JP7299087B2 - Rubber-like composition and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber-like composition containing cellulose coated with a compound having a 9,9-bisarylfluorene skeleton and a method for producing the same.

Cellulose, which is a plant-derived fiber, has a low environmental load, is a sustainable resource, and has excellent properties such as high elastic modulus, high strength, and low coefficient of linear expansion. Therefore, it is used in a wide range of applications, such as materials for paper, films and sheets, resin composite materials (for example, resin reinforcing agents), and the like. Also in rubber compositions, cellulose is added as a reinforcing agent in order to improve the mechanical properties of the rubber.

Japanese Patent Application Laid-Open No. 2005-75856 (Patent Document 1) describes a finely powdered cellulose fiber prepared from natural plant fibers and having an average particle size of 100 μm as a rubber composition capable of achieving both excellent low heat build-up and rigidity. A tire rubber composition containing 2 to 100 parts by weight per 100 parts by weight of diene rubber is disclosed. In addition, Japanese Patent Application Laid-Open No. 2005-133025 (Patent Document 2) describes a rubber composition having excellent abrasion resistance, which contains 5 to 75 parts by weight of starch and a fiber diameter of 1 μm or less with respect to 100 parts by weight of a diene rubber component. A rubber composition comprising 0.1 to 40 parts by weight of bacterial cellulose is disclosed.

Therefore, in order to improve the compatibility between rubber and cellulose, Japanese Patent No. 4581116 (Patent Document 3) discloses a vulcanized rubber composition having excellent breaking properties and less energy loss at the interface between rubber and cellulose. 1 to 50 parts by weight of chemically modified microfibril cellulose having an average fiber diameter of 4 nm to 1 μm (more preferably 7 to 15 parts by weight) is disclosed. This document describes acetylation, alkyl esterification, complex esterification, β-ketoesterification, and arylcarbamation as methods for chemically modifying microfibril cellulose.

JP 2005-75856 A JP-A-2005-133025 Japanese Patent No. 4581116

However, in the rubber composition of Patent Document 1, since the compatibility between rubber and cellulose is low, it is difficult to uniformly disperse cellulose, cellulose aggregates in the rubber, and the rupture characteristics of the rubber deteriorate. do. Moreover, even in the rubber compositions of Patent Documents 2 and 3, mechanical properties such as strength, elongation and hardness cannot be improved, probably because the affinity between rubber and chemically modified microfibril cellulose is low. Furthermore, in order to improve these properties, a large amount of chemically modified microfibril cellulose is required, making it difficult to achieve both properties.

Accordingly, an object of the present invention is to provide a rubbery composition capable of improving mechanical properties such as strength, elongation and hardness, and a method for producing the same.

As a result of intensive studies to achieve the above object, the present inventors added a compound having a cellulose and a 9,9-bis(aryl)fluorene skeleton and a softening agent to a mixture of a rubber component and a reinforcing agent. By mixing, a rubber-like composition in which cellulose is uniformly dispersed in the rubber can be prepared, and mechanical properties such as strength, elongation and hardness of the rubber-like composition can be improved. bottom.

That is, the rubber-like composition of the present invention comprises a rubber component (A), cellulose (B), a fluorene compound (C) having a 9,9-bis(aryl)fluorene skeleton, a reinforcing agent (D) and a softening agent (E ), and when formed into a sheet, the number of aggregated portions of the cellulose (B) having a major axis of 200 μm or more is 30/(10 cm) ² or less on the surface of the sheet. The fluorene compound (C) may be a compound represented by the following formula (1).

(Wherein, ring Z is an arene ring, R ¹ and R ² are substituents, X ¹ is a heteroatom-containing functional group, k is an integer of 0 to 4, n is an integer of 1 or more, and p is an integer of 0 or more. show).

In the above formula (1), X ¹ is a group -[(OA) _m1 -Y ¹ ] (wherein A is an alkylene group, Y ¹ is a hydroxyl group or a glycidyloxy group, and m1 is an integer of 0 or more). and in particular Y ¹ may be a hydroxyl group. The fluorene compound (C) may adhere to at least part of the surface of the cellulose (B). The cellulose (B) and the fluorene compound (C) are not covalently bonded. The cellulose (B) may be cellulose nanofibers. The reinforcing agent (D) may contain carbon black. The rubbery composition may further contain a silane coupling agent (F). The rubber component (A) may be a vulcanizable or crosslinkable rubber and/or thermoplastic elastomer.

The present invention includes a first mixing step of mixing the rubber component (A) and the reinforcing agent (D) to prepare a first mixture, the first mixture, cellulose (B) and 9,9-bis ( A second mixing step of mixing a fluorene compound (C) having an aryl)fluorene skeleton and a second softening agent that is part of the softening agent (E) to prepare a second mixture. It also includes a method of manufacturing a product. This production method further includes a first premixing step of premixing the cellulose (B) and the fluorene compound (C) to prepare a first premix, and in the second mixing step, A method of mixing the first mixture, the first preliminary mixture, and the second softener to prepare a second mixture may be used. The production method further includes a second premixing step of premixing the cellulose (B), the fluorene compound (C), and the second softener to prepare a second premix, In the mixing step of (1), the first mixture and the second preliminary mixture may be mixed to prepare the second mixture. In the second mixing step, the silane coupling agent (F) may be further mixed to prepare a second mixture. In the manufacturing method, the rubber-like composition further contains a plasticizer (G), a vulcanizing agent (H) and a vulcanizing aid (I), and in the first mixing step, the softening agent (E) is added. It may be mixed with the balance of the first softening agent, the plasticizer (G), the vulcanizing agent (H) and the vulcanizing aid (I) to prepare a first mixture. In the production method, the rubber component (A) is a vulcanizable or crosslinkable rubber, and the unvulcanized rubber composition obtained in the second mixing step is vulcanized to obtain a vulcanized rubber composition. A vulcanization step may be further included.

The present invention also includes a molded article formed from the rubber-like composition. This molded body may be a hose member, a seal member, a tire, a belt or an anti-vibration rubber.

In the present invention, since cellulose, a compound having a 9,9-bis(aryl)fluorene skeleton, and a softening agent are added to a mixture of a rubber component and a reinforcing agent, the cellulose is uniformly distributed in the rubber component. It can be dispersed, and the mechanical properties such as strength, elongation and hardness of the rubbery composition can be improved at the same time.

1 is a scanning electron microscope (SEM) photograph of cellulose nanofibers used in Example 1. FIG. FIG. 2 is a scanning electron microscope (SEM) photograph of a portion where defibration of the composite of BPEF and cellulose nanofibers obtained in Example 1 has progressed. FIG. 3 is a scanning electron microscope (SEM) photograph of a portion of the composite of BPEF and cellulose nanofibers obtained in Example 1 where defibration did not proceed sufficiently.

The rubber-like composition of the present invention comprises a rubber component (A), cellulose (B), a fluorene compound (C) having a 9,9-bis(aryl)fluorene skeleton, a reinforcing agent (D) and a softening agent (E). including.

[Rubber component (A)]
The rubber component (A) includes vulcanizable or crosslinkable rubbers and thermoplastic elastomers. Rubbers and thermoplastic elastomers can be used alone or in combination of two or more.

The rubber is not particularly limited, and conventional rubber components can be used. Examples of conventional rubber components include diene rubber, olefin rubber, acrylic rubber (ACM, ANM), butyl rubber (IIR), epichlorohydrin rubber (CO), polysulfide rubber (OT, EOT), urethane rubber, (U), silicone rubber (Q), fluororubber (FFKM, FKM), sulfur-containing rubber, and the like. These rubber components can be used alone or in combination of two or more. Among these rubbers, diene rubbers and/or olefin rubbers are preferable because the fluorene compound (C) has a large effect of improving the dispersibility of cellulose (B).

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

Examples of olefinic rubber 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), maleic acid-modified chlorinated polyethylene (M-CM), and the like. Examples of the diene unit (non-conjugated diene unit) contained in the olefinic rubber include units derived from dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, and ethylidenenorbornene. These olefinic rubbers can be used alone or in combination of two or more.

The copolymer rubber may be a random or block copolymer, and block copolymers include copolymers having AB type, ABA type, tapered type, or radial teleblock type structures. .

Of these, diene rubbers such as SBR and NBR, and olefin rubbers such as EPDM are preferred.

The thermoplastic elastomer may be any resin having rubber-like properties. The glass transition temperature of the thermoplastic elastomer can be appropriately selected from a range of about -50°C to 100°C depending on the application, for example -20°C to 80°C, preferably 0 to 50°C (eg 5 to 40°C), and further It is preferably 10-30°C, most preferably 15-25°C. In the present specification and claims, the glass transition temperature can be measured by a conventional method using a differential scanning calorimeter.

The hardness of the thermoplastic elastomer is 95° or less, for example, 50 to 90°, preferably 60 to 85°, more preferably 65 to 80° (especially 70 to 78°). If the hardness is too high, mechanical properties such as elongation may deteriorate.

The melt flow rate (MFR) of the thermoplastic elastomer may be 0.5 g/10 minutes or more, for example 0.5 to 20 g/10 minutes, by a method according to JIS K7210 (190°C, 2.16 kgf). , preferably 1 to 10 g/10 min, more preferably 1.5 to 5 g/10 min, most preferably 2 to 3 g/10 min. If the MFR is too small, the mechanical properties of the composition and the dispersibility of cellulose (B) in the composition may deteriorate.

As a specific thermoplastic elastomer, a commonly used thermoplastic elastomer can be used. Commonly used thermoplastic elastomers include, for example, olefinic thermoplastic elastomers, styrene thermoplastic elastomers, vinyl chloride thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, polyurethane thermoplastic elastomers, fluorine thermoplastic elastomers, Examples include plastic elastomers. These thermoplastic elastomers can be used alone or in combination of two or more. Among these thermoplastic elastomers, a styrene-based thermoplastic elastomer is preferable because the fluorene compound (C) has a large effect of improving the dispersibility of the cellulose (B).

The styrenic thermoplastic elastomer may be an elastomer having a hard portion composed of styrene units and a soft portion composed of diene units, such as a styrene-diene block copolymer or a hydrogenated product thereof. Styrene-diene block copolymers or hydrogenated products thereof include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers (SBS), and hydrogenated styrene. -butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene- and isoprene-styrene block copolymer (SEPS). In block copolymers, the terminal blocks may consist of either styrene blocks or diene blocks. Among these, (hydrogenated) styrene-butadiene block copolymers such as SBS and SEBS are preferred.

[Cellulose (B)]
Cellulose (B) includes pulp having a low content of non-cellulose components such as lignin and hemicellulose, for example, plant-derived cellulose raw materials {e.g., wood [e.g., conifers (pine, fir, spruce, hemlock, cedar, etc.), Broadleaf trees (beech, birch, poplar, maple, etc.)], herbs [hemp (hemp, flax, manila hemp, ramie, etc.), straw, bagasse, mitsumata, etc.], seed fiber (cotton linter, bombax cotton, kapok) etc.), bamboo, sugar cane, etc.}, animal-derived cellulose raw materials (such as sea squirt cellulose), bacterial-derived cellulose raw materials (such as cellulose contained in nata de coco), and the like. These celluloses can be used alone or in combination of two or more. Among these celluloses, cellulose derived from wood pulp (eg, softwood pulp, hardwood pulp, etc.), seed hair fiber pulp (eg, cotton linter pulp), and the like are preferred. The pulp may be mechanical pulp obtained by mechanically treating pulp material, but chemical pulp obtained by chemically treating pulp material is preferable because the content of non-cellulose components is small.

Cellulose (B) may be granular or the like, but is usually fibrous. When the cellulose (B) is fibrous cellulose (cellulose fibers), the fiber diameter of the cellulose (B) may be on the order of microns. It is preferable to have The average fiber diameter of the cellulose fibers is, for example, 1-1000 nm (eg, 2-800 nm), preferably 3-500 nm (eg, 5-300 nm), more preferably 10-200 nm, most preferably 15-100 nm. If the average fiber diameter is too large, properties such as strength of the rubber-like composition may deteriorate. The maximum fiber diameter of the cellulose fibers is, for example, 3 to 1000 nm (eg 4 to 900 nm), preferably 5 to 700 nm (eg 10 to 500 nm), more preferably 15 to 400 nm, most preferably 20 to 300 nm. In many cases, such nanometer-sized cellulose fibers do not substantially contain micrometer-sized cellulose fibers.

The average fiber length of the cellulose fibers can be selected, for example, from a range of about 0.01 μm or more (for example, 0.01 to 500 μm, preferably 0.1 to 400 μm), usually 1 μm or more (for example, 5 to 300 μm), preferably 10 μm or more. (for example, 20 to 200 μm), more preferably 30 μm or more (especially 50 to 150 μm). If the average fiber length is too short, the mechanical properties of the rubber-like composition may deteriorate, and if it is too long, the dispersibility in the rubber-like composition may deteriorate.

The ratio (aspect ratio) of the average fiber length to the average fiber diameter of the cellulose fibers is, for example, 5 or more (for example, about 5 to 10,000), preferably 10 or more (for example, about 10 to 5,000), more preferably 20 or more (for example, 20 to about 3000), particularly 50 or more (eg about 50 to 2000), 100 or more (eg about 100 to 1000), further 200 or more (eg about 200 to 800). On the other hand, if the aspect ratio is too small, the effect of reinforcing the rubber component will be reduced, and if the aspect ratio is too large, uniform dispersion will be difficult and the fibers may be easily decomposed (or damaged).

In the present specification and claims, the average fiber diameter, average fiber length and aspect ratio of cellulose fibers are calculated by randomly selecting 50 fibers from scanning electron micrograph images and averaging them. You may

Cellulose nanofibers may be nanofibers obtained by conventional methods, such as physical methods such as high-pressure homogenizer method, underwater counter-collision method, grinder method, ball mill method, biaxial kneading method, TEMPO catalyst, Nanofibers obtained by chemical methods using phosphoric acid, dibasic acid, sulfuric acid, hydrochloric acid, etc. may also be used.

Cellulose (B) may be highly crystalline cellulose (or cellulose fiber), and the crystallinity of cellulose (B) is, for example, 40 to 100% (eg, 50 to 100%), preferably 60 to 100. %, more preferably 70 to 100%, most preferably 75 to 99%, and the crystallinity is usually 60% or more (eg, 60 to 98%). Examples of the crystal structure of cellulose (B) include type I, type II, type III, type IV, etc. Type I crystal structure, which is excellent in linear expansion characteristics and elastic modulus, is preferred. The degree of crystallinity can be measured using a powder X-ray diffractometer (“Ultima IV” manufactured by Rigaku Corporation) or the like.

Cellulose (B) may contain non-cellulose components such as hemicellulose and lignin, and in the case of cellulose fibers (especially cellulose nanofibers), the proportion of non-cellulose components in fibrous cellulose is 30% by mass or less, preferably It is 20% by mass or less, more preferably 10% by mass or less. The cellulosic fibers may be cellulosic fibers substantially free of non-cellulosic components (particularly cellulosic fibers free of non-cellulosic components).

The degree of polymerization of cellulose (B) may be 500 or more, preferably 600 or more (for example, about 600 to 100,000) from the viewpoint of the mechanical properties of the composition. The viscosity average degree of polymerization is, for example, 100-10000, preferably 200-5000, more preferably 300-2000.

The viscosity average degree of polymerization can be measured by the viscosity method described in TAPPI T230. That is, 0.04 g of modified cellulose nanofiber (or raw material cellulose nanofiber) is precisely weighed, 10 mL of water and 10 mL of 1M copper ethylenediamine aqueous solution are added, and the mixture is stirred for about 5 minutes to dissolve the modified cellulose. The resulting solution is placed in an Ubbelohde viscosity tube and the flow rate is measured at 25°C. A mixed solution of 10 mL of water and 10 mL of 1M copper ethylenediamine aqueous solution is measured as a blank. Using the intrinsic viscosity [η] calculated based on these measured values, the viscosity-average degree of polymerization can be calculated according to the following formula described in the wood science experiment manual (edited by the Japan Wood Research Institute, Buneidou Publishing).

Viscosity average degree of polymerization=175×[η].

The proportion of cellulose (B) (in particular, cellulose fibers such as cellulose nanofibers) can be selected from the range of about 0.1 to 30 parts by mass, for example 0.2 to 30 parts by mass, with respect to 100 parts by mass of the rubber component (A). 25 parts by weight, preferably 0.3 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, most preferably 1 to 10 parts by weight. Furthermore, in the present invention, cellulose (B) (particularly cellulose fibers such as cellulose nanofibers) can be uniformly dispersed by the fluorene compound (C), which will be described later. Characteristics and heat resistance can be improved, and the ratio of cellulose (B) is, for example, 0.1 to 10 parts by mass, preferably 0.3 to 7 parts by mass, more preferably 0.3 to 7 parts by mass, with respect to 100 parts by mass of the rubber component (A). is 0.5 to 5 parts by weight, most preferably 1 to 3 parts by weight. If the proportion of cellulose (B) is too small, the mechanical properties of the rubber-like composition may deteriorate, and if it is too large, the moldability of the rubber-like composition may deteriorate.

[Fluorene compound (C)]
The fluorene compound (C) having aryl groups at the 9 and 9-positions functions as a compatibilizer or dispersant for uniformly dispersing the cellulose (B) in the rubber component (A). By uniformly dispersing the cellulose (B) therein, the mechanical properties of the rubber-like composition can be greatly improved.

Such a fluorene compound may be a compound having a 9,9-bisarylfluorene skeleton, and may be, for example, a fluorene compound represented by the formula (1).

In formula (1), examples of the arene ring represented by ring Z include monocyclic arene rings such as benzene ring, polycyclic arene rings, etc. Polycyclic arene rings include condensed polycyclic arene Rings (condensed polycyclic hydrocarbon rings), ring-assembled arene rings (ring-assembled aromatic hydrocarbon rings), and the like are included.

Condensed polycyclic arene rings include, for example, condensed bicyclic arene rings (e.g., condensed bicyclic C _10-16 arene rings such as naphthalene ring), condensed tricyclic arenes (e.g., anthracene ring, phenanthrene ring, etc.) ) and other condensed bi- to tetracyclic arene rings. Preferred condensed polycyclic arene rings include naphthalene ring, anthracene ring and the like, and naphthalene ring is particularly preferred.

The ring-assembled arene ring includes biarene ring [for example, biC _6-12 arene ring such as biphenyl ring, binaphthyl ring, phenylnaphthalene ring (eg, 1-phenylnaphthalene ring, 2-phenylnaphthalene ring, etc.)], tellarene Rings (eg, ter-C _6-12 arene rings such as terphenylene ring) can be exemplified. Preferred ring-assembled arene rings include biC _6-10 arene rings, particularly biphenyl rings, and the like.

The two rings Z substituted at the 9-position of fluorene may be different or the same, but usually they are the same ring in many cases. Among the rings Z, benzene ring, naphthalene ring, biphenyl ring (especially benzene ring) and the like are preferable.

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

Examples of heteroatom-containing functional groups represented by X 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 be usually 1 to 3, preferably 1 or 2.

Examples of the functional group include the group -[(OA) _m1 -Y ¹ ] (wherein Y ¹ is a hydroxyl group, a glycidyloxy group, an amino group, an N-substituted amino group or a mercapto group, and A is an alkylene group , m1 is an integer of 0 or more), a group —(CH ₂ ) _m2 —COOR ³ (wherein R ³ is a hydrogen atom or an alkyl group, and m2 is an integer of 0 or more).

In the group -[(OA) _m1 -Y ¹ ], the N-substituted amino group of Y ¹ is, for example, an N-monoalkylamino group (N-monoC _1-4 alkylamino group such as methylamino or ethylamino group etc.), N-monohydroxyalkylamino groups such as hydroxyethylamino group (N-monohydroxy C _1-4 alkylamino group etc.), and the like.

The alkylene group A includes a linear or branched alkylene group, and examples of the linear alkylene group include C _2-6 alkylene groups such as ethylene, trimethylene, and tetramethylene groups (preferably linear A chain C _2-4 alkylene group, more preferably a linear C _2-3 alkylene group, especially an ethylene group) can be exemplified. A branched C _3-6 alkylene group (preferably a branched C _3-4 alkylene group, especially a propylene group) such as a 1,3-butanediyl group can be mentioned.

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

In the group —(CH ₂ ) _m2 —COOR ³ , the alkyl group represented by R ³ includes linear or branched groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group. C _1-6 alkyl groups can be exemplified. Preferred alkyl groups are C _1-4 alkyl groups, especially C _1-2 alkyl groups. m2, which indicates the number of repeating methylene groups (average number of added moles), may be 0 or an integer of 1 or more (for example, 1 to 6, preferably 1 to 4, more preferably about 1 to 2). m2 may generally be 0 or 1-2.

Among these, the group X ¹ is preferably a group -[(OA) _m1 -Y ¹ ] (wherein A is an alkylene group, Y ¹ is a hydroxyl group or a glycidyloxy group, and m1 is an integer of 0 or more). , a group in which Y ¹ is a hydroxyl group —[(OA) _m1 —OH] [wherein A is a C _2-6 alkylene group such as an ethylene group. (eg a C _2-4 alkylene group, especially a C _2-3 alkylene group), where m1 is an integer from 0 to 5 (eg 0 or 1)] is particularly preferred.

In the above formula (1), n representing the number of groups X ¹ substituted on the ring Z may be 1 or more, preferably 1 to 3, more preferably 1 or 2 (especially 1). In addition, the substitution number n may be the same or different in each ring Z.

The group X ¹ can be substituted at any suitable position on the ring Z, for example when the ring Z is a benzene ring, the 2,3,4 positions (especially the 3 and/or 4 positions, especially the 4 position), and when the ring Z is a naphthalene ring, it is often substituted at any of the 5-8 positions of the naphthyl group, for example, the 9-position of fluorene The 1-position or 2-position of the naphthalene ring is substituted (substituted in a 1-naphthyl or 2-naphthyl relationship), and the 1,5-position, 2,6-position, etc. relationship (especially n is 1 , the group X ¹ is often substituted in the 2,6-position relationship). Moreover, when n is 2 or more, the substitution position is not particularly limited. Further, in the ring-assembled arene ring Z, the substitution position of the group X ¹ is not particularly limited. good. For example, the 3- or 4-position of the biphenyl ring Z may be attached to the 9-position of the fluorene, and when the 3-position of the biphenyl ring Z is attached to the 9-position of the fluorene, the substitution position of the group X ¹ is Any of the 2, 4, 5, 6, 2', 3' and 4' positions may be acceptable, and preferably the 6-position may be substituted.

In the above formula (1), the substituent R ² includes a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, linear or branched C _1-10 alkyl groups such as s-butyl group, t-butyl group, preferably linear or branched C _1-6 alkyl groups, more preferably linear or branched chain C _1-4 alkyl group, etc.), cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl (tolyl) group, dimethylphenyl (xylyl) group, etc.), biphenyl group, C _6-12 aryl group such as naphthyl group], aralkyl group (benzyl group, C _6-10 aryl-C _1-4 alkyl group such as phenethyl group, etc.), alkoxy groups (e.g., linear or branched C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy groups), cycloalkoxy groups (e.g., cyclo C _5-10 cycloalkoxy groups such as a hexyloxy group), aryloxy groups (e.g. C _6-10 aryloxy groups such as a phenoxy group), aralkyloxy groups (e.g. C _6-10 aryl-C _1-4 alkyloxy group, etc.), alkylthio group (e.g., C _1-10 alkylthio group such as methylthio group, ethylthio group, propylthio group, n-butylthio group, t-butylthio group, etc.), cycloalkylthio group ( For example, a C _5-10 cycloalkylthio group such as a cyclohexylthio group), an arylthio group (for example, a C _6-10 arylthio group such as a thiophenoxy group), an aralkylthio group (for example, a C _{6- 10} aryl-C _1-4 alkylthio group), acyl group (eg, C _1-6 acyl group such as acetyl group), nitro group, cyano group and the like.

Among these substituents ^R2 , representative examples are halogen atoms, hydrocarbon groups (alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups), alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. etc. Preferred substituents R ² include alkoxy groups (such as linear or branched C _1-4 alkoxy groups such as methoxy groups), in particular alkyl groups (especially linear or branched C _1-4 alkyl groups) are preferred. In addition, when the substituent R ² is an aryl group, the substituent R ² may form the ring-assembled arene ring together with the ring Z. The types of substituents R ² may be the same or different on the same or different rings Z.

The coefficient p of the substituent R ² can be appropriately selected depending on the type of the ring Z, and may be, for example, an integer of about 0 to 8, an integer of 0 to 4, preferably 0 to 3 (eg, 0 to 2 ), more preferably 0 or 1. In particular, when p is 1, ring Z may be a benzene ring, naphthalene ring or biphenyl ring, and substituent ^R2 may be a methyl group.

Examples of the substituent R ¹ include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a carboxyl group, an alkoxycarbonyl group (e.g., a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group, etc.), alkyl groups (C _1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group), aryl groups (C _6-10 aryl groups such as phenyl group) and the like.

Among these substituents R ¹ , linear or branched C _1-4 alkyl groups (especially C _1-3 alkyl groups such as methyl groups), carboxyl groups or C _1-2 alkoxy-carbonyl groups, cyano Groups and halogen atoms are preferred. The substitution number k is an integer from 0 to 4 (eg 0 to 3), preferably an integer from 0 to 2 (eg 0 or 1), especially 0. The number of substitutions k may be the same or different, and when k is 2 or more, the types of substituents R ¹ may be the same or different, and the two benzene rings of the fluorene ring are substituted. The types of substituents R ¹ may be the same or different. Further, the substitution position of the substituent R ¹ is not particularly limited, and may be, for example, 2- to 7-positions (2-, 3- and/or 7-positions, etc.) of the fluorene ring.

Among _these ^{, preferred} fluorene compounds include 9,9 ^- bis( 9,9-bis(hydroxy C _{6- 12} aryl) fluorene; 9,9-bis(di- or trihydroxy C _6-12 aryl) fluorene such as 9,9-bis(3,4-dihydroxyphenyl) fluorene; 9,9-bis(3-methyl-4 9,9-bis(mono- or di-C _1-4 alkyl-hydroxy C _6-12 aryl)fluorene such as -hydroxyphenyl)fluorene; 9,9-bis(C _6-12 aryl-hydroxy C _6-12 aryl)fluorene such as 9-bis(4-phenyl-3-hydroxyphenyl)fluorene; 9,9-bis[4-(2-hydroxyethoxy ) phenyl]fluorene, 9,9-bis(hydroxy(poly)C _2-4 alkoxy-C _6-12 aryl)fluorene such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene 9,9-bis(C _1-4 alkyl-hydroxy(poly)C _2-4 alkoxy-C _6-12 such as 9,9-bis[3-methyl-4-(2-hydroxyethoxy)phenyl]fluorene; 9, such as 9,9-bis[3-phenyl-4-(2-hydroxyethoxy)phenyl]fluorene and 9,9-bis[4-phenyl-3-(2-hydroxyethoxy)phenyl]fluorene; , 9-bis(C _6-12 aryl-hydroxy(poly)C _2-4 alkoxy-C _6-12 aryl)fluorene.

When the group X ¹ is a group -[(OA) _m1 -Y ¹ ] (wherein Y ¹ represents a glycidyloxy group), preferred fluorene compounds include 9,9-bis(glycidyloxyaryl)fluorene , for example, 9,9-bis(3-glycidyloxyphenyl)fluorene, 9,9-bis(4-glycidyloxyphenyl)fluorene, 9,9-bis(5-glycidyloxy-1-naphthyl)fluorene, 9, 9,9-bis(glycidyloxy C _6-10 aryl)fluorene such as 9-bis(6-glycidyloxy-2-naphthyl)fluorene; 9,9-bis(glycidyloxy(poly)alkoxyaryl)fluorene, such as 9,9-bis(4-(2-glycidyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-glycidyloxypropoxy)phenyl)fluorene, 9,9-bis(5-(2-glycidyl) 9,9-bis(glycidyloxy(poly)C _2-4 alkoxy C such as oxyethoxy)-1-naphthyl)fluorene, 9,9-bis(6-(2-glycidyloxyethoxy)-2-naphthyl)fluorene 9,9-bis(mono _or DiC _1-4 alkyl-glycidyloxy C _6-10 aryl)fluorene; 9,9-bis(alkyl-glycidyloxy(poly)alkoxyaryl)fluorene, such as 9,9-bis(3-methyl-4-( 9,9-bis(mono- or di-C _1-4 alkyl-glycidyloxy(poly)C _2-4 alkoxyC _6-10 aryl)fluorene such as 2-glycidyloxyethoxy)phenyl)fluorene; 9,9-bis( 9,9-bis(C _6-10 aryl-glycidyloxyC _6-10 aryl)fluorene such as aryl-glycidyloxyaryl)fluorene, for example 9,9-bis(3-phenyl-4-glycidyloxyphenyl)fluorene 9,9-bis(aryl-glycidyloxy(poly)alkoxyaryl)fluorene, such as 9,9-bis(3-phenyl-4-(2-glycidyloxyethoxy)phenyl)fluorene. (C _6-10 aryl-glycidyloxy(poly)C _2-4 alkoxyC _6-10 aryl)fluorene; 9,9-bis(di(glycidyloxy)aryl)fluorene, such as 9,9-bis(3, 9,9-bis(di(glycidyloxy)C _6-10 aryl)fluorene such as 4-di(glycidyloxy)phenyl)fluorene; 9,9-bis(di(glycidyloxy(poly)alkoxy)aryl)fluorene, For example, 9,9-bis(di(glycidyloxy(poly)C _2-4 alkoxy)C _6-10 aryl) such as 9,9-bis(3,4-di(2-glycidyloxyethoxy)phenyl)fluorene Fluorene etc. can be illustrated.

These fluorene compounds (C) can be used alone or in combination of two or more. In addition, "(poly)alkoxy" is used to include both an alkoxy group and a polyalkoxy group.

The fluorene compound (C) may exist independently or free from the cellulose (B) in the composition. (C) is preferably present in close proximity to or in contact with cellulose (B) in the composition, and is particularly preferably complexed to form a complex. When conjugated, the fluorene compound (C) may adhere to and bind to the cellulose (B), and the form of conjugate is not particularly limited. The fluorene compound (C) may coat at least part of the surface of the cellulose (B), and the granular fluorene compound (C) may adhere to the cellulose (B).

When the cellulose (B) and the fluorene compound (C) are composited, the cellulose (B) may be composited without being modified (chemically modified) with the fluorene compound (C). That is, in the present invention, it can be inferred that both are not bonded by a covalent bond such as an ether bond or an ester bond, but are relatively loosely bonded or have affinity through a hydrogen bond or the like. Therefore, cellulose (B) (especially nanofibers) has a high degree of freedom in the composition, can improve the mechanical properties (elongation, etc.) of the composition, and can easily be applied when a tensile stress such as stretching is applied. Unraveled and arranged in the direction of tension. In the present specification and claims, the presence or absence of a covalent bond between the cellulose (B) and the fluorene compound (C) is determined by washing with a solvent in which the fluorene compound (C) dissolves. can be easily determined by a method of quantifying the fluorene compound (C).

When the fluorene compound (C) covers the surface of the cellulose (B), the average thickness of the film formed of the fluorene compound (C) may be 1 nm or more, for example 1 to 1000 nm, preferably 5 to 1 nm. 800 nm, more preferably 10 to 500 nm. If the thickness of the coating is too thin, the dispersibility of cellulose (B) in the composition may deteriorate.

Since the composite of the fluorene compound (C) and cellulose (B) is uniformly dispersed in the rubber-like composition, the composition has excellent mechanical properties. The dispersion diameter of the complex in the composition is, for example, 10-1000 nm, preferably 10-500 nm, more preferably 10-200 nm.

The ratio of the fluorene compound (C) can be selected from a range of about 1 to 100 parts by mass with respect to 100 parts by mass of the cellulose (B), for example 10 to 90 parts by mass, preferably 20 to 80 parts by mass, more preferably It is about 30 to 70 parts by mass (especially 40 to 60 parts by mass). In the present invention, since the ratio of the fluorene compound (C) is relatively large, the dispersibility of the cellulose (B) can be highly improved, and even if the cellulose (B) is nanofibers, it can be effectively and uniformly dispersed. If the proportion of the fluorene compound (C) is too low, the dispersibility of the cellulose (B) in the composition may decrease, resulting in deterioration of the mechanical properties of the composition. There is a risk that the mechanical properties of the

[Reinforcing agent (D)]
The rubber-like composition of the present invention [especially a vulcanized rubber composition in which the rubber component (A) is rubber] is prepared by adding the rubber component (A), cellulose (B ) and in addition to the fluorene compound (C), a reinforcing agent (D) is further included.

As the reinforcing agent (D), conventional reinforcing agents can be used, for example, granular reinforcing agents (carbonaceous materials such as carbon black and graphite; calcium oxide, magnesium oxide, barium oxide, iron oxide, copper oxide, titanium oxide, metal oxides such as aluminum oxide (alumina); metal silicates such as calcium silicate and aluminum silicate; metal carbides such as silicon carbide and tungsten carbide; metal nitrides such as titanium nitride, aluminum nitride and boron nitride; Metal carbonates such as magnesium and calcium carbonate; Metal sulfates such as calcium sulfate and barium sulfate; mineral materials such as clay), fibrous reinforcing agents (inorganic fibers such as glass fiber, carbon fiber, boron fiber, whisker and wollastonite; organic fibers such as polyester fiber and polyamide fiber). These reinforcing agents can be used alone or in combination of two or more.

Among these reinforcing agents, granular reinforcing agents such as carbon black and silica (especially granular inorganic reinforcing agents) are widely used, and the mechanical properties of the rubber-like composition can be greatly improved by combining them with the fluorene compound (C). Therefore, carbon black is preferred. In the present invention, the fluorene compound (C) not only improves the dispersibility of the cellulose (B) in the rubber component, but also has high compatibility with the granular reinforcing agent (especially carbon black), and improves the dispersibility of the granular reinforcing agent. can.

Examples of carbon black include acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black, coated carbon black, graft carbon black and the like. These carbon blacks can be used alone or in combination of two or more.

The average particle diameter (arithmetic mean particle diameter) of carbon black can be selected from the range of about 5 to 200 nm, for example 10 to 150 nm, preferably 15 to 100 nm, more preferably 20 to 80 nm, most preferably 30 to 50 nm. If the average particle size of the carbon black is too small, uniform dispersion may become difficult, and if it is too large, the mechanical properties of the vulcanized rubber composition may deteriorate.

The ratio of the reinforcing agent (D) can be selected from the range of about 3 to 300 parts by mass with respect to 100 parts by mass of the rubber component (A), for example 5 to 200 parts by mass, preferably 8 to 150 parts by mass, more preferably 10 to 100 parts by weight, most preferably 15 to 80 parts by weight. If the proportion of the reinforcing agent is too small, the effect of improving the mechanical properties of the rubber-like composition may be reduced. .

[Softener (E)]
The rubbery composition of the present invention [in particular, a vulcanized rubber composition in which the rubber component (A) is rubber] is used to improve the dispersibility of cellulose (B) in the composition and the mechanical properties of the composition. , the rubber component (A), the cellulose (B), the fluorene compound (C) and the reinforcing agent (D), further comprising a softening agent (E).

The softening agent (E) includes oils and the like as softening agents compatible with the rubber component (A) and capable of reducing the viscosity of the rubber-like composition (particularly, the unvulcanized rubber composition). Examples of oils include paraffinic oils, naphthenic oils, and process oils. These softeners can be used alone or in combination of two or more. Among these softeners, oils such as paraffinic oils and naphthenic oils are preferred.

In particular, in the present invention, a second softening agent, which is a part of these softening agents (E), is combined with cellulose (B) and fluorene compound (C) to combine rubber component (A) and reinforcing agent (D). By adding to the mixture and mixing, the dispersibility of cellulose (B) in the rubber composition can be highly improved. As the second softening agent, the above oils are preferred, and naphthenic oils are particularly preferred. On the other hand, as the first softening agent, which is the remainder of the softening agent (E), the above-mentioned oils are preferred, and process oils are particularly preferred.

Further, even when the softener (E) is blended in order to improve the moldability, the softener (E) contains the fluorene compound (C). It is possible to suppress the deterioration of the mechanical properties of the vulcanized rubber composition containing).

The ratio of the softening agent (E) can be appropriately selected according to the type of the rubber component (A), and can be selected from the range of about 0.1 to 500 parts by mass with respect to 100 parts by mass of the rubber component (A). .5 to 400 parts by mass (eg 1 to 300 parts by mass), preferably 1 to 200 parts by mass, more preferably 3 to 100 parts by mass. When the rubber component (A) is a diene rubber, for example, 3 to 50 parts by mass, preferably 5 to 30 parts by mass, more preferably 8 to 20 parts by mass, most preferably 100 parts by mass of the rubber component (A). It is preferably 10 to 15 parts by mass. When the rubber component (A) is an olefin rubber, the ratio of the softener (E) is, for example, 10 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the rubber component (A). It is preferably 30 to 100 parts by weight, most preferably 40 to 60 parts by weight. If the proportion of the softening agent (E) is too small, the effect of improving the dispersibility of the cellulose (B) may decrease, and if it is too large, the mechanical properties of the rubber-like composition may decrease.

[Silane coupling agent (F)]
The rubber-like composition of the present invention [particularly, a vulcanized rubber composition in which the rubber component (A) is rubber] comprises a rubber component (A), cellulose (B), a fluorene compound ( In addition to C), reinforcing agent (D) and softening agent (E), a silane coupling agent (F) may be further included.

As the silane coupling agent (F), a conventional silane coupling agent such as an alkoxysilyl group-containing silane coupling agent, a halogen-containing silane coupling agent, a vinyl group-containing silane coupling agent, an ethylenically unsaturated bond group-containing Examples include silane coupling agents, epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, carboxyl group-containing silane coupling agents, and silanol group-containing silane coupling agents. These silane coupling agents can be used alone or in combination of two or more.

Among these, silane coupling agents commonly used in rubber are preferred, and sulfur atom-containing silane coupling agents are particularly preferred.

Sulfur atom-containing silane coupling agents include, for example, disulfides [bis(tri-C _1-4 alkoxysilyl-C _2-4 alkyl) disulfides such as bis(3-(triethoxysilyl)propyl) disulfide], tetra Sulfides (pertetrasulfides or tetrasulfanes) {bis(tri-C _1-4 alkoxysilyl-C _2-4 alkyl)tetrasulfides such as bis[3-(triethoxysilyl)-propyl]tetrasulfide} , mercaptoalkyltrialkoxysilanes (mercaptoC2-4alkyltriC1-4alkoxysilanes such as 3-mercaptopropyltrimethoxysilane, _3- mercaptopropyltriethoxysilane, etc.) or _their condensates (oligomers), mercaptoalkylalkyl Dialkoxysilanes (such as mercapto C _2-4 alkyl C _1-4 alkyl di-C _1-4 alkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane) and the like. At least part of the mercapto groups in the mercaptoalkyltrialkoxysilane oligomer may form an ester with a carboxylic acid. Examples of carboxylic acids include _C4-24 saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. These sulfur-containing silane coupling agents can be used alone or in combination of two or more.

The ratio of the silane coupling agent (F) can be appropriately selected according to the type of the rubber component (A), and can be selected from the range of about 0.05 to 5 parts by mass with respect to 100 parts by mass of the rubber component (A). For example, it is 0.1 to 3 parts by mass, preferably 0.2 to 2 parts by mass, more preferably 0.3 to 1 part by mass, and most preferably 0.4 to 0.8 parts by mass. If the proportion of the silane coupling agent (F) is too small, the effect of improving the tear strength may be reduced, and if it is too large, the mechanical properties of the rubber-like composition may be reduced.

[Plasticizer (G)]
The rubber-like composition of the present invention [especially a vulcanized rubber composition in which the rubber component (A) is a rubber] comprises a rubber component (A), a cellulose (B), a fluorene compound ( In addition to C), reinforcing agent (D) and softening agent (E), a plasticizer (G) may be further included. Examples of plasticizers (G) include stearic acid, metal stearates, waxes, paraffins, and fatty acid amides. These plasticizers can be used alone or in combination of two or more. Among these, higher fatty acids such as stearic acid are preferred. The ratio of the plasticizer (G) is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the rubber component (A). . If the proportion of the plasticizer (G) is too small, the effect of improving moldability may be reduced, and if it is too large, the mechanical properties of the rubber-like composition may be reduced.

[Vulcanizing agent (H)]
The rubber-like composition of the present invention usually contains a vulcanizing agent (H) when the rubber component (A) is rubber. As the vulcanizing agent (H), a commonly used vulcanizing agent can be used depending on the type of rubber. Vulcanizing agents (H) include sulfur vulcanizing agents and organic peroxides.

Examples of sulfur-based vulcanizing agents include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, surface-treated sulfur, sulfur chloride (sulfur monochloride, sulfur dichloride, etc.), morpholine disulfide, and alkylphenol disulfide. etc.

Examples of organic peroxides include diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide; oxide, 1,1-di-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, 1,3-bis(t- dialkyl peroxides such as butylperoxy-isopropyl)benzene; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide; n-butyl-4,4-di-t-butylperoxide and peroxy esters such as oxyvalerate and 2,5-dimethylhexane-2,5-di(peroxylbenzoate).

These vulcanizing agents can be used alone or in combination of two or more. Among these, sulfur and dialkyl peroxide such as dicumyl peroxide are widely used.

The ratio of the vulcanizing agent (H) can be selected from the range of about 0.1 to 30 parts by mass with respect to 100 parts by mass of rubber. 0.5 to 8 parts by mass, more preferably 0.6 to 5 parts by mass. In the case of organic peroxides, for example, 1 to 25 parts by mass, preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass. Department.

[Vulcanization aid (I)]
When the rubber component (A) is rubber, the rubbery composition of the present invention may further contain a vulcanization aid (I) to accelerate vulcanization. Vulcanization aids (or co-crosslinking agents) (H) include, for example, organic vulcanization accelerators [e.g., N-cyclohexyl-2-benzothiazylsulfenamide (CBS), Nt-butyl-2 - sulfenamide accelerators such as benzothiazylsulfenamide (TBBS); thiuram accelerators such as tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD); 2-mercaptobenzothiazole (MBT) , zinc salt of MBT, dibenzothiazyl disulfide (MBTS); thiourea accelerators, such as trimethylthiourea (TMU), diethylthiourea (EDE); DOTG); dithiocarbamate accelerators such as sodium dimethyldithiocarbamate; xanthate accelerators such as zinc isopropyl xanthate; aldehyde-amine or aldehyde-ammonia accelerators such as hexanemethylenetetramine. etc.], polyfunctional (iso)cyanurates [e.g., triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), etc.], polydienes (e.g., 1,2-polybutadiene, etc.), metal salts of unsaturated carboxylic acids [ For example, (meth)acrylic acid polyvalent metal salts such as zinc (meth)acrylate], polyfunctional (meth)acrylates [for example, alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, pentaerythritol tetra Alkane polyol poly (meth) acrylate such as (meth) acrylate], aromatic maleimide (arene bismaleimide such as N,N'-m-phenylenedimaleimide, etc.), inorganic auxiliary agent [zinc oxide (zinc white), oxide magnesium etc.] etc. are mentioned.

These vulcanizing aids can be used alone or in combination of two or more. Among these, sulfenamide accelerators such as CBS, thiuram accelerators such as TMTD, and inorganic aids such as zinc oxide are widely used.

The proportion of vulcanization aid (I) is, for example, 4 to 30 parts by weight, preferably 5 to 25 parts by weight, more preferably 10 to 20 parts by weight, per 100 parts by weight of rubber. The proportion of the organic vulcanization accelerator is, for example, 1 to 10 parts by mass, preferably 3 to 8 parts by mass, more preferably 5 to 7 parts by mass, per 100 parts by mass of rubber. The proportion of the inorganic auxiliary agent (particularly zinc white) is, for example, 3 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 7 to 10 parts by weight, per 100 parts by weight of rubber.

[Other additives (J)]
The rubbery composition of the present invention may contain conventional additives depending on the type of rubber component (A). Commonly used additives include, for example, resin components (thermoplastic resins, thermosetting resins, etc.), solvents, vulcanization retarders, dispersants, aging or antioxidants (aromatic amine-based, benzimidazole-based anti-aging agents etc.), colorants (e.g., dyes and pigments), tackifiers, coupling agents (F), stabilizers (ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), release agents, lubricants, flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), damping agents, flame retardant aids, antistatic agents, conductive agents, flow control agents, leveling agents, antifoaming agents, surface modifiers , stress reducing agents, nucleating agents, crystallization accelerators, antibacterial agents, preservatives and the like.

These other additives can be used alone or in combination of two or more. The ratio of other additives is, for example, 0.1 to 50 parts by mass, preferably 0.5 to 30 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the rubber component (A).

[Characteristics of rubber-like composition]
The rubber-like composition of the present invention comprises the rubber component (A), cellulose (B), a fluorene compound (C) having a 9,9-bis(aryl)fluorene skeleton, a reinforcing agent (D) and a softening agent (E). and adding at least part of the cellulose (A), the fluorene compound (C) and the softening agent (E) to the mixture of the rubber component (A) and the reinforcing agent (D) By mixing, the cellulose (B) can be uniformly dispersed in the rubber composition. In particular, since the cellulose (B) can be highly uniformly dispersed in the rubber composition, the method of adding at least part of the cellulose (A), the fluorene compound (C) and the softening agent (E) is , A method of adding a preliminary mixture prepared by mixing the cellulose (B) and the fluorene compound (C) in advance is preferable, and the cellulose (B), the fluorene compound (C) and the softening agent (E) are added. Particularly preferred is the method of adding a premix prepared by premixing at least a portion thereof. Although the mechanism by which the dispersibility of cellulose is improved is not clear, the fluorene compound (C) exhibits a compatibilizing effect, and the softening agent (E) is not mixed together with the rubber component (A). By using a part of the agent (E) in advance in combination with cellulose and a fluorene compound, a wet state is formed (or fluidity is imparted) to suppress aggregation of the cellulose (B), and the cellulose (B) and the fluorene compound (C) can be uniformly mixed.

Therefore, the rubber-like composition of the present invention is excellent in the dispersibility of the cellulose (B), and when molded into a sheet, the cellulose (B) having a major axis of 200 μm or more on the surface of the sheet-like molded product. ) may be 30/(10 cm) ² or less [for example, 10/(10 cm) ² or less], preferably 5/(10 cm) ² or less, more preferably 3/(10 cm) ) ² or less, more preferably 1/(10 cm) ² or less, most preferably 0/(10 cm) ^{2 or less} . If the number of aggregates exceeds 30 pieces/(10 cm) ² , the mechanical properties of the rubber-like composition deteriorate.

In the present specification and claims, the number of cellulose aggregates can be obtained as an average value of n=5 or more (especially n=10) measured by visual observation. Visual observation may be made based on an enlarged photograph, if necessary. Further, the average value may be an average value obtained by measuring a plurality of locations on one sheet-like molded article, or may be an average value obtained by measuring a plurality of 10 cm square sheet-shaped molded articles. Furthermore, the plurality of sheet-shaped moldings does not necessarily have an area of 10 cm square, and when sheets with different areas are measured, the number of aggregated portions measured may be a numerical value converted from the area ratio.

Furthermore, in the present specification and claims, the major axis of the aggregated portion means the distance (that is, the maximum diameter) indicating the maximum length among the distances between any two points on the outer periphery of the aggregated portion. . In addition, when the reinforcing agent (D) contains carbon black, the agglomerated parts turn white in the black molded article, and can be easily observed visually.

[Method for producing rubber-like composition]
The rubber-like composition of the present invention comprises a first mixing step of mixing a rubber component (A) and a reinforcing agent (D) to prepare a first mixture, the first mixture, cellulose (B) and a fluorene compound. Obtained through a second mixing step of mixing (C) with a second softening agent which is part of the softening agent (E) to prepare a second mixture.

(First mixing step)
In the first mixing step, the method of mixing the rubber component (A) and the reinforcing agent (D) can be appropriately selected according to the type of the rubber component (A). In the first mixing step, the first mixture may be prepared by mixing with other additives. Other additives include a first softening agent which is the remainder of the softening agent (E), a plasticizer (G), a vulcanizing agent (H), and a vulcanizing aid (I). As will be described later, the silane coupling agent (F) is preferably added in the second mixing step.

As a mixing method, a conventional method used for kneading a rubber-like composition, such as a method using a mixing roller, a kneader, a Banbury mixer, an extruder (single-screw or twin-screw extruder, etc.), or the like can be used. Among these, a kneader such as a pressurized kneader is preferred.

The mixing temperature can be selected according to the type of rubber component, and is, for example, 30 to 250°C, preferably 40 to 200°C, more preferably 50 to 180°C, most preferably 80 to 160°C.

(Second mixing step)
In the present invention, by mixing the cellulose (B) and the fluorene compound (C) with the first mixture in the second mixing step, in the composition, the surface of the cellulose (B) is the fluorene compound (C ), but by also mixing a second softener with cellulose (B) and said fluorene compound (C), cellulose (B) (especially nanofibers) in the composition can improve the dispersibility of

In the second mixing step, the cellulose (B), the fluorene compound (C) and the second softening agent may be added in the second mixing step without premixing, but From the viewpoint that the dispersibility of the cellulose (B) can be highly improved, it is preferable to add a pre-mixture that has undergone a pre-mixing step, as will be described later.

The ratio of the second softening agent can be selected from the range of about 10 to 100% by mass with respect to the entire softening agent (E), for example, 20 to 90% by mass, preferably 30 to 80% by mass, more preferably 50 to 90% by mass. 70% by mass.

As a mixing method, the mixing method exemplified in the first mixing step can be used.

When the rubber component (A) is rubber, it is preferably mixed with a Banbury mixer, and after mixing, it is subjected to the vulcanization step described below. The kneading may be performed with or without heating. When heating, the kneading temperature is, for example, 30 to 250°C, preferably 40 to 200°C, more preferably 50 to 180°C, and most preferably 80 to 160°C.

On the other hand, when the rubber component (A) is a thermoplastic elastomer, a method of melt-kneading using an extruder such as a twin-screw extruder is preferable, and the melt-kneaded rubber-like composition is subjected to a conventional molding method such as injection molding. It can be molded. The kneading temperature is, for example, about 60 to 270°C, preferably about 80 to 250°C, more preferably about 100 to 230°C.

(Preliminary mixing step)
In the present invention, in the first premixing step, the cellulose (B) and the fluorene compound (C) are mixed to prepare the first premix, so that at least part of the surface of the cellulose (B) is fluorene The proportion of the composite can be increased even in the second mixture mixed with the rubber component, probably because the composite coated with the compound (C) can be efficiently formed. Furthermore, in the second pre-mixing step, the second softener is also mixed with the cellulose (B) and the fluorene compound (C) to prepare a second pre-mixture, whereby the softener causes the cellulose (B) to aggregate. The cellulose (B) can be highly uniformly dispersed in the rubber-like composition, probably because at least part of the surface of the cellulose (B) can be coated with the fluorene compound (C) while suppressing the

The first preliminary mixture may be only a composite in which at least a portion of the surface of cellulose (B) is coated with the fluorene compound (C), and this composite, cellulose (B) and/or the fluorene compound It may be a mixture with (C). The proportion of the complex in the first premix is, for example, 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more.

The second preliminary mixture may be a mixture of a composite in which at least a portion of the surface of cellulose (B) is coated with the fluorene compound (C) and a second softener, wherein the composite and the second 2 softener and cellulose (B) and/or fluorene compound (C). The proportion of the complex in the second premix excluding the second softener is, for example, 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more.

In premixing, when the cellulose (B) is nanofibers, when the cellulose nanofibers (in particular, microfibrillated fibers, nanofibers with an average fiber diameter of nanometer size) are dried, the fibers become entangled and cannot be redispersed. Sometimes. Therefore, it is usually preferable to premix cellulose (B) (especially cellulose nanofibers) with fluorene compound (C) as a mixture with water, for example, as a water-impregnated body (water wet body) or an aqueous dispersion. The mixture of cellulose nanofibers and water may be commercially available.

The cellulose concentration in the mixture of cellulose (B) and water (in particular, the solid content concentration of cellulose nanofibers) is, for example, 1 to 80% by mass, preferably 3 to 50% by mass, more preferably 5 to 30% by mass, most preferably It is preferably 10 to 25% by mass. If the solid content concentration is too low, the efficiency of compounding may decrease, and if it is too high, the handleability may decrease.

A mixture of cellulose (B) and water and the fluorene compound (C) may be premixed in the absence of a solvent. A method of mixing in the presence of a solvent is preferred from the viewpoint of efficient compounding.

As the solvent, an amphipathic solvent having an affinity for both water and the fluorene compound is preferred. Examples of amphiphilic solvents include alcohols (butanol, cyclohexanol, 1-methoxy-2-propanol, etc.), cellosolves and carbitols (ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether, polyethylene glycol dimethyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), lactones (butyrolactone, caprolactone, etc.), esters (methyl acetate, ethyl acetate, acetic acid butyl, etc.), lactams (butyrolactam, caprolactam, etc.), amides (dimethylformamide, dimethylacetamide, etc.), sulfoxides (dimethylsulfoxide, etc.), and the like. These solvents can be used alone or in combination of two or more. Among these, cellosolves, carbitols, ketones, lactones, lactams, amides, and sulfoxides, both ends of which are etherified with alkyl groups, are commonly used because they are easy to distill off, and cyclohexanone and the like are commonly used. Alicyclic ketones, cellosolves such as diethylene glycol dimethyl ether, and the like can be preferably used. When these amphipathic solvents are used, they are easily distilled off, and even if the composite containing the solvent is mixed with the rubber component (A), the solvent can be suppressed from remaining in the composition.

The proportion of the solvent may be 100 parts by mass or more, for example 100 to 10000 parts by mass, preferably 300 to 5000 parts by mass, with respect to the total 100 parts by mass of the mixture of cellulose (B) and water and the fluorene compound (C). parts, more preferably 500 to 3000 parts by mass, most preferably 1000 to 2000 parts by mass.

The mixing method in premixing may be melt-kneading, or stirring using a magnetic stirrer or a stirring blade commonly used in chemical reactions. When stirring, the rotational speed of stirring is preferably high, for example 10 rpm or more (eg 10 to 10000 rpm), preferably 50 rpm or more (eg 50 to 7000 rpm), more preferably 100 rpm or more (eg 100 to 5000 rpm), particularly 200 rpm or more. Stirring at a rotational speed of about (eg, 200 to 3000 rpm) may be used.

When nanofibers are used as the cellulose (B), the fluorene compound (C) and the solvent may be blended in advance with the cellulose before defibration in the fibrillation step for obtaining the nanofibers.

The ratio of the second softening agent added in the second preliminary mixing step is, for example, 10 to 1000 parts by mass, preferably 50 to 500 parts by mass, more preferably 80 to 100 parts by mass with respect to 100 parts by mass of cellulose (B). 300 parts by weight, most preferably 100 to 200 parts by weight. If the ratio of the second softening agent is too small, the dispersibility of cellulose in the rubber-like composition may deteriorate, and if it is too large, the mechanical properties of the rubber-like composition may deteriorate.

The resulting dispersion containing cellulose (B) and fluorene compound (C) (or the dispersion further containing a second softening agent) is dried to remove water and a solvent for mixing with rubber component (A). It is preferably prepared as an impregnated body of water and solvent by distilling off the majority. As a method for distilling off the water and the solvent, a conventional method such as a method of heating and/or reducing pressure can be used, and the method of heating and reducing pressure is preferable from the viewpoint of productivity.

As a heating method, a conventional method, for example, a method using a stationary hot air dryer, a vacuum dryer, a rotary evaporator, a mixing dryer (conical dryer, Nauta dryer, etc.) can be used. . The heating temperature is, for example, 40 to 200°C, preferably 60 to 150°C, more preferably 70 to 100°C.

As a method for reducing the pressure, a conventional method such as a method using an oil pump, an oilless pump, an aspirator, or the like can be used. The pressure in the decompression method is, for example, 0.00001 to 0.05 MPa, preferably about 0.00001 to 0.03 MPa.

The preliminary mixture obtained by the drying treatment may contain a predetermined amount of water and solvent in order to uniformly disperse the cellulose (B) in the rubber component (A). The total ratio of water and solvent is 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight, more preferably 100 to 500 parts by weight, based on a total of 100 parts by weight of cellulose (B) and fluorene compound (C) after drying. It is about parts by mass (especially 150 to 400 parts by mass). In addition, the preliminary mixture may contain a solvent without containing water from the viewpoint of improving kneadability, and the ratio of the solvent is the total of the cellulose (B) and the fluorene compound (C) after drying treatment. It is about 10 to 1000 parts by weight, preferably 20 to 700 parts by weight, and more preferably about 30 to 500 parts by weight per 100 parts by weight.

(Vulcanization process)
When the rubber component (A) is rubber, a vulcanized rubber composition is obtained through a vulcanization step in which the unvulcanized rubber composition obtained in the second mixing step is molded into a predetermined shape and vulcanized. be done. In the vulcanization step, the vulcanization temperature can be selected according to the type of rubber, and is, for example, about 100 to 250°C, preferably 150 to 200°C, more preferably about 160 to 190°C.

The rubber-like composition obtained by such a method may be molded articles of various shapes. As described above, the resulting molded article has excellent dispersibility of cellulose (B), and the number of aggregated portions of cellulose (B) having a major axis of 200 μm or more on the surface is 30 pieces/(10 cm) ^{2 .} or less [for example, 10 pieces/(10 cm) ² or less], preferably 5 pieces/(10 cm) ² or less, more preferably 3 pieces/(10 cm) ² or less, more preferably 1 piece/(10 cm) ^{2 or less} Below, the most preferable number is 0/(10 cm) ² .

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. Raw materials and evaluation methods used are as follows.

(Raw materials used)
BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemicals Co., Ltd. SBR: "JSR 1502" manufactured by JSR Corporation
CB N234: "SEAST 7HM" manufactured by Tokai Carbon Co., Ltd.
Process oil: "Vivatec 500 (TDAE)" manufactured by H&R Co., Ltd.
Naphthenic oil: "SNH-22" manufactured by Sankyo Yuka Kogyo Co., Ltd.
Zinc white: "Zinc white No. 1" manufactured by Mitsui Mining & Smelting Co., Ltd.
Stearic acid: "Bead stearic acid Tsubaki" manufactured by NOF Corporation
Sulfur: "Powder Sulfur" manufactured by Tsurumi Chemical Co., Ltd.
Accelerator CBS: "Noccellar CZ-G" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
Silane coupling agent A: "Silanogran SI-69" manufactured by Evonik
Silane coupling agent B: "NXT-Z45" manufactured by Momentive.

(Tensile test)
25 to 300% tensile stress, tensile strength and elongation were measured according to JIS K6251.

(Tear strength)
The tear strength was measured according to JIS K6252.

(Durometer hardness)
The durometer hardness was measured according to JIS K6253 Type A.

(density)
Density was measured according to JIS K6268.

(Cellulose dispersibility)
The number of agglomerates having a major diameter of 200 μm or more on the surface of 10 sheet-shaped moldings after vulcanization pressing was measured, and the average value was obtained.

Reference Example 1 (SBR/Blank)
Each component in the ratio shown in Table 1 was kneaded at a temperature of 150° C. using a pressurized kneader (manufactured by Moriyama Co., Ltd., volume 10 liters) to prepare an unvulcanized rubber composition. The obtained composition was press-vulcanized at a vulcanization temperature of 180° C. to obtain a sheet-like vulcanized rubber composition (length 99 mm×width 96 mm×thickness 2 mm).

Example 1 (SBR/BPEF-CNF premix/naphthenic oil)
(First pre-mixing step)
1800 g of cyclohexanone and 15 g of BPEF were added to 150 g of a water wet body containing plant-derived cellulose nanofibers (containing 20% by mass of solids and 30 g of cellulose nanofibers) containing 50% by mass or more of fibers with a diameter of 100 nm or less that were defibrated by a grinder method. (50 parts by mass of BPEF per 100 parts by mass of cellulose nanofibers) was added and stirred at 600 rpm for 10 minutes using a stirrer (manufactured by Shinto Kagaku Co., Ltd., "Three One Motor"). Vacuum was applied at 80° C. to obtain 150 g of wet first premix (BPEF-CNF composite). FIG. 1 shows an SEM photograph of the cellulose nanofibers used as the raw material. The cellulose nanofibers were continuous fibers (long fibers) with an average fiber diameter of 114 nm. Furthermore, when the obtained BPEF-CNF composite was observed with an SEM, as shown in FIG. As shown, the surface of the cellulose fibers was coated with BPEF at locations where defibration did not proceed sufficiently.

(First mixing step)
Each component in the ratio shown in Table 2 was kneaded at a temperature of 150° C. using a pressurized kneader (manufactured by Moriyama Co., Ltd., capacity 10 liters) to prepare a first mixture (unvulcanized rubber composition).

(Second mixing step)
For 100 parts by mass of the first mixture, using a Banbury mixer (manufactured by Kobe Steel, Ltd., capacity 1.8 liters), at 150 ° C., the first preliminary mixture is added to 3 mass in terms of cellulose fiber solid content. and 4.5 parts by mass of naphthenic oil were added to prepare a second mixture (an unvulcanized rubber composition containing a BPEF-CNF composite).

(Vulcanization process)
The obtained second mixture was press-vulcanized at a vulcanization temperature of 180° C. to obtain a sheet-like vulcanized rubber composition (length 99 mm×width 96 mm×thickness 2 mm).

Example 2 (SBR/naphthenic oil-BPEF-CNF premix)
(Second preliminary mixing step)
1800 g of cyclohexanone and naphthene are added to 150 g of a water wet body containing plant-derived cellulose nanofibers (containing 20% by mass of solids and 30 g of cellulose nanofibers) containing 50% by mass or more of fibers with a diameter of 100 nm or less disentangled by a grinder method. 45 g of oil and 15 g of BPEF (150 parts by mass of naphthenic oil and 50 parts by mass of BPEF with respect to 100 parts by mass of cellulose nanofibers) were added, stirred at 600 rpm for 10 minutes using the stirrer, and then heated to 80°C using a rotary evaporator. 150 g of a second premix (a mixture of BPEF-CNF complex and naphthenic oil) was obtained by depressurizing at .

(Second mixing step)
To 100 parts by mass of the first mixture obtained in Example 1, using the Banbury mixer, at 150 ° C., 3 parts by mass of the second preliminary mixture was added in terms of cellulose fiber solid content, and the second A mixture (an unvulcanized rubber composition comprising a mixture of BPEF-CNF composite and naphthenic oil) was prepared.

(Vulcanization process)
The obtained second mixture was press-vulcanized at a vulcanization temperature of 180° C. to obtain a sheet-like vulcanized rubber composition (length 99 mm×width 96 mm×thickness 2 mm).

Example 3 (SBR/naphthenic oil-BPEF-CNF premix/silane coupling agent A)
(Second mixing step)
For 100 parts by mass of the first mixture obtained in Example 1, using the Banbury mixer, at 150 ° C., the second preliminary mixture obtained in Example 2 was added to 3 mass in terms of cellulose fiber solid content. and 0.3 parts by mass of silane coupling agent A to prepare a second mixture (an unvulcanized rubber composition containing a mixture of BPEF-CNF composite and naphthenic oil and silane coupling agent A).

(Vulcanization process)
The obtained second mixture was press-vulcanized at a vulcanization temperature of 180° C. to obtain a sheet-like vulcanized rubber composition (length 99 mm×width 96 mm×thickness 2 mm).

Example 4 (SBR/naphthenic oil-BPEF-CNF premix/silane coupling agent B)
(Second mixing step)
For 100 parts by mass of the first mixture obtained in Example 1, using the Banbury mixer, at 150 ° C., the second preliminary mixture obtained in Example 2 was added to 3 mass in terms of cellulose fiber solid content. 0.3 parts by mass of silane coupling agent B was added to prepare a second mixture (a mixture of BPEF-CNF composite and naphthenic oil and an unvulcanized rubber composition containing silane coupling agent B). .

(Vulcanization process)
The obtained second mixture was press-vulcanized at a vulcanization temperature of 180° C. to obtain a sheet-like vulcanized rubber composition (length 99 mm×width 96 mm×thickness 2 mm).

Table 3 shows the evaluation results of the vulcanized rubber compositions obtained in Reference Example 1 and Examples 1-4.

As is clear from the results in Table 3, the vulcanized rubber compositions obtained in Examples had a better balance of tensile properties, tear properties, and rigidity than the vulcanized rubber compositions obtained in Reference Example 1. Are better. Further, Examples 2 to 4 in which naphthenic oil was premixed have excellent dispersibility without coagulation of cellulose fibers. Furthermore, Examples 3 and 4, in which a silane coupling agent is added, are particularly excellent in tear resistance.

The rubber-like composition of the present invention can be used in various industrial parts (conveyor belts, rubber cover rolls, gaskets, printing rolls, conveyor belts and other belts, oil seals and other sealing members, packings, oil-resistant hoses and other hose members, etc.). , building materials (vibration damping materials such as window frame rubber, anti-vibration rubber, carpet bagging materials, etc.), transportation equipment materials (automotive materials, tires, belts such as power transmission belts, etc.), electrical and electronic equipment materials (electric wires coating, etc.), and among others, it is suitable for sealing members, hose members, tires, belts such as conveyor belts and power transmission belts, and anti-vibration rubbers.

Claims (17)

containing a rubber component (A), cellulose (B), a fluorene compound (C) having a 9,9-bis(aryl)fluorene skeleton, a reinforcing agent (D) and a softening agent (E),
The rubber component (A) is vulcanizable or crosslinkable and is at least one selected from rubbers and thermoplastic elastomers,
The ratio of the fluorene compound (C) to 100 parts by mass of the cellulose (B) is 30 to 70 parts by mass,
The softening agent (E) contains oils,
A rubber-like composition wherein, when molded into a sheet, the number of aggregated portions of the cellulose (B) having a major axis of 200 μm or more on the surface of the sheet is 30 pieces/(10 cm) ² or less. 2. The rubbery composition according to claim 1, wherein the fluorene compound (C) is a compound represented by the following formula (1).

(Wherein, ring Z is an arene ring, R ¹ and R ² are substituents, X ¹ is a heteroatom-containing functional group, k is an integer of 0 to 4, n is an integer of 1 or more, and p is an integer of 0 or more. show) In formula (1), X ¹ is a group -[(OA) _m1 -Y ¹ ] (wherein A is an alkylene group, Y ¹ is a hydroxyl group or a glycidyloxy group, and m1 is an integer of 0 or more). A rubbery composition according to claim 2. A rubbery composition according to claim 3, wherein ^Y1 is a hydroxyl group. The rubber-like composition according to any one of claims 1 to 4, wherein the fluorene compound (C) is attached to at least part of the surface of the cellulose (B). 6. The rubbery composition according to claim 5, wherein the cellulose (B) and the fluorene compound (C) are not covalently bonded. The rubber-like composition according to any one of claims 1 to 6, wherein the cellulose (B) is cellulose nanofibers. The rubbery composition according to any one of claims 1 to 7, wherein the reinforcing agent (D) comprises carbon black. The rubbery composition according to any one of claims 1 to 8, further comprising a silane coupling agent (F). A first mixing step of mixing the rubber component (A) and the reinforcing agent (D) to prepare a first mixture, the first mixture, cellulose (B) and a 9,9-bis(aryl)fluorene skeleton A second mixing step of mixing a fluorene compound (C) and a softening agent (E) to prepare a second mixture,
The rubber component (A) is vulcanizable or crosslinkable and is at least one selected from rubbers and thermoplastic elastomers,
The ratio of the fluorene compound (C) to 100 parts by mass of the cellulose (B) is 30 to 70 parts by mass,
The method for producing a rubbery composition according to any one of claims 1 to 9 , wherein the softener (E) contains oils. Further comprising a first premixing step of premixing cellulose (B) and a fluorene compound (C) having a 9,9-bis(aryl)fluorene skeleton to prepare a first premix, and second mixing 11. A method according to claim 10 , wherein the step comprises mixing the first mixture, the first pre-mixture and the softening agent (E) to prepare the second mixture. A second pre-mixing step of pre-mixing cellulose (B), a fluorene compound (C) having a 9,9-bis(aryl)fluorene skeleton, and a softening agent (E) to prepare a second pre-mixture is further performed. 11. The method of claim 10 , comprising, in the second mixing step, mixing the first mixture and the second premix to prepare the second mixture. The production method according to any one of claims 10 to 12 , wherein in the second mixing step, the second mixture is prepared by further mixing with the silane coupling agent (F). The rubbery composition further comprises a plasticizer (G), a vulcanizing agent (H) and a vulcanizing aid (I), wherein the plasticizer (G) is stearic acid, metal stearate, wax, paraffin, and containing at least one selected from fatty acid amides, and further mixed with the softening agent (E), the plasticizer (G), the vulcanizing agent (H) and the vulcanizing aid (I) in the first mixing step The production method according to any one of claims 10 to 13 , wherein the first mixture is prepared by The rubber component (A) is a vulcanizable or crosslinkable rubber, and further comprising a vulcanization step of vulcanizing the unvulcanized rubber composition obtained in the second mixing step to obtain a vulcanized rubber composition. Item 15. The production method according to any one of Items 10 to 14 . A molded article formed from the rubber-like composition according to any one of claims 1 to 9 . 17. The molded article according to claim 16 , which is a hose member, seal member, tire, belt or anti-vibration rubber.

Images