending on the type of rubber. Examples of the kneading method include a method using a roll kneader such as a mixing roller, and a method using an internal kneader such as a Banbury mixer, an intermix, a kneader, or an extruder (e.g., a single-screw or twin-screw extruder). Of these kneading methods, the kneading method using an internal kneader is preferred, and the kneading method using a kneader is particularly preferred, as it is easy to knead the fibrous filler (A) uniformly.

[0262] The kneading temperature can be appropriately selected depending on the type of rubber, and may be a temperature equal to or higher than the melting point or melting temperature of the organic material (B), for example, 80 to 200°C, preferably 100 to 150°C, further preferably 105 to 140°C, further preferably 110 to 135°C, and most preferably 115 to 130°C.

[0263] The screw rotation speed is, for example, 5 to 500 rpm, preferably 10 to 100 rpm, and more preferably 30 to 50 rpm. The kneading time is, for example, 0.5 to 60 minutes, preferably 1 to 30 minutes, and more preferably 3 to 10 minutes.

[0264] (Molded Article) The molded article of the present disclosure can be produced by molding the rubber composition by a conventional molding method. The conventional molding method may be a method including a vulcanization step of vulcanizing (or crosslinking) the rubber composition.

[0265] In the vulcanization step, the vulcanization temperature can be selected depending on the type of rubber, and is, for example, 100 to 250°C, preferably 130 to 200°C, more preferably 140 to 190°C, and even more preferably 145 to 180°C.

[0266] The shape of the molded article of the present disclosure is not particularly limited and can be selected depending on the application, and examples thereof include one-dimensional structures such as linear or thread-like structures, two-dimensional structures such as film-like, sheet-like, and plate-like structures, and three-dimensional structures such as block-like, rod-like, tubular, hollow, etc. In particular, since the rubber composition of the present disclosure allows molded articles to be produced with high productivity by injection molding, even three-dimensional structures can be produced with high productivity.

[0267] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The raw materials, equipment and evaluation methods used in the examples are as follows.

[0268] [Raw materials] (Plant-derived fibrous filler) Cellulose fiber: A sheet of plant-derived pulp (chemically unmodified fiber, average fiber diameter 40 μm, average fiber length 1 mm or more) cut into chips of approximately 4 mm × 4 mm square, bulk density 0.15 g / cm ３

[0269] (Organic Materials) BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, "BPEF" manufactured by Osaka Gas Chemicals Co., Ltd., molecular weight 438.5, solid at room temperature, powder, average particle size 3 μm Stearic acid: manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 284.5, solid at room temperature, powder, average particle size 2 μm Stearic acid amide: manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 283.5, solid at room temperature, powder, average particle size 2 μm BisA-2EO: 4,4'-isopropylidenebis(2-phenoxyethanol), manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd., molecular weight 316.4, solid at room temperature, powder, average particle size 2 μm PEG200: polyethylene glycol 200, manufactured by Tokyo Chemical Industry Co., Ltd., average molecular weight 190 to 210, liquid at room temperature

[0270] (Thermoplastic resins) High-density polyethylene resin (HDPE): "Novatec HD HJ490" manufactured by Japan Polyethylene Corporation Polyacetal resin (POM): "Duracon M450-44" manufactured by Polyplastics Co., Ltd. Polybutylene terephthalate resin (PBT): "Novaduran 5010R5" manufactured by Mitsubishi Engineering Plastics Corporation Polyamide 6 resin (PA6): "Unitika Nylon A1030BRL" manufactured by Unitika Ltd.

[0271] (Rubber) SBR: "ESBR 1502" manufactured by ENEOS Material Co., Ltd.

[0272] [Equipment used] Mixer: Kawata Co., Ltd. "Super Mixer SMV-20B" Extrusion granulator: Dalton Co., Ltd. "Disc Pelletter F-5 Type", die diameter 3 mm Twin-screw extruder: Technovel Co., Ltd. "MFU25W-45MG-NH" Injection molding machine: Thermo Fisher Scientific Co., Ltd. "HAAKE MiniJet Pro" Batch kneader: Technovel Co., Ltd. "MSR-60" Manual hydraulic vacuum heating press: Imoto Machinery Co., Ltd.

[0273] [Granulation Properties] In Examples 1 to 6 and Comparative Examples 1 and 2, the cellulose fiber, organic material, and water were granulated in an extrusion granulator, and the granulation properties were evaluated according to the following criteria.

[0274] Acceptable: Granulation was performed stably and the product solidified into pellets. Unacceptable: The product did not solidify into pellets and could not be granulated.

[0275] [Granule Shape] The shapes of the granules obtained in Examples 1 to 6 were evaluated according to the following criteria.

[0276] ○: Almost pellet-like △: Pellet-like, but with many cracks and splinters on the surface

[0277] [Bulk Density] 100 mL of the granules obtained in Examples 1 to 6 and the flocculants obtained in Comparative Examples 4 and 5 were placed in a 100 mL measuring cylinder without tapping, the mass of the contents was measured, and the bulk density was calculated according to the following formula.

[0278] Bulk density (g / cm３ ) = mass of contents (g) / capacity (100 cm ３ )

[0279] [Feedability] In Examples 7 to 15 and Comparative Examples 3 to 12, when preparing the resin compositions, the feedability of raw materials to the feeder of the twin-screw extruder, which is a kneader, was evaluated according to the following criteria.

[0280] Pass: Raw materials were supplied to the kneader stably. Fail: Bridging occurred and raw materials could not be supplied to the kneader.

[0281] [Aggregation of Resin Composition or Rubber Composition] The resin compositions (kneaded products) obtained in Examples 7 to 15 and Comparative Examples 6, 8, 10, and 12, or the rubber compositions (kneaded products) obtained in Examples 16 to 18 were observed for the presence or absence of aggregates on their surfaces, and the results were evaluated according to the following criteria.

[0282] None: No agglomerates were observed on the surface of the kneaded product (details are as follows)

[0283] (Resin: Of 50 randomly selected pellets of the kneaded material (approximately 3 mm in diameter and 3 mm in length), there is one or less pellet containing an agglomerate with a diameter of 0.5 mm or more. Rubber: When a press sheet measuring 75 mm x 75 mm x 2 mm is prepared at a temperature of 150°C, there is one or less agglomerate with a diameter of 0.5 mm or more in the press sheet.)

[0284] Slight: A small amount of agglomerates was observed on the surface of the kneaded product (details are as follows)

[0285] (Resin: Of 50 randomly selected pellets of kneaded material (approximately 3mm diameter, 3mm length), 2 to 5 pellets contained aggregates with a diameter of 0.5mm or more. Rubber: When a press sheet measuring 75mm x 75mm x 2mm was prepared at a temperature of 150°C, the press sheet contained 2 to 5 aggregates with a diameter of 0.5mm or more.)

[0286] Many aggregates were observed on the surface of the kneaded material (details are as follows).

[0287] (Resin: Of 50 randomly selected pellets of kneaded material (approximately 3mm diameter, 3mm length), 6 or more pellets contain aggregates with a diameter of 0.5mm or more. Rubber: When a press sheet measuring 75mm x 75mm x 2mm is prepared at a temperature of 150°C, the press sheet contains 6 or more aggregates with a diameter of 0.5mm or more.)

[0288] [Flexural Strength and Flexural Modulus] The flexural strength and flexural modulus of the rectangular test specimens obtained in Examples 7 to 15 and Comparative Examples 3 and 6 to 12 were measured in accordance with ISO 178.

[0289] [Durometer Hardness] The durometer hardness of the sheet-like test pieces obtained in Examples 16 to 18 and Comparative Example 13 was measured in accordance with ISO 7619-1.

[0290] Example 1: 100 parts by mass of cellulose fiber, 33.3 parts by mass of BPEF, and 166.7 parts by mass of water were stirred for 10 minutes at 2000 rpm using a mixer. The resulting mixture was granulated in an unheated state using an extrusion granulator to produce wet granules, and the granulation properties were evaluated. Subsequently, the resulting wet granules were dried at 100°C for 8 hours using a vacuum dryer to remove moisture, yielding granule A. The shape of the resulting granule A was evaluated.

[0291] Example 2 Granules B were produced in the same manner as in Example 1 except that the ratio of BPEF and water was changed to the ratio shown in Table 1, and the granulation properties and shape of granules B were evaluated.

[0292] Example 3 Granules C were produced in the same manner as in Example 1 except that the ratio of BPEF and water was changed to the ratio shown in Table 1, and the granulation properties and shape of the granules C were evaluated.

[0293] Example 4 Granules D were produced in the same manner as in Example 1 except that stearic acid was used instead of BPEF, and the granulation properties and shape of granules D were evaluated.

[0294] Example 5 Granules E were produced in the same manner as in Example 1 except that stearic acid amide was used instead of BPEF, and the granulation properties and shape of granules E were evaluated.

[0295] Example 6 Granules F were produced in the same manner as in Example 1 except that BisA-2EO was used instead of BPEF, and the granulation properties and shape of granules F were evaluated.

[0296] [Comparative Example 1] 100 parts by mass of cellulose fiber and 100 parts by mass of water were stirred for 10 minutes at a rotation speed of 2000 rpm using a mixer. The resulting mixture was granulated using an extrusion granulator, but the mixture did not solidify into pellets, and granulation was not possible.

[0297] Comparative Example 2: 100 parts by mass of cellulose fiber, 33.3 parts by mass of PEG 200, and 166.7 parts by mass of water were stirred for 10 minutes at 2000 rpm using a mixer. The resulting mixture was granulated using an extrusion granulator, but the mixture did not solidify into pellets, and granulation was not possible.

[0298] The compositions and evaluation results of Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1.

[0299]

[0300] As is clear from Table 1, in Comparative Example 1, which contained only cellulose fiber and water, the product did not solidify and could not be granulated, whereas in Examples 1 to 3, in which BPEF was added in addition to cellulose fiber and water, stable granulation was possible. Comparing Examples 1 to 3, in Example 3, which contained a relatively small amount of BPEF, noticeable cracks and burrs were observed in the granules, whereas in Examples 1 and 2, which contained a relatively large amount of BPEF, there were no problems with the shape of the granules. Furthermore, in Examples 4 to 6, in which various organic materials were used instead of BPEF, granulation was possible without any problems, just like in Examples 1 and 2. On the other hand, in Comparative Example 2, in which PEG 200, a liquid compound comparative material, was used instead of BPEF, the product did not solidify and granulation was not possible, just like in Comparative Example 1.

[0301] Example 7: 86.7 parts by mass of HDPE and 13.3 parts by mass of the granules A obtained in Example 1 were kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and the feedability and cohesion properties were evaluated. During kneading, the HDPE was top-fed using the top feeder of the extruder, and the granules A were side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 200°C and a mold temperature of 30°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0302] Example 8: 86.7 parts by mass of HDPE, 1.6 parts by mass of BPEF, and 11.7 parts by mass of granules B obtained in Example 2 were kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and its feedability and cohesion were evaluated. During kneading, HDPE and BPEF were top-fed using the top feeder of the extruder, and granules B was side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 200°C and a mold temperature of 30°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0303] Example 9: 86.7 parts by mass of HDPE, 2.3 parts by mass of BPEF, and 11.0 parts by mass of the granules C obtained in Example 3 were kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and its feedability and coagulation properties were evaluated. During kneading, HDPE and BPEF were top-fed using the top feeder of the extruder, and granules C were side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 200°C and a mold temperature of 30°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0304] [Examples 10 to 12] Strip-shaped test pieces were produced in the same manner as in Example 7, except that granules D to F were used instead of granule A, and the feeding property and cohesiveness were evaluated, and the bending strength and bending modulus of the test pieces were measured.

[0305] Comparative Example 3: HDPE was mixed using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare pelletized resin, and feedability was evaluated. During mixing, HDPE was top-fed using the top feeder of the extruder. The resulting resin pellets were injection-molded using an injection molding machine at a cylinder temperature of 200°C and a mold temperature of 30°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0306] Comparative Example 4 Preparation of Flocculant A Flocculant A was obtained in the same manner as in Example 1, except that the granulation was not performed using an extrusion granulator, but instead moisture was removed by vacuum drying. The obtained flocculant A was flocculant-like and had a bulk density of 0.06 g / cm. ３ It was.

[0307] (Preparation of strip-shaped test pieces) Kneading was attempted in the same manner as in Example 7, except that cotton-like material A was used instead of granules A. However, due to the low bulk density of cotton-like material A, poor feeding to the kneader occurred, and a kneaded product could not be produced.

[0308] Comparative Example 5 (Preparation of Cotton-like Material B) 200 g of water was added to 100 g of cellulose fiber and mixed in a household mixer to obtain 300 g of a water-wet material with a solid content of 33% by mass. 300 g of propylene glycol monomethyl ether acetate and 33.3 g of BPEF were added to the obtained water-wet material, and the mixture was stirred. After stirring, the water and propylene glycol monomethyl ether acetate were removed under reduced pressure at 80°C to obtain Cotton-like Material B. The bulk density of the obtained Cotton-like Material B was 0.05 g / cm ３ It was.

[0309] (Preparation of strip-shaped test pieces) Kneading was attempted in the same manner as in Example 7, except that cotton-like material B was used instead of granules A. However, due to the low bulk density of cotton-like material B, poor feeding to the kneader occurred, and it was not possible to produce a kneaded product.

[0310] Comparative Example 6: 86.7 parts by mass of HDPE, 3.3 parts by mass of BPEF, and 10.0 parts by mass of cellulose fiber were kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and its feedability and cohesion were evaluated. During kneading, HDPE and BPEF were top-fed using the top feeder of the extruder, and cellulose fiber was side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 200°C and a mold temperature of 30°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0311] The compositions and evaluation results of Examples 7 to 12 and Comparative Examples 3 to 6 are shown in Table 2.

[0312]

[0313] As is clear from Table 2, Examples 7 to 9, which contained BPEF-containing granules and HDPE, showed improved bending strength and bending modulus compared to Comparative Example 3, which contained only HDPE. Meanwhile, in Comparative Examples 4 and 5, an attempt was made to knead HDPE with a flocculent material, but the low bulk density of the flocculent material caused poor feeding into the kneader, making it impossible to produce a kneaded product. In Comparative Example 6, HDPE, cellulose fiber, and BPEF were kneaded, but the cellulose fiber was poorly dispersed, resulting in numerous aggregates on the surface of the kneaded product. Perhaps due to these aggregates, the bending strength and bending modulus of Comparative Example 6 were inferior to those of Examples 7 to 9. Furthermore, in Example 9, which used granules with a relatively low amount of BPEF, some aggregates were observed on the surface of the kneaded product. This is thought to be due to the inability to completely suppress the aggregation of cellulose fibers during drying when the amount of BPEF used during granulation is relatively low. Perhaps due to these aggregates, the bending strength and bending modulus of Example 9 were slightly lower than those of Examples 7 and 8. Examples 10 to 12, which contained HDPE and various organic material-containing granules other than BPEF, had no problems with feedability to the kneader or surface agglomerates, similar to Examples 7 and 8, which used BPEF-containing granules. However, because the skeleton of the organic material used was softer than that of BPEF and did not have a polycyclic aromatic ring, the flexural strength and flexural modulus of Examples 10 to 12 were inferior to those of Examples 7 to 8.

[0314] Example 13: 86.7 parts by mass of POM and 13.3 parts by mass of the granules A obtained in Example 1 were kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and the feedability and cohesion properties were evaluated. During kneading, the POM was top-fed using the top feeder of the extruder, and the granules A were side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 210°C and a mold temperature of 40°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0315] Example 14: 86.7 parts by mass of PBT and 13.3 parts by mass of the granules A obtained in Example 1 were kneaded using a twin-screw extruder at a temperature of 230°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and the feedability and coagulation properties were evaluated. During kneading, the PBT was top-fed using the top feeder of the extruder, and the granules A were side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 70°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0316] [Example 15] 86.7 parts by mass of PA6 and 13.3 parts by mass of the granules A obtained in Example 1 were kneaded using a twin-screw extruder at a temperature of 230°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and the feedability and coagulation properties were evaluated. During kneading, PA6 was top-fed using the top feeder of the extruder, and granules A was side-fed using the side feeder of the extruder. The obtained resin composition was injection-molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 80°C to obtain strip-shaped test pieces. The flexural strength and flexural modulus of the obtained test pieces were measured.

[0317] Comparative Example 7: POM was kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare pelletized resin, and its feedability was evaluated. During kneading, the POM was top-fed using the top feeder of the extruder. The resulting resin pellets were injection-molded using an injection molding machine at a cylinder temperature of 210°C and a mold temperature of 40°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0318] Comparative Example 8: 86.7 parts by mass of POM, 3.3 parts by mass of BPEF, and 10.0 parts by mass of cellulose fiber were kneaded using a twin-screw extruder at a temperature of 200°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and its feedability and cohesion were evaluated. During kneading, the POM and BPEF were top-fed using the top feeder of the extruder, and the cellulose fiber was side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 210°C and a mold temperature of 40°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0319] Comparative Example 9: PBT was kneaded using a twin-screw extruder at a temperature of 230°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare pelletized resin, and the feedability was evaluated. During kneading, PBT was top-fed using the top feeder of the extruder. The obtained resin pellets were injection-molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 70°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the obtained test specimens were measured.

[0320] [Comparative Example 10] 86.7 parts by mass of PBT, 3.3 parts by mass of BPEF, and 10.0 parts by mass of cellulose fiber were kneaded using a twin-screw extruder at a temperature of 230°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and its feedability and cohesion were evaluated. During kneading, PBT and BPEF were top-fed using the top feeder of the extruder, and cellulose fiber was side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 70°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0321] [Comparative Example 11] PA6 was kneaded using a twin-screw extruder at a temperature of 230°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare pelletized resin, and the feedability was evaluated. During kneading, PA6 was top-fed using a top feed. The obtained resin pellets were injection-molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 80°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the obtained test specimens were measured.

[0322] [Comparative Example 12] 86.7 parts by mass of PA6, 3.3 parts by mass of BPEF, and 10.0 parts by mass of cellulose fiber were kneaded using a twin-screw extruder at a temperature of 230°C, a screw rotation speed of 150 rpm, and a discharge rate of approximately 10 kg / h to prepare a pellet-shaped resin composition, and its feedability and cohesion were evaluated. During kneading, PA6 and BPEF were top-fed using the top feeder of the extruder, and the cellulose fiber was side-fed using the side feeder of the extruder. The resulting resin composition was injection-molded using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 80°C to obtain strip-shaped test specimens. The flexural strength and flexural modulus of the resulting test specimens were measured.

[0323] The compositions and evaluation results of Examples 13 to 15 and Comparative Examples 7 to 12 are shown in Table 3.

[0324]

[0325] As is clear from Table 3, Examples 13, 14, and 15, which contained the corresponding resin and granules, had improved bending strength and bending modulus compared to Comparative Examples 7, 9, and 11, which contained only resin. In contrast, Comparative Examples 8, 10, and 12, in which the resin, cellulose fiber, and BPEF were kneaded, had insufficient dispersibility of the cellulose fiber, and many aggregates were observed on the surface of the kneaded product. Perhaps due to these aggregates, the bending strength and bending modulus of Comparative Examples 8, 10, and 12 were inferior to those of Examples 13, 14, and 15, which contained the corresponding resin and granules.

[0326] Example 16 A block rubber composition was prepared by kneading 93.3 parts by mass of SBR and 6.7 parts by mass of the granules A obtained in Example 1 for 5 minutes using a batch kneader at a temperature of 120°C and a screw rotation speed of 40 rpm. The obtained rubber composition was pressed for 2 minutes using a manual hydraulic vacuum heating press at a hot platen temperature of 150°C to obtain a sheet-like test piece.

[0327] Example 17 A block rubber composition was prepared by kneading 93.3 parts by mass of SBR, 0.9 parts by mass of BPEF, and 5.8 parts by mass of the granules B obtained in Example 2 for 5 minutes using a batch kneader at a temperature of 120°C and a screw rotation speed of 40 rpm. The obtained rubber composition was pressed for 2 minutes using a manual hydraulic vacuum heating press at a hot platen temperature of 150°C to obtain a sheet-like test piece.

[0328] Example 18 A block rubber composition was prepared by kneading 93.3 parts by mass of SBR, 1.2 parts by mass of BPEF, and 5.5 parts by mass of the granules C obtained in Example 3 for 5 minutes using a batch kneader at a temperature of 120°C and a screw rotation speed of 40 rpm. The obtained rubber composition was pressed for 2 minutes using a manual hydraulic vacuum heating press at a hot platen temperature of 150°C to obtain a sheet-like test piece.

[0329] Comparative Example 13 SBR was pressed for 2 minutes using a manual hydraulic vacuum heating press at a hot plate temperature of 150° C. to obtain a sheet-like test piece.

[0330] The compositions and evaluation results of Examples 16 to 18 and Comparative Example 13 are shown in Table 4.

[0331]

[0332] As is clear from Table 4, compared to Comparative Example 13, which contained only SBR, Examples 16 to 18, which contained SBR and granules, showed improved hardness. Comparing Examples 16 to 18, a tendency for the amount of surface aggregates of the kneaded material to increase in the order of Examples 16, 17, and 18, in which the amount of BPEF in the granules decreased. This is thought to be because the smaller the amount of BPEF during granule preparation, the less adequately the cellulose fibers are suppressed from coagulating during drying. Perhaps due to these aggregates, the hardness decreased in the order of Examples 16, 17, and 18, in which the amount of BPEF in the granules decreased. Furthermore, a tendency for aggregates to form more easily in the rubber composition was observed compared to the resin composition using the same granules (Examples 16 and 7, and Example 17 and 8). This is thought to be due to the fact that the batch kneader used for rubber kneading has lower shear forces than the twin-screw extruder used for resin kneading, making aggregates more likely to form.

[0333] The granules of the present disclosure have excellent dispersibility in resins and rubbers and can be used as reinforcing agents for resins and rubbers. Resin compositions containing the granules of the present disclosure can be used in various fields of resin molded products [e.g., automobile parts, electrical and electronic parts, building materials (wall materials, etc.), civil engineering materials, agricultural materials, packaging materials (containers, cushioning materials, etc.), household materials (daily commodities, etc.), optical components, etc.]. Rubber compositions containing the granules of the present disclosure can be used in various industrial components (belts such as conveyor belts; rolls such as rubber cover rolls and printing rolls; gaskets; seals such as oil seals; packings; hoses such as oil-resistant hoses, etc.), building components (window frame rubber, vibration damping materials, carpetbagging materials, etc.), transportation components (automotive components, tires, power transmission belts, etc.), and electrical and electronic device components (wire coatings, etc.).

Claims

1. A composite material comprising a fibrous filler (A) derived from a plant and an organic material (B) and having a bulk density of 0.1 to 0.5 g / cm ３ wherein the average fiber diameter of the fibrous filler (A) is 0.5 to 100 μm, the organic material (B) is solid at room temperature and normal pressure, the molecular weight of the organic material (B) is 100 to 1000, the organic material (B) is a compound having a hydrophobic skeleton and a polar group, the hydrophobic skeleton contains at least one selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons, the polar group contains at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and an amide group, and the proportion of the organic material (B) is 1 to 70 parts by mass per 100 parts by mass of the fibrous filler (A).

2. The granules according to claim 1, which are used for kneading with resin or rubber.

3. The granules according to claim 1 or 2, wherein the organic material (B) is a non-fibrous organic material having a melting point of 100°C or higher.

4. The granule according to claim 1 or 2, wherein the hydrophobic skeleton is a polycyclic aromatic ring.

5. The granule according to claim 1 or 2, wherein the organic material (B) is a compound represented by the following formula (1): (Wherein, ring Z is an arene ring, R １ and R ２ is a substituent, X １ represents a heteroatom-containing functional group, k represents an integer of 0 to 4, n represents an integer of 1 or more, and p represents an integer of 0 or more.

6. In the formula (1), X １ is the group -(OA) ｍ１ The granule according to claim 5, wherein A is an alkylene group and m1 is an integer of 0 or more.

7. The granule according to claim 1 or 2, wherein the fibrous filler (A) is a cellulose fiber.

8. A method for producing a resin composition, comprising a resin kneading step of kneading the granules according to claim 1 or 2 with a resin.

9. A method for producing a rubber composition, comprising a rubber kneading step of kneading the granules according to claim 1 or 2 with rubber.

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