阅读说明：本技术 橡胶状组合物及其制造方法 (Rubber-like composition and process for producing the same ) 是由 山田昌宏 阪本浩规 杉本雅行 广田真之 细木佑美 村濑裕明 于 2019-11-22 设计创作，主要内容包括：将橡胶成分(A)、纤维素(B)和具有9,9-双(芳基)芴骨架的芴化合物(C)组合来制备橡胶状组合物。上述芴化合物(C)可以是下述式(1)表示的化合物。(式中,环Z表示芳烃环,R～1和R～2表示取代基,X～1表示含有杂原子的官能团,k表示0～4的整数,n表示1以上的整数,p表示0以上的整数)。上述橡胶状组合物能够提高强度、延伸度和硬度等机械特性。(A rubber-like composition was prepared by combining a rubber component (a), cellulose (B), and a fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton. The fluorene compound (C) may be a compound represented by the following formula (1). (wherein, the ring Z represents an aromatic hydrocarbon ring, R 1 And R 2 Represents a substituent group, X 1 Represents a functional group containing a hetero atom, 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). The rubber-like composition can improve mechanical properties such as strength, elongation and hardness.)

1. A rubber-like composition comprising a rubber component (A), cellulose (B), and a fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton.

2. A rubber-like composition according to claim 1, wherein the fluorene compound (C) is a compound represented by the following formula (1),

wherein ring Z represents an aromatic hydrocarbon ring, R¹And R²Represents a substituent group, X¹Represents a functional group containing a hetero atom, 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.

3. The rubber-like composition according to claim 2, wherein, in the formula (1), X¹Is a group- [ (OA)_m1-Y¹]In the formula, A represents an alkylene group, Y¹Represents a hydroxyl group or a glycidyloxy group, and m1 represents an integer of 0 or more.

4. The rubber-like composition of claim 3, wherein Y is¹Is a hydroxyl group.

5. A rubber-like composition according to any one of claims 1 to 4, wherein the fluorene compound (C) is attached to at least a part of the surface of the cellulose (B).

6. A rubber-like composition as described in claim 5, wherein the cellulose (B) and the fluorene compound (C) are not covalently bonded to each other.

7. A rubber-like composition according to any one of claims 1 to 6, wherein the cellulose (B) is a cellulose nanofiber.

8. A rubber-like composition according to any one of claims 1 to 7, wherein the rubber component (A) is a vulcanizable or crosslinkable rubber and/or a thermoplastic elastomer.

9. The rubber-like composition according to any one of claims 1 to 8, wherein the rubber component (A) contains at least 1 selected from the group consisting of diene rubbers and olefin rubbers.

10. A rubber-like composition according to any one of claims 1 to 8, wherein the rubber component (A) comprises a styrene-based thermoplastic elastomer.

11. A rubber-like composition according to any one of claims 1 to 10, wherein the cellulose (B) is contained in an amount of 0.1 to 30 parts by mass per 100 parts by mass of the rubber component (A), and the fluorene compound (C) is contained in an amount of 1 to 100 parts by mass per 100 parts by mass of the cellulose (B).

12. A method for producing a rubber-like composition according to any one of claims 1 to 11, which comprises a mixing step of mixing the rubber component (A), the cellulose (B), and the fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton.

13. The production method according to claim 12, wherein in the mixing step, the cellulose (B) and the fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton are premixed to prepare a premix, and the premix is then mixed with the rubber component (a).

14. The production method according to claim 12 or 13, wherein the rubber component (a) is a vulcanizable or crosslinkable rubber, and the production method further comprises a vulcanization step of vulcanizing the unvulcanized rubber composition obtained in the mixing step to obtain a vulcanized rubber composition.

15. A molded article comprising the rubber-like composition according to any one of claims 1 to 11.

16. The molded article of claim 15, which is a hose member, a sealing member, a tire, a belt or a vibration-proof rubber.

Technical Field

The present invention relates to a rubber-like composition (or rubber composition) containing a cellulose covered with a compound having a 9, 9-bisarylfluorene skeleton and a rubber component, and a method for producing the same.

Background

Cellulose, which is a plant-derived fiber, is a persistent resource with a small environmental load, and has excellent properties such as a high elastic modulus, high strength, and a low linear expansion coefficient. Therefore, the resin composition can be used in a wide range of applications, for example, materials such as paper, films, sheets, and the like, composite materials of resins (for example, reinforcing agents for resins), and the like. In addition, cellulose may be added to the rubber composition as a reinforcing agent to improve the mechanical properties of the rubber.

Jp 2005-75856 (patent document 1) discloses a rubber composition for a tire, which is prepared from natural plant fibers and contains 2 to 100 parts by weight of fine powdery cellulose fibers having an average particle diameter of 100 μm per 100 parts by weight of diene rubber, as a rubber composition having both excellent low heat build-up property and rigidity. Further, Japanese patent laid-open No. 2005-133025 (patent document 2) discloses a rubber composition having excellent abrasion resistance, which contains 5 to 75 parts by weight of starch and 0.1 to 40 parts by weight of bacterial cellulose having a fiber diameter of 1 μm or less, based on 100 parts by weight of a diene rubber component.

However, these rubber compositions have low compatibility between rubber and cellulose, and therefore, the fracture characteristics and the like are lowered.

Therefore, in order to improve the compatibility between rubber and cellulose, japanese patent No. 4581116 (patent document 3) discloses, as a vulcanized rubber composition having excellent fracture characteristics and less energy loss at the interface between rubber and cellulose, a vulcanized rubber composition containing 1 to 50 parts by weight (more preferably 7 to 15 parts by weight) of chemically modified microfibrous cellulose having an average fiber diameter of 4nm to 1 μm, based on 100 parts by weight of a rubber component containing at least one of natural rubber, modified natural rubber, acrylonitrile-butadiene rubber, and polybutadiene rubber. In this document, acetylation, alkyl esterification, complex esterification, β -ketone esterification, and aryl carbamate are described as methods for chemically modifying microfibrous cellulose.

However, in this rubber composition, the rubber may have a low affinity for chemically modified microfibrous cellulose, and therefore, the mechanical properties such as strength, elongation, and hardness cannot be improved. Further, in order to improve these properties, a large amount of chemically modified microfibrous cellulose is required, and it is difficult to achieve all of the properties at the same time.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2005-75856 (claims 1 and [0007] paragraph)

Patent document 2: japanese laid-open patent publication No. 2005-133025 (claims)

Patent document 3: japanese patent No. 4581116 publication (claims, paragraphs [0003], [0006], [0039 ])

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a rubber-like composition having improved mechanical properties such as strength, elongation and hardness, and a process for producing the same.

Means for solving the problems

As a result of intensive studies to achieve the above object, the present inventors have found that mechanical properties such as strength, elongation, and hardness of a rubber-like composition can be improved by blending a rubber component with a combination of cellulose and a compound having a 9, 9-bis (aryl) fluorene skeleton, and have completed the present invention.

That is, the rubber-like composition (or rubber composition) of the present invention comprises a rubber component (a), a cellulose (B), and a fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton. The fluorene compound (C) may be a compound represented by the following formula (1).

[ solution 1]

(wherein, the ring Z represents an aromatic hydrocarbon ring, R¹And R²Represents a substituent group, X¹Represents a functional group containing a hetero atom, 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).

In the above formula (1), X¹May be a group- [ (OA)_m1-Y¹](wherein A represents an alkylene group, Y¹Represents a hydroxyl group or a glycidyloxy group, m1 represents an integer of 0 or more), particularly Y¹May be a hydroxyl group. The fluorene compound (C) may be attached to at least a part of the surface of the cellulose (B). The cellulose (B) and the fluorene compound (C) are not covalently bonded to each other. The cellulose (B) may be a cellulose nanofiber. The above rubber component (A) may be a vulcanizable or crosslinkable rubber and/or a thermoplastic elastomer. The rubber component (a) may contain at least 1 selected from the group consisting of diene rubbers and olefin rubbers. The rubber component (a) may contain a styrene-based thermoplastic elastomer. The proportion of the cellulose (B) is about 0.1 to 30 parts by mass relative to 100 parts by mass of the rubber component (A). The ratio of the fluorene compound (C) is about 1 to 100 parts by mass relative to 100 parts by mass of the cellulose (B).

The present invention also includes a method for producing the rubber-like composition (or rubber composition) described above, which includes a mixing step of mixing the rubber component (a), the cellulose (B), and the fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton. In the mixing step, the cellulose (B) and the fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton may be premixed to prepare a premix, and the premix may be mixed with the rubber component (a). When the rubber component (a) is a vulcanizable or crosslinkable rubber, the production method may further include a vulcanization step of vulcanizing the unvulcanized rubber composition obtained in the mixing step to obtain a vulcanized rubber composition.

The present invention also includes a molded article formed of the rubber-like composition (or rubber composition). The molded body may be a hose member, a sealing member, a tire, a belt, or a vibration-proof rubber.

Effects of the invention

In the present invention, by combining cellulose with a compound having a 9, 9-bis (aryl) fluorene skeleton, the cellulose can be uniformly dispersed in the rubber component, and the mechanical properties such as strength, elongation, and hardness of the rubber-like composition (or rubber composition) can be improved.

Drawings

Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the cellulose nanofibers used in reference example 2.

Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the cellulose nanofibers used in reference example 3.

Fig. 3 is a Scanning Electron Microscope (SEM) photograph of the composite of BPEF and cellulose nanofibers obtained in example 2 at the position where the fibers were unwound.

Fig. 4 is a Scanning Electron Microscope (SEM) photograph of the composite of BPEF and cellulose nanofibers obtained in example 2 at a position where the defibration was not sufficiently performed.

Detailed Description

The rubber-like composition (or rubber composition) of the present invention comprises a rubber component (a), cellulose (B), and a fluorene compound (C) having a 9, 9-bis (aryl) fluorene skeleton.

[ rubber component (A) ]

The rubber component (A) contains a vulcanizable or crosslinkable rubber or thermoplastic elastomer. The rubber and the thermoplastic elastomer may be used singly or in combination of 2 or more.

The rubber is not particularly limited, and a conventional rubber can be used. Examples of the conventional rubber 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), fluorine rubber (FFKM, FKM), sulfur-containing rubber, and the like. These rubbers may be used alone or in combination of 2 or more. Among these rubbers, diene-based rubbers and/or olefin-based rubbers are preferable from the viewpoint of having a large effect of improving the dispersibility of the cellulose (B) by the fluorene compound (C).

Examples of the diene rubber 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), etc. These diene rubbers may be hydrogenated rubbers (for example, hydrogenated BR, hydrogenated NBR, hydrogenated SBR, etc.). These diene rubbers may be used alone or in combination of 2 or more.

Examples of the olefin-based 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, methylene norbornene, ethylidene norbornene, and the like. These olefinic rubbers may be used alone or in combination of 2 or more.

The copolymer rubber may be a random or block copolymer, and the block copolymer includes a copolymer having an AB type, ABA type, tapered type, or radial block type structure.

Among them, diene rubbers such as SBR and NBR, and olefin rubbers such as EPDM are preferable.

The thermoplastic elastomer may be any resin having rubber-like properties. The glass transition temperature of the thermoplastic elastomer is suitably selected from the range of about-50 ℃ to about 100 ℃, for example about-20 ℃ to about 80 ℃, preferably about 0 ℃ to about 50 ℃ (for example about 5 ℃ to about 40 ℃), and more preferably about 10 ℃ to about 30 ℃ (particularly about 15 ℃ to about 25 ℃), depending on the use of the composition. Note that in the present specification and claims, the glass transition temperature can be measured by a conventional method using a differential scanning calorimeter.

In a durometer hardness test (type a) according to JIS K6253, the thermoplastic elastomer has a hardness of 95 ° or less, for example, 50 to 90 °, preferably 60 to 85 °, more preferably 65 to 80 ° (particularly, 70 to 78 °). If the hardness is too high, mechanical properties of the composition such as elongation may be reduced.

In the method (190 ℃, 2.16kgf) according to JIS K7210, the Melt Flow Rate (MFR) of the thermoplastic elastomer may be 0.5g/10 min or more, for example, 0.5 to 20g/10 min, preferably 1 to 10g/10 min, more preferably 1.5 to 5g/10 min (particularly, 2 to 3g/10 min). When the MFR is too small, there is a possibility that the mechanical properties of the composition and the dispersibility of the cellulose (B) in the composition may be lowered.

Specifically, as the thermoplastic elastomer, a conventional thermoplastic elastomer can be utilized. Examples of conventional thermoplastic elastomers include: olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, fluorine-based thermoplastic elastomers, and the like. These thermoplastic elastomers may be used alone or in combination of 2 or more. Among these thermoplastic elastomers, a styrene-based thermoplastic elastomer is preferable from the viewpoint of having a large effect of improving the dispersibility of the cellulose (B) by the fluorene compound (C).

The styrene-based thermoplastic elastomer is an elastomer in which the hard portion includes a styrene-based unit and the soft portion includes a diene-based unit, and may be, for example, a styrene-diene-based block copolymer or a hydrogenated product thereof. Examples of the styrene-diene block copolymer or the hydrogenated product thereof include: styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers (SBS), hydrogenated styrene-butadiene-styrene block copolymers (SEBS), styrene-isoprene block copolymers, hydrogenated styrene-isoprene block copolymers (SEP), styrene-isoprene-styrene block copolymers (SIS), hydrogenated styrene-isoprene-styrene block copolymers (SEPs), and the like. In the block copolymer, the end block may include any of a styrene block or a diene block. Among them, a (hydrogenated) styrene-butadiene block copolymer such as SBS or SEBS is preferable.

[ cellulose (B) ]

Examples of the cellulose (B) include: pulp containing a small amount of non-cellulose components such as lignin and hemicellulose, for example, pulp produced from a plant-derived cellulose raw material { e.g., wood [ e.g., coniferous trees (e.g., pine, fir, juniper, japanese hemlock, fir, etc.), broad-leaved trees (beech, birch, poplar, maple, etc.) ], herbs [ hemp (e.g., hemp, flax, abaca, ramie, etc.), rice straw, bagasse, daphne, etc. ], seed cotton fibers (e.g., cotton linter, babassu (bombax), kapok, etc.), bamboo, sugarcane, etc. }, an animal-derived cellulose raw material (e.g., sea squirt cellulose), a bacteria-derived cellulose raw material (e.g., cellulose contained in Nata de coco), and the like. These celluloses may be used alone or in combination of 2 or more. Among these celluloses, a pulp derived from wood pulp (e.g., needle pulp, broad-leaf pulp, etc.), seed cotton fiber pulp (e.g., linter pulp), and the like are preferable. The slurry may be a mechanical slurry obtained by mechanically treating a slurry material, but is preferably a chemical slurry obtained by chemically treating a slurry material, from the viewpoint of reducing the content of non-cellulose components.

The cellulose (B) may be in the form of particles, etc., but is usually in the form of fibers. When the cellulose (B) is fibrous cellulose (cellulose fiber), the fiber diameter of the cellulose (B) may be in the order of micrometers, but is preferably in the order of nanometers from the viewpoint of improving the mechanical properties of the rubber-like composition. The average fiber diameter of the cellulose fiber may be, for example, 1 to 1000nm (e.g., 2 to 800nm), preferably 3 to 500nm (e.g., 5 to 300nm), and more preferably 10 to 200nm (particularly, 15 to 100 nm). When the average fiber diameter is too large, properties such as strength of the rubber-like composition may be deteriorated. The maximum fiber diameter of the cellulose fiber may be, for example, 3 to 1000nm (e.g., 4 to 900nm), preferably 5 to 700nm (e.g., 10 to 500nm), and more preferably 15 to 400nm (particularly, 20 to 300 nm). In many cases, such nano-sized cellulose fibers are substantially free of cellulose fibers having a fiber diameter of a micrometer.

The average fiber length of the cellulose fibers may be, for example, about 0.01 to 500 μm (e.g., about 0.1 to 400 μm), and is usually 1 μm or more (e.g., about 5 to 300 μm), preferably 10 μm or more (e.g., about 20 to 200 μm), and more preferably 30 μm or more (particularly, about 50 to 150 μm). When the average fiber length is too short, the mechanical properties of the rubber-like composition may be lowered, and conversely, when the average fiber length is too long, the dispersibility of the cellulose fibers in the rubber-like composition may be lowered.

The ratio (aspect ratio) of the average fiber length to the average fiber diameter of the cellulose fibers may be, for example, 5 or more (for example, about 5 to 10000), preferably 10 or more (for example, about 10 to 5000), more preferably 20 or more (for example, about 20 to 3000), particularly 50 or more (for example, about 50 to 2000), and may be 100 or more (for example, about 100 to 1000), and more preferably 200 or more (for example, about 200 to 800). When the aspect ratio is too small, the effect of reinforcing the rubber component is low, and when the aspect ratio is too large, uniform dispersion is 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 the cellulose fibers can be calculated by selecting 50 fibers at random from an image of a scanning electron microscope photograph and adding the average.

The cellulose nanofibers may be nanofibers obtained by a conventional method, for example, a physical method such as a high-pressure homogenizer method, an Aqueous Counter Collision method (Aqueous Collision), a polishing method, a ball milling method, a twin-screw kneading method, or nanofibers obtained by a chemical method using a TEMPO catalyst, phosphoric acid, a dibasic acid, sulfuric acid, hydrochloric acid, or the like.

The cellulose (B) may be a cellulose (or cellulose fiber) having high crystallinity, and the crystallinity of the cellulose (B) may be, for example, about 40 to 100% (e.g., about 50 to 100%), preferably about 60 to 100%, more preferably about 70 to 100% (particularly about 75 to 99%), and usually about 60% or more (e.g., about 60 to 98%). The crystalline structure of the cellulose (B) may be, for example, type I, type II, type III, type IV, or the like, and preferably is a type I crystalline structure excellent in linear expansion characteristics, elastic modulus, or the like. The crystallinity can be measured using a powder X-ray diffraction apparatus ("Ultima IV" manufactured by Rigaku corporation) or the like.

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

From the viewpoint of mechanical properties of the composition, the degree of polymerization of the cellulose (B) may be 500 or more, preferably 600 or more (for example, about 600 to 10 ten thousand), and when the cellulose (B) is a nanofiber, the viscosity average degree of polymerization may be, for example, about 100 to 10000, preferably about 200 to 5000, and more preferably about 300 to 2000.

The viscosity average degree of polymerization can be determined by the viscosity method described in TAPPI T230. Specifically, 0.04g of modified cellulose nanofibers (or raw cellulose nanofibers) were precisely weighed, 10mL of water and 10mL of a 1M aqueous solution of copper ethylenediamine were added, and the mixture was stirred for about 5 minutes to dissolve the modified cellulose. The resulting solution was charged into an Ubbelohde viscometer, and the flow rate was measured at 25 ℃. A mixture of 10mL of water and 10mL of a 1M aqueous solution of copper ethylenediamine was used as a control for the measurement. The viscosity average degree of polymerization can be calculated from the intrinsic viscosity [ η ] calculated based on these measured values, according to the following formula described in a manual of experiments on wood science (edited by the japanese society for lumber, published by the wenyongtang).

Viscosity average polymerization degree 175 × [ η ].

The proportion of the cellulose (B) (particularly, cellulose fiber such as cellulose nanofiber) may be selected from the range of about 0.1 to 30 parts by mass, for example, about 0.2 to 25 parts by mass, preferably about 0.3 to 20 parts by mass, and more preferably about 0.5 to 15 parts by mass (particularly, about 1 to 10 parts by mass) with respect to 100 parts by mass of the rubber component (a). Further, in the present invention, cellulose (B) (particularly, cellulose fibers such as cellulose nanofibers) can be uniformly dispersed by the fluorene compound (C) described later, and mechanical properties, heat resistance, and the like can be improved even if the proportion of cellulose (B) is small, and the proportion of cellulose (B) is, for example, about 0.1 to 10 parts by mass, preferably about 0.3 to 7 parts by mass, and more preferably about 0.5 to 5 parts by mass (particularly about 1 to 3 parts by mass) relative to 100 parts by mass of the rubber component (a). When the proportion of the cellulose (B) is too small, the mechanical properties of the rubber-like composition may be deteriorated, and conversely, when the proportion of the cellulose (B) is too large, the moldability of the rubber-like composition may be deteriorated.

[ fluorene compound (C) ]

The fluorene compound (C) having an aryl group at the 9, 9-position is used as a compatibilizing agent or a dispersing agent for uniformly dispersing the cellulose (B) in the rubber component (a), and by uniformly dispersing the cellulose (B) in the rubber component (a), 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 above formula (1).

In the above formula (1), examples of the aromatic hydrocarbon ring represented by the ring Z include monocyclic aromatic hydrocarbon rings such as benzene rings, polycyclic aromatic hydrocarbon rings, and the like, and the polycyclic aromatic hydrocarbon ring includes condensed polycyclic aromatic hydrocarbon rings (condensed polycyclic hydrocarbon rings), ring-aggregated aromatic hydrocarbon rings (ring-aggregated aromatic hydrocarbon rings), and the like.

Examples of the fused polycyclic aromatic hydrocarbon ring include: fused bicyclic aromatic hydrocarbon rings (e.g., fused bicyclic C such as naphthalene ring)_10-16Aromatic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (e.g., anthracene rings, phenanthrene rings, etc.), fused two-to four-ring aromatic hydrocarbon rings, and the like. Preferred fused polycyclic aromatic hydrocarbon rings include naphthalene rings, anthracene rings, and the like, and naphthalene rings are particularly preferred.

As the aromatic hydrocarbon ring of the ring assembly, there can be exemplified: a biaryl ring [ e.g., a biphenyl ring, a binaphthyl ring, a phenylnaphthalene ring (e.g., a 1-phenylnaphthalene ring, a 2-phenylnaphthalene ring, etc.) ]_6-12Aromatic hydrocarbon ring and the like]A terphenyl ring (e.g., a terphenyl ring, etc. terphenyl ring)_6-12Aromatic hydrocarbon rings, etc.). As a preferable aromatic hydrocarbon ring having a ring assembly, there may be mentioned BiC_6-10Aromatic hydrocarbon rings, particularly biphenyl rings, and the like.

The 2 rings Z substituted in the 9-position of the fluorene may be the same or different, but are usually mostly the same ring. Among the rings Z, preferred are benzene rings, naphthalene rings, biphenyl rings (particularly benzene rings), and the like.

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

As a result of X¹Examples of the functional group containing a hetero atom include a functional group containing at least 1 kind of hetero atom selected from oxygen, sulfur and nitrogen atoms. The number of hetero atoms contained in such a functional group is not particularly limited, and may be usually 1 to 3, preferably 1 or 2.

As mentioned aboveExamples of the functional group include: group- [ (OA)_m1-Y¹](in the formula, Y¹Is hydroxy, glycidyloxy, amino, N-substituted amino or mercapto, A is alkylene, m1 is an integer of 0 or more), a group- (CH)₂)_m2-COOR³(in the formula, R³A hydrogen atom or an alkyl group, and m2 is an integer of 0 or more).

In the group- [ (OA)_m1-Y¹]In (b) as Y¹Examples of the N-substituted amino group of (a) include: n-monoalkylamino (N-mono C) groups such as methylamino and ethylamino_1-4Alkylamino, etc.), N-monohydroxyalkylamino (N-monohydroxy C) such as hydroxyethylamino, etc_1-4Alkylamino, etc.), and the like.

The alkylene group a includes a linear or branched alkylene group, and examples of the linear alkylene group include: ethylene, trimethylene, tetramethylene and the like C_2-6Alkylene (preferably straight chain C)_2-4Alkylene, more preferably straight chain C_2-3Alkylene, especially ethylene); examples of the branched alkylene group include: branched C such as propylene, 1, 2-butanediyl and 1, 3-butanediyl_3-6Alkylene (preferably branched C)_3-4Alkylene, particularly propylene), and the like.

M1 representing the number of repeating oxyalkylene groups (average addition mole number) of the oxyalkylene group (OA) is selected from the range of 0 or more (for example, 0 to 15, preferably 0 to 10 or so), and may be, for example, 0 to 8 (for example, 1 to 8), preferably 0 to 5 (for example, 1 to 5), more preferably 0 to 4 (for example, 1 to 4), particularly 0 to 3 (for example, 1 to 3), and usually 0 to 2 (for example, 0 to 1). When m1 is 2 or more, the alkylene groups A may be the same or different in kind. In addition, in the same or different rings Z, the kinds of alkylene groups a may be the same or different.

In the group- (CH)₂)_m2-COOR³In (1) as R³Examples of the alkyl group include: straight or branched C such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and the like_1-6An alkyl group. Preferred alkyl is C_1-4Alkyl, especially C_1-2An alkyl group. M2 representing the number of repetitions (average molar number of addition) of methylene may be 0 orAn integer of 1 or more (e.g., 1 to 6, preferably 1 to 4, and more preferably about 1 to 2). m2 can be 0 or 1-2.

Wherein, the group X¹Preferably a group- [ (OA)_m1-Y¹](wherein A is an alkylene group and Y is¹Hydroxyl group or glycidyloxy group, and m1 is an integer of 0 or more), from the viewpoint of having a large effect of improving the dispersibility of the cellulose (B), Y is particularly preferable¹Radicals being hydroxy- [ (OA)_m1-OH][ wherein A is C such as ethylene_2-6Alkylene (e.g. being C)_2-4Alkylene, especially C_2-3Alkylene) and m1 is an integer of 0 to 5 (e.g., 0 or 1)]。

In the above formula (1), represents a group X substituted on the ring Z¹The number n of (a) may be 1 or more, preferably 1 to 3, more preferably 1 or 2 (particularly 1). Note that the number of substitution n may be the same or different in each ring Z.

Group X¹The substituent X may be substituted at an appropriate position of the ring Z, for example, when the ring Z is a benzene ring, it is often substituted at the 2, 3, 4-positions (particularly, the 3-and/or 4-positions, particularly, the 4-position) of the phenyl group, and when the 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 1-or 2-position (substituted in the relation of 1-naphthalene or 2-naphthalene) of the naphthalene ring is substituted at the 9-position of the fluorene, and the substituent X is often substituted at the 1, 5-or 2, 6-positions (particularly, the relation of the 2, 6-positions when n is 1) relative to the substituted position¹. When n is 2 or more, the substitution position is not particularly limited. In addition, in the aromatic hydrocarbon ring Z of the ring assembly, the group X¹The substitution position of (b) is not particularly limited, and may be, for example, on an aromatic hydrocarbon ring bonded to the 9-position of fluorene and/or an aromatic hydrocarbon ring adjacent to the aromatic hydrocarbon ring. For example, the 3-or 4-position of the biphenyl ring Z may be bonded to the 9-position of fluorene, and when the 3-position of the biphenyl ring Z is bonded to the 9-position of fluorene, the group X¹The substitution position(s) of (b) may be any of the positions 2,4, 5, 6, 2 ', 3 ', and 4 ', and preferably may be at the position 6.

In the above formula (1), as the substituent R²Examples thereof include: halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group (methyl group, ethyl group, propyl group, isopropyl group)Straight or branched C such as a phenyl group, butyl group, sec-butyl group or tert-butyl group_1-10Alkyl, preferably straight or branched C_1-6Alkyl, more preferably straight-chain or branched C_1-4Alkyl, etc.), cycloalkyl (C such as cyclopentyl, cyclohexyl, etc.)_5-10Cycloalkyl group, etc.), aryl group [ phenyl group, alkylphenyl group (methylphenyl group, dimethylphenyl group, etc.), biphenyl group, naphthyl group, etc. ]_6-12Aryl radicals]Aralkyl (C such as benzyl or phenethyl)_6-10aryl-C_1-4Alkyl, etc.), alkoxy (e.g., methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, t-butoxy, etc., and the like_1-10Alkoxy, etc.), cycloalkoxy (e.g., C such as cyclohexyloxy, etc.)_5-10Cycloalkoxy group and the like), aryloxy group (e.g., C such as phenoxy group and the like)_6-10Aryloxy group and the like), aralkyloxy group (e.g., C such as benzyloxy group and the like)_6-10aryl-C_1-4Alkoxy, etc.), alkylthio (e.g., methylthio, ethylthio, propylthio, n-butylthio, t-butylthio, etc. C_1-10Alkylthio, etc.), cycloalkylthio (e.g., C such as cyclohexylthio, etc.)_5-10Cycloalkylthio and the like), arylthio (e.g., C such as thiophenoxy and the like)_6-10Arylthio, etc.), aralkylthio (e.g., C such as benzylthio, etc.)_6-10aryl-C_1-4Alkylthio, etc.), acyl (e.g., C such as acetyl, etc.)_1-6Acyl, etc.), nitro, cyano, etc.

In these substituents R²In (b), as representative groups, there may be mentioned: halogen atom, hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), alkoxy group, acyl group, nitro group, cyano group, substituted amino group, etc. As preferred substituents R²Preferably an alkoxy group (linear or branched C such as methoxy group)_1-4Alkoxy group, etc.), particularly preferably an alkyl group (particularly a linear or branched C group such as methyl group)_1-4Alkyl groups). To illustrate, when the substituent R²When it is aryl, the substituent R²May form an aromatic hydrocarbon ring of the above-mentioned ring assembly together with ring Z. In the same or different rings Z, substituents R²May be the same or different.

Substituent R²The coefficient p of (A) can be appropriately selected depending on the kind of the ring Z and the like, and for example, it may beAbout 0 to 8, and 0 to 4, preferably 0 to 3 (for example, 0 to 2), and more preferably 0 or 1. In particular when p is 1, ring Z is a benzene, naphthalene or biphenyl ring, substituent R²May be a methyl group.

As substituents R¹Examples thereof include: cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), carboxyl group, alkoxycarbonyl group (e.g., C such as methoxycarbonyl group)_1-4Alkoxy-carbonyl group and the like), alkyl (C such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and the like_1-6Alkyl, aryl (phenyl, etc. C)_6-10Aryl), and the like.

In these substituents R¹Among them, preferred is a linear or branched C_1-4Alkyl (especially C such as methyl)_1-3Alkyl), carboxyl or C_1-2Alkoxy-carbonyl, cyano, halogen atom. The number of substitution 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 substitution numbers k may be the same or different from each other, and when k is 2 or more, the substituent R¹May be the same as or different from each other, a substituent R substituted on 2 benzene rings of the fluorene ring¹May be the same or different. In addition, the substituent R¹The substitution position(s) 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 them, as a preferred fluorene compound, the group X¹Is a group- [ (OA)_m1-Y¹](in the formula, Y¹Representing a hydroxyl group), for example: 9, 9-bis (hydroxy-C) fluorenes such as 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (5-hydroxy-1-naphthyl) fluorene and 9, 9-bis (6-hydroxy-2-naphthyl) fluorene_6-12Aryl) fluorene; 9, 9-bis (di-or trihydroxy C) s such as 9, 9-bis (3, 4-dihydroxyphenyl) fluorene_6-12Aryl) fluorene; 9, 9-bis (mono-or di-C) such as 9, 9-bis (3-methyl-4-hydroxyphenyl) fluorene_1-4Alkyl-hydroxy C_6-12Aryl) fluorene; 9, 9-bis (C) such as 9, 9-bis (3-phenyl-4-hydroxyphenyl) fluorene and 9, 9-bis (4-phenyl-3-hydroxyphenyl) fluorene_6-12Aryl-hydroxy C_6-12Aryl) fluorene; 9, 9-bis [4- (2-hydroxyethoxy) phenyl]Fluorene, 9-bis [6- (2-hydroxyethoxy) -2-naphthyl]9, 9-bis (hydroxy (poly) C) s such as fluorene_2-4Alkoxy radicalradical-C_6-12Aryl) fluorene; 9, 9-bis [ 3-methyl-4- (2-hydroxyethoxy) phenyl]9, 9-bis (C) such as fluorene_1-4Alkyl-hydroxy (poly) C_2-4alkoxy-C_6-12Aryl) fluorene; 9, 9-bis [ 3-phenyl-4- (2-hydroxyethoxy) phenyl]Fluorene, 9-bis [ 4-phenyl-3- (2-hydroxyethoxy) phenyl]9, 9-bis (C) such as fluorene_6-12Aryl-hydroxy (poly) C_2-4alkoxy-C_6-12Aryl) fluorene, and the like.

As a radical X¹Is a group- [ (OA)_m1-Y¹](in the formula, Y¹Represents a glycidyloxy group), examples of the preferred fluorene compound include: 9, 9-bis (glycidyloxy C-fluorene such as 9, 9-bis (3-glycidyloxyphenyl) fluorene, 9, 9-bis (4-glycidyloxyphenyl) fluorene, 9, 9-bis (5-glycidyloxy-1-naphthyl) fluorene and 9, 9-bis (6-glycidyloxy-2-naphthyl) fluorene_6-10Aryl) fluorene; 9, 9-bis (glycidoxy (poly) alkoxyaryl) fluorenes, for example, 9, 9-bis (4- (2-glycidoxyethoxy) phenyl) fluorene, 9, 9-bis (4- (2-glycidoxypropyloxy) phenyl) fluorene, 9, 9-bis (5- (2-glycidoxyethoxy) -1-naphthyl) fluorene, 9, 9-bis (6- (2-glycidoxyethoxy) -2-naphthyl) fluorene and the like, 9, 9-bis (glycidoxy (poly) C_2-4Alkoxy radical C_6-10Aryl) fluorene; 9, 9-bis (mono-or di-C) fluorenes, e.g., 9, 9-bis (3-methyl-4-glycidyloxyphenyl) fluorenes_1-4Alkyl-glycidyloxy C_6-10Aryl) fluorene; 9, 9-bis (alkyl-glycidoxy (poly) alkoxyaryl) fluorenes, for example, 9, 9-bis (mono-or di-C) fluorenes such as 9, 9-bis (3-methyl-4- (2-glycidoxyethoxy) phenyl) fluorene_1-4Alkyl-glycidyloxy (poly) C_2-4Alkoxy radical C_6-10Aryl) fluorene; 9, 9-bis (C) fluorenes, e.g., 9, 9-bis (3-phenyl-4-glycidyloxyphenyl) fluorenes_6-10Aryl-glycidyloxy C_6-10Aryl) fluorene; 9, 9-bis (aryl-glycidoxy (poly) alkoxyaryl) fluorenes, for example, 9, 9-bis (C) fluorene such as 9, 9-bis (3-phenyl-4- (2-glycidoxyethoxy) phenyl) fluorene_6-10Aryl-glycidyloxy (poly) C_2-4Alkoxy radical C_6-10Aryl) fluorene; 9, 9-bis (di (glycidyloxy) aryl) fluorene, for example, 9, 9-bis (di (glycidyloxy) C such as 9, 9-bis (3, 4-di (glycidyloxy) phenyl) fluorene_6-10Aryl) fluorene; 9, 9-bis (di (glycidoxy (poly) alkoxy) aryl) fluorenes, for example, 9, 9-bis (di (glycidoxy (poly) C) fluorenes such as 9, 9-bis (3, 4-bis (2-glycidoxyethoxy) phenyl) fluorene_2-4Alkoxy) C_6-10Aryl) fluorene, and the like.

These fluorene compounds (C) may be used alone or in combination of 2 or more. As used herein, "(poly) alkoxy" is intended to include both alkoxy and polyalkoxy groups.

The fluorene compound (C) may be present in the composition independently of or in a free form from the cellulose (B), and at least a part of the fluorene compound (C) is preferably present in the composition in proximity to or in contact with the cellulose (B), and particularly preferably forms a complex by complexing them, from the viewpoint of improving the dispersibility of the cellulose (B). When the fluorene compound (C) is formed into a composite, the fluorene compound (C) may be bonded to the cellulose (B) by adhering to the cellulose (B), and the form of the composite is not particularly limited. The fluorene compound (C) may cover at least a part of the surface of the cellulose (B), or the granular fluorene compound (C) may be attached to the cellulose (B).

When the cellulose (B) and the fluorene compound (C) are combined, the cellulose (B) may be combined without being modified (chemically modified) by the fluorene compound (C). That is, in the present invention, it is presumed that the two are bonded not by a covalent bond such as an ether bond or an ester bond but by a hydrogen bond or the like with relatively moderate bonding or affinity. Therefore, the cellulose (B) (particularly, nanofibers) has a high degree of freedom in the composition, and can improve the mechanical properties (e.g., extensibility) of the composition, and can be easily aligned in the stretching direction by being disentangled when a tensile stress such as stretching is applied. In the present specification and claims, the presence or absence of a covalent bond between the cellulose (B) and the fluorene compound (C) can be easily determined by a method of washing with a solvent in which the fluorene compound (C) is dissolved and quantifying the fluorene compound (C) in the washing liquid.

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

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

The proportion of the fluorene compound (C) may be selected from a range of about 1 to 100 parts by mass, for example, about 10 to 90 parts by mass, preferably about 20 to 80 parts by mass, and more preferably about 30 to 70 parts by mass (particularly about 40 to 60 parts by mass) with respect to 100 parts by mass of the cellulose (B). In the present invention, since the ratio of the fluorene compound (C) is large, the dispersibility of the cellulose (B) can be highly improved, and the cellulose (B) can be effectively and uniformly dispersed even in the form of nanofibers. When the proportion of the fluorene compound (C) is too small, dispersibility of the cellulose (B) in the composition may be reduced to lower mechanical properties of the composition, and on the contrary, when the proportion of the fluorene compound (C) is too large, mechanical properties of the composition may be reduced.

[ enhancer (D) ]

The rubber-like composition of the present invention [ particularly, a vulcanized rubber composition in which the rubber component (a) is a rubber ] may contain a reinforcing agent (D) in addition to the rubber component (a), the cellulose (B), and the fluorene compound (C) in order to improve mechanical properties such as hardness and strength.

As the reinforcing agent (D), conventional reinforcing agents can be used, and examples thereof include: particulate reinforcing agents (carbonaceous materials such as carbon black and graphite, metal oxides such as calcium oxide, magnesium oxide, barium oxide, iron oxide, copper oxide, titanium oxide, and alumina (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 carbonate and calcium carbonate, metal sulfates such as calcium sulfate and barium sulfate, mineral materials such as zeolite, diatomaceous earth, calcined diatomaceous earth, activated clay, silica, talc, mica, kaolin, sericite, bentonite, montmorillonite, and clay), fibrous reinforcing agents (inorganic fibers such as glass fibers, carbon fibers, boron fibers, whiskers, and wollastonite, and organic fibers such as polyester fibers and polyamide fibers), and the like. These enhancers may be used singly or in combination of 2 or more.

Among these reinforcing agents, a particulate reinforcing agent (particularly a particulate inorganic reinforcing agent) such as carbon black or silica is generally used, and carbon black is preferable from the viewpoint of greatly improving the mechanical properties of the rubber-like composition by combining with the fluorene compound (C). In the present invention, the fluorene compound (C) not only improves the dispersibility of the cellulose (B) in the rubber component but also has a high compatibility with the particulate reinforcing agent (particularly, carbon black), and the dispersibility of the particulate reinforcing agent can be improved.

Examples of the carbon black include: acetylene black, lamp black, pyrolytic carbon black, furnace black, channel black, ketjen black, coating carbon black, grafted carbon black, and the like. These carbon blacks may be used alone or in combination of 2 or more.

The average particle diameter (arithmetic average particle diameter) of the carbon black may be selected from the range of about 5 to 200nm, for example, about 10 to 150nm, preferably about 15 to 100nm, and more preferably about 20 to 80nm (particularly about 30 to 50 nm). When the average particle diameter of the carbon black is too small, uniform dispersion may be difficult, and when the average particle diameter of the carbon black is too large, mechanical properties of the vulcanized rubber composition may be deteriorated.

The proportion of the reinforcing agent (D) may be selected from the range of about 3 to 300 parts by mass, for example, about 5 to 200 parts by mass, preferably about 8 to 150 parts by mass, and more preferably about 10 to 100 parts by mass (particularly about 15 to 80 parts by mass) relative to 100 parts by mass of the rubber component (A). When the proportion of the reinforcing agent is too small, the effect of improving the mechanical properties of the rubber-like composition may be reduced, and conversely, when the proportion of the reinforcing agent is too large, the elongation, strength and the like of the vulcanized rubber composition may be reduced.

[ softening agent (E) ]

In order to improve dispersibility of the cellulose (B) in the composition and moldability of the composition, the rubber-like composition [ particularly, a vulcanized rubber composition in which the rubber component (a) is rubber ] of the present invention may contain a softening agent (E) in addition to the rubber component (a), the cellulose (B) and the fluorene compound (C).

The softener (E) includes oils and the like as softeners which are compatible with the rubber component (a) and can lower the viscosity of the rubber-like composition (particularly, unvulcanized rubber composition). Examples of the oils include: paraffin oil, naphthenic oil, processing oil, etc. These softening agents may be used alone or in combination of 2 or more. Among these softening agents, oils such as paraffin-based oils and naphthenic-based oils are preferable.

In the present invention, when the softener (E) is added to improve moldability, the fluorene compound (C) is contained, so that the softening agent (E) can suppress the deterioration of the mechanical properties of the rubber-like composition (particularly, a vulcanized rubber composition containing an olefin rubber such as EPDM).

The proportion of the softener (E) may be suitably selected depending on the kind of the rubber component (a), and may be selected from a range of about 0.1 to 500 parts by mass, for example, about 0.5 to 400 parts by mass (for example, about 1 to 300 parts by mass), preferably about 1 to 200 parts by mass, and more preferably about 3 to 100 parts by mass, relative to 100 parts by mass of the rubber component (a). When the rubber component (a) is an olefin rubber, the proportion of the softener (E) may be, for example, 10 to 200 parts by mass, preferably 20 to 150 parts by mass, and more preferably 30 to 100 parts by mass (particularly, 40 to 60 parts by mass) per 100 parts by mass of the rubber component (a). When the proportion of the softener (E) is too small, the effect of the fluorene compound (C) to improve the dispersibility of the cellulose (B) may be reduced, and conversely, when the proportion of the softener (E) is too large, the mechanical properties of the rubber-like composition may be reduced.

[ plasticizer (F) ]

The rubber-like composition of the present invention [ particularly, a vulcanized rubber composition in which the rubber component (a) is a rubber ] may contain a plasticizer (F) in addition to the rubber component (a), the cellulose (B), and the fluorene compound (C) in order to improve moldability and the like. Examples of the plasticizer (F) include: stearic acid, metal stearates, waxes, paraffins, fatty amides, and the like. These plasticizers may be used alone or in combination of 2 or more. Among them, higher fatty acids such as stearic acid are preferable. The proportion of the plasticizer (F) is, for example, about 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass, and more preferably about 1 to 3 parts by mass, per 100 parts by mass of the rubber component (A). When the proportion of the plasticizer (F) is too small, the effect of improving the moldability of the rubber-like composition may be reduced, and on the contrary, when the proportion of the plasticizer (F) is too large, the mechanical properties of the rubber-like composition may be reduced.

[ vulcanizing agent (G) ]

When the rubber component (A) of the rubber-like composition of the present invention is a rubber, the rubber-like composition usually contains a vulcanizing agent (G). As the vulcanizing agent (G), a conventional vulcanizing agent can be used depending on the kind of the rubber. The vulcanizing agent (G) includes a sulfur-based vulcanizing agent and an organic peroxide.

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

Examples of the organic peroxide include: diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, and 2, 4-dichlorobenzoyl peroxide; dialkyl peroxides such as di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, 1-dibutylperoxy-3, 3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -hexane, and 1, 3-bis (tert-butylperoxyisopropyl) benzene; hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, and diisopropylbenzene hydroperoxide; peroxy esters such as n-butyl 4, 4-di-tert-butylperoxyvalerate and 2, 5-dimethylhexane-2, 5-bis (peroxybenzoate).

These vulcanizing agents may be used alone or in combination of 2 or more. Among them, a dialkyl peroxide such as sulfur and dicumyl peroxide is generally used.

The proportion of the vulcanizing agent (G) may be selected from the range of about 0.1 to 30 parts by mass per 100 parts by mass of the rubber, and when the vulcanizing agent (G) is a sulfur-based vulcanizing agent, it is, for example, about 0.1 to 10 parts by mass, preferably about 0.5 to 8 parts by mass, and more preferably about 0.6 to 5 parts by mass, and when the vulcanizing agent (G) is an organic peroxide, it is, for example, about 1 to 25 parts by mass, preferably about 3 to 20 parts by mass, and more preferably about 5 to 15 parts by mass.

[ vulcanization Assistant (H) ]

When the rubber component (A) of the rubber-like composition of the present invention is a rubber, a vulcanization aid (H) may be contained for accelerating vulcanization. Examples of the vulcanization aid (or co-crosslinking agent) (H) include: organic vulcanization accelerators [ e.g., sulfenamide accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and N-tert-butyl-2-benzothiazolesulfenamide (TBBS) ]; thiuram accelerators such as tetramethylthiuram monosulfide (TMTM) and tetramethylthiuram disulfide (TMTD); thiazole accelerators such as 2-Mercaptobenzothiazole (MBT), zinc salt of MBT, and dibenzothiazyl disulfide (MBTS); thiourea accelerators such as Trimethylthiourea (TMU) and diethylthiourea (EDE); guanidine accelerators such as Diphenylguanidine (DPG) and di-o-tolylguanidine (DOTG); dithiocarbamate accelerators such as sodium dimethyldithiocarbamate; xanthate accelerators such as zinc isopropyl xanthate; aldehyde-amine or aldehyde-ammonia accelerators such as hexamethylenetetramine, polyfunctional (iso) cyanurates [ e.g., triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC) ], polydienes (e.g., 1, 2-polybutadiene), metal salts of unsaturated carboxylic acids [ e.g., polyvalent metal (meth) acrylates such as zinc (meth) acrylate ], polyfunctional (meth) acrylates [ e.g., alkanediol di (meth) acrylates such as ethylene glycol di (meth) acrylate and alkanepolyol poly (meth) acrylates such as neopentyltetraol tetra (meth) acrylate ], aromatic maleimides such as aromatic bismaleimides such as aromatic maleimide (N, N' -m-phenylenedimaleimide), and inorganic auxiliary agents [ e.g., zinc oxide and magnesium oxide ].

These vulcanization aids may be used singly or in combination of 2 or more. Among them, sulfenamide accelerators such as CBS, thiuram accelerators such as TMTD, and inorganic auxiliaries such as zinc oxide are generally used.

The proportion of the vulcanization aid (H) may be, for example, 4 to 30 parts by mass, preferably 5 to 25 parts by mass, and more preferably about 10 to 20 parts by mass, based on 100 parts by mass of the rubber. The proportion of the organic vulcanization accelerator may be, for example, 1 to 10 parts by mass, preferably 3 to 8 parts by mass, and more preferably about 5 to 7 parts by mass, based on 100 parts by mass of the rubber. The proportion of the inorganic auxiliary (particularly zinc oxide) may be, for example, 3 to 20 parts by mass, preferably 5 to 15 parts by mass, and more preferably about 7 to 10 parts by mass, based on 100 parts by mass of the rubber.

[ other additives (I) ]

The rubber-like composition of the present invention may further contain conventional additives depending on the kind of the rubber component (A). Examples of conventional additives include: a resin component (thermoplastic resin, thermosetting resin, etc.), a solvent, a vulcanization retarder, a dispersant, an anti-aging or antioxidant (aromatic amine-based, benzimidazole-based, etc.), a colorant (e.g., dye, pigment, etc.), a thickener, a coupling agent (e.g., silane coupling agent), a stabilizer (e.g., ultraviolet absorber, light stabilizer, heat stabilizer, etc.), a mold release agent, a lubricant, a flame retardant (e.g., phosphorus-based flame retardant, halogen-based flame retardant, inorganic flame retardant, etc.), a vibration damper, a flame retardant aid, an antistatic agent, a conductive agent, a flow regulator, a leveling agent, a defoaming agent, a surface modifier, a stress reducer, a nucleating agent, a crystallization accelerator, an antibacterial agent, a preservative, etc.

These other additives may be used alone or in combination of 2 or more. The proportion of the other additives is, for example, about 0.1 to 50 parts by mass, preferably about 0.5 to 30 parts by mass, and more preferably about 1 to 10 parts by mass, based on 100 parts by mass of the rubber component (A).

[ Process for producing rubber-like composition ]

The rubber-like composition of the present invention can be obtained by a mixing step of mixing the rubber component (a), the cellulose (B), and the fluorene compound (C) having an aryl group at the 9, 9-positions.

In the mixing step, the rubber component (a), the cellulose (B), and the fluorene compound (C) may be added together and mixed, but in the composition, it is preferable to prepare a premix by premixing the cellulose (B) and the fluorene compound (C) before mixing with the rubber component (a) from the viewpoint of promoting the formation of a composite in which the surface of the cellulose (B) is covered with the fluorene compound (C) and improving the dispersibility of the cellulose (B) (particularly, nanofibers) in the composition. By premixing, it is possible to efficiently form a composite in which at least a part of the surface of the cellulose (B) is covered with the fluorene compound (C) before mixing with the rubber component (a), and thus the ratio of the composite can be increased in a composition mixed with the rubber component.

The premix may be a composite in which at least a part of the surface of the cellulose (B) is covered with the fluorene compound (C), or may be a mixture of the composite with the cellulose (B) and/or the fluorene compound (C). The proportion of the composite in the premix is, for example, 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more.

In the case where the cellulose (B) is a nanofiber in the preliminary mixing, the cellulose nanofiber (particularly, a microfibrillated fiber, a nanofiber having an average fiber diameter of a nanometer size) may be dried, and the fiber may be entangled and not redispersed. Therefore, in general, the cellulose (B) (particularly cellulose nanofibers) is preferably premixed with the fluorene compound (C) in the form of a mixture with water, for example, an impregnated body with water (a wet body with water) or an aqueous dispersion. The mixture of cellulose nanofibers and water may be commercially available.

The cellulose concentration (particularly, the solid content concentration of the cellulose nanofibers) in the mixture of the cellulose (B) and water is, for example, about 1 to 80 mass%, preferably about 3 to 50 mass%, and more preferably about 5 to 30 mass% (particularly about 10 to 25 mass%). When the solid content concentration is too low, the efficiency of the composite formation may be lowered, and on the contrary, when the solid content concentration is too high, the handleability may be lowered.

The premixing of the mixture of the cellulose (B) and water with the fluorene compound (C) may be performed in the absence of a solvent, but is preferably performed in the presence of a solvent from the viewpoint of enabling the cellulose (B) and the fluorene compound (C) to be effectively combined.

As the solvent, an amphiphilic solvent having affinity for both water and the fluorene compound is preferable. Examples of the amphiphilic solvent include: alcohols (butanol, cyclohexanol, 1-methoxy-2-propanol, etc.), cellosolves or 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 (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.), and the likeAlkanes, tetrahydrofuran, etc.), lactones (butyrolactone, caprolactone, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), lactams (butyrolactam, caprolactam, etc.), amides (dimethylformamide, dimethylacetamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), and the like. These solvents may be used alone or in combination of 2 or more. Among them, from the viewpoint of easy removal by distillation, cellosolves etherified at both ends with an alkyl group, carbitols, ketones, lactones, lactams, amides, sulfoxides and the like are generally used, and alicyclic ketones such as cyclohexanone, cellosolves such as diethylene glycol dimethyl ether and the like are preferably used. When these amphiphilic solvents are used, the solvents are not likely to remain in the composition even when the composite and the rubber component (a) are mixed in a state containing the solvents, in addition to being easily distilled off.

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, and more preferably 500 to 3000 parts by mass (particularly 1000 to 2000 parts by mass) per 100 parts by mass of the total of the mixture of the cellulose (B), the water, and the fluorene compound (C).

The premixing method may be a melt kneading method, or may be a method using a magnetic stirrer or stirring paddle widely used in chemical reactions. In the stirring, the rotation speed of the stirring is preferably high, and the stirring can be performed at the following rotation speeds: for example, 10rpm or more (for example, 10 to 10000rpm), preferably 50rpm or more (for example, 50 to 7000rpm), more preferably 100rpm or more (for example, 100 to 5000rpm), and particularly about 200rpm or more (for example, 200 to 3000 rpm).

When nanofibers are used as the cellulose (B), the cellulose (B) may be commercially available nanofibers or nanofibers obtained by defibrating cellulose. In the cellulose defibration, the fluorene compound (C) and the solvent may be mixed in the cellulose before the defibration to perform the defibration.

In order to mix with the rubber component (a), it is preferable to prepare a water-solvent impregnated body by drying a dispersion liquid containing the cellulose (B) and the fluorene compound (C) to remove most of the water and the solvent by distillation. As the distillation removal method of water and solvent, conventional methods such as a method of heating and/or reducing pressure can be used, and the method of heating and reducing pressure is preferred from the viewpoint of productivity.

As a method of heating, a conventional method, for example, a method using a stationary hot air dryer, a vacuum dryer, a rotary evaporator, a hybrid dryer (a cone dryer, a Nauta (Nauta) dryer, or the like) or the like can be used. The heating temperature is, for example, 40 to 200 ℃, preferably 60 to 150 ℃, and more preferably about 70 to 100 ℃.

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

The composite of the cellulose (B) and the fluorene compound (C) obtained by the drying treatment may contain a predetermined amount of water and a solvent from the viewpoint of uniformly dispersing the cellulose (B) in the rubber component (a). The total ratio of water and solvent is 10 to 2000 parts by mass, preferably 50 to 1000 parts by mass, and more preferably about 100 to 500 parts by mass (particularly 150 to 400 parts by mass) per 100 parts by mass of the total of the cellulose (B) and the fluorene compound (C) after the drying treatment. The composite may contain only a solvent in a proportion of 10 to 1000 parts by mass, preferably 20 to 700 parts by mass, and more preferably about 30 to 500 parts by mass, based on 100 parts by mass of the total of the cellulose (B) and the fluorene compound (C) after the drying treatment, from the viewpoint of improving the kneading property.

In the mixing step, the method of mixing the rubber component (a) with the composite of the cellulose (B) and the fluorene compound (C) obtained in the premixing step may be appropriately selected depending on the kind of the rubber component (a).

When the rubber component (a) is a rubber, it is preferable to prepare a composition for mixing with the above-mentioned composite by kneading the rubber and an additive such as a vulcanizing agent in advance by a conventional method, for example, a method using a mixing roll, a kneader, a banbury mixer, an extruder (a single-screw or twin-screw extruder or the like) or the like, before mixing the rubber with the above-mentioned composite. Among them, kneaders such as a pressure kneader are preferable. The above-mentioned composite may be added to the composition kneaded by these methods using a roll to be kneaded. The kneading may be carried out without heating or under heating. The kneading temperature is, for example, 30 to 250 ℃, preferably 40 to 200 ℃, and more preferably 50 to 180 ℃ (particularly 80 to 160 ℃) when heating.

When the rubber component (a) is rubber, the unvulcanized rubber composition obtained in the mixing step is subjected to a vulcanization step of vulcanizing in a state of being molded into a predetermined shape to obtain a vulcanized rubber composition. In the vulcanization step, the vulcanization temperature may be selected according to the type of rubber, and is, for example, 100 to 250 ℃, preferably 150 to 200 ℃, and more preferably about 160 to 190 ℃.

When the rubber component (a) is a thermoplastic elastomer, the thermoplastic elastomer and the composite can be melt-kneaded by a conventional method, for example, a method using a mixing roll, a kneader, a banbury mixer, an extruder (a single-screw or twin-screw extruder, etc.), etc. to prepare a rubber-like composition, or can be molded by a conventional molding method such as injection molding. Among them, extruders such as twin-screw extruders are preferable. The kneading temperature is, for example, 60 to 270 ℃, preferably 80 to 250 ℃, and more preferably about 100 to 230 ℃.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The raw materials and evaluation methods used below are as follows.

(use of raw materials)

And BPEF: 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, manufactured by Osaka gas Chemicals, Inc

BCF: 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene, manufactured by Osaka gas Chemicals, Inc

BPFG: 9, 9-bis (4-glycidoxyphenyl) fluorene manufactured by Osaka gas chemistry, Inc

EPDM: "JSR EP 21" manufactured by JSR strain "

SBR: "JSR 1502" manufactured by JSR Strain "

SBS: "タフプレン A" manufactured by Asahi Kasei (Asahi Kasei) (Co., Ltd.) "

Bisphenol a type epoxy resin: "JeR 828" manufactured by Mitsubishi chemical corporation "

CB HAF: シースト 3 manufactured by east China sea carbon corporation "

CB N234: シースト 7HM manufactured by Tohai carbon corporation "

Naphthenic oil: ダイアナプロセス NS-100 manufactured by shinning-chang Gai (strain) "

Processing oil: "Vivatec 500 (TDAE)" manufactured by H & R "

Zinc oxide: zinc oxide No. 1 manufactured by Mitsui metal mining "

Stearic acid: "ビーズステアリン acid つばき" manufactured by Nichisu oil Co., Ltd "

Sulfur: powdered sulfur made by Hejia chemical "

Accelerator TT: ノクセラー TT-P manufactured by Dai Xinjiang chemical industry "

Accelerator M: ノクセラー M-P manufactured by Dai-Nei-Xin chemical industry "

Accelerator CBS: the model "ノクセラー CZ-G" manufactured by Dainio institute of chemical industry (Ltd.) is emerging.

(tensile test)

The tensile stress, tensile strength and elongation at 25 to 300% were measured according to JIS K6251.

(hardness tester)

The durometer hardness was measured according to JIS K6253 type A.

(Density)

The density was measured according to JIS K6268.

Reference example 1 (EPDM/control)

The respective components in the proportions shown in Table 1 were kneaded at a temperature of 150 ℃ by using a pressure kneader (manufactured by モリヤマ, Ltd., capacity 10L) to prepare an unvulcanized rubber composition. The resulting composition was press-vulcanized at a vulcanization temperature of 170 ℃ to obtain a vulcanized rubber composition.

[ Table 1]

Composition (I)	Proportion (parts by mass)
		EPDM	100
CB HAF	80
		Naphthenic oil	50
Zinc oxide	5
		Stearic acid	1
Sulfur	1.5
		Accelerator TT	1
Accelerator M	0.5
		Total up to	239

Reference example 2(EPDM/B-CNF)

[ Synthesis of modified cellulose nanofibers ]

After 100g of an aqueous dispersion of cellulose nanofibers (solid content concentration: 15 mass%) was dispersed in 500g of N, N-dimethylacetamide (DMAc) and centrifuged, the precipitated solid content was further dispersed in 500g of DMAc and centrifuged again, whereby the solvent was replaced, and a mixture of cellulose nanofibers and DMAc (cellulose content: about 10 mass%) was obtained. The mixture was transferred to a 1000mL three-necked flask, and DMAc350g, 15g of 9, 9-bis (4-glycidoxyphenyl) fluorene (BPFG) and 10g of Diazabicycloundecene (DBU) were added thereto, followed by stirring at 120 ℃ for 3 hours. The resulting mixture was collected by centrifugation, and the procedure of washing with 1200mL of DMAc was repeated 3 times to obtain a modified cellulose nanofiber (B-CNF). The modification ratio of the fluorene compound was measured by the following method, and the result was 12% by mass. An SEM photograph of the cellulose nanofibers as the raw material used was observed by SEM ("JSM-6510" manufactured by japan electronics corporation), and is shown in fig. 1.

[ modification ratio of fluorene Compound bonded to modified (modified) cellulose nanofiber ]

The modification ratio of the fluorene compound (hereinafter also referred to as the modification ratio of fluorene) was analyzed by Raman analysis using a Raman microscope (XploRA, manufactured by HORIBA JOBIN YVON Co., Ltd.) through an aromatic ring (1604 cm)^-1) Intra-ring CH with cellulose (1375 cm)^-1) Intensity ratio of absorption bands (I)₁₆₀₄/I₁₃₇₅) To calculate. In the calculation, a predetermined amount of a fluorene compound was added to diacetylcellulose (manufactured by Daicel corporation) contained therein, a film was formed by a solution casting method, and the strength ratio (I) was used according to the amount of the fluorene compound₁₆₀₄/I₁₃₇₅) And (5) preparing a calibration curve. All samples were measured 3 times, and the average value of the values calculated from the results was defined as the fluorene modification ratio (modification ratio).

[ preparation of vulcanized rubber composition ]

To the unvulcanized rubber composition obtained in reference example 1,3 parts by mass of the modified cellulose nanofibers (B-CNF) in terms of solid content based on 100 parts by mass of the composition of reference example 1 was added using a 6-inch roll to prepare an unvulcanized rubber composition containing the modified cellulose nanofibers, and a vulcanized rubber composition was obtained in the same manner as in reference example 1.

Reference example 3 (EPDM/epoxy resin-CNF composite)

[ preparation of composite of bisphenol A epoxy resin and cellulose nanofiber ]

To 150g (20 mass% in solid content, containing 30g of cellulose nanofibers) of a water-wet body containing plant-derived cellulose nanofibers having a diameter of 100nm or less, which had been defibrated by a buffing method at 50 mass% or more, 1800g of cyclohexanone and 15g of bisphenol a-type epoxy resin (50 parts by mass of epoxy resin per 100 parts by mass of cellulose nanofibers) were added, and the mixture was stirred at 600rpm for 10 minutes using a stirrer ("スリーワンモータ" manufactured by shin-chan science corporation), and then reduced in pressure at 80 ℃ using a rotary evaporator to obtain 150g of a wet epoxy resin-CNF composite. Fig. 2 shows an SEM photograph of cellulose nanofibers as a raw material used. The cellulose nanofibers are continuous fibers (long fibers) having an average fiber diameter of 114 nm.

(preparation of vulcanized rubber composition)

An epoxy resin-CNF composite was added to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 1 using a 6-inch roll in an amount of 3 parts by mass in terms of solid content to prepare an unvulcanized rubber composition containing the epoxy resin-CNF composite, and a vulcanized rubber composition was obtained in the same manner as in reference example 1.

Example 1(EPDM/BPFG-CNF Complex)

[ preparation of composite of BPFG and cellulose nanofiber ]

BPFG-CNF composite (50 parts by mass of BPFG to 100 parts by mass of cellulose nanofibers) was obtained in the same manner as in reference example 3, except that BPFG was used instead of the bisphenol a epoxy resin.

(preparation of vulcanized rubber composition)

An unvulcanized rubber composition containing a BPFG-CNF composite was prepared by adding 3 parts by mass of the BPFG-CNF composite in terms of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 1 using a 6-inch roll, and a vulcanized rubber composition was obtained in the same manner as in reference example 1.

Example 2(EPDM/BPEF-CNF Complex)

[ preparation of composite of BPEF and cellulose nanofiber ]

A BPEF-CNF composite (50 parts by mass of BPEF with respect to 100 parts by mass of cellulose nanofibers) was obtained in the same manner as in reference example 3, except that BPEF was used instead of the bisphenol a epoxy resin. As a result of observing the composite by SEM, as shown in fig. 3, particulate BPEF was attached to the surface of the cellulose nanofibers at the position where the defibration proceeded, and as shown in fig. 4, the surface of the cellulose nanofibers was covered with BPEF at the position where the defibration did not proceed sufficiently.

[ preparation of vulcanized rubber composition ]

An unvulcanized rubber composition containing a BPEF-CNF composite was prepared by adding a BPEF-CNF composite in an amount of 3 parts by mass in terms of the amount of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 1 using a 6-inch roll, and a vulcanized rubber composition was obtained in the same manner as in reference example 1.

Example 3(EPDM/BCF-CNF Complex)

[ preparation of composite of BCF and cellulose nanofiber ]

A BCF-CNF composite (50 parts by mass of BCF to 100 parts by mass of cellulose nanofibers) was obtained in the same manner as in reference example 3, except that BCF was used instead of the bisphenol a type epoxy resin.

[ preparation of vulcanized rubber composition ]

An unvulcanized rubber composition containing a BCF-CNF composite was prepared by adding 3 parts by mass of a BCF-CNF composite in terms of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 1 using a 6-inch roll, and a vulcanized rubber composition was obtained in the same manner as in reference example 1.

The evaluation results of the vulcanized rubber compositions obtained in reference examples 1 to 3 and examples 1 to 3 are shown in Table 2.

[ Table 2]

From the results in table 2, it is understood that the vulcanized rubber compositions obtained in the examples are superior in the balance between the tensile properties and the rigidity as compared with the vulcanized rubber compositions obtained in the reference examples. Examples 1 to 3 (particularly examples 2 and 3) are similar to reference example 2 containing a cellulose nanofiber modified with a fluorene compound in that the modulus (tensile stress) in the longitudinal direction is improved, although the same is true for the case of containing a fluorene compound. It can be concluded that the result is because: in examples 1 to 3, the fluorene compound and the cellulose nanofibers were non-covalently bonded and had a higher degree of freedom than in reference example 2.

Reference example 4 (SBR/control)

The respective components in the proportions shown in Table 3 were kneaded at a temperature of 150 ℃ by using a pressure kneader (manufactured by モリヤマ, Ltd., capacity 10L) to prepare an unvulcanized rubber composition. The resulting composition was press-vulcanized at a vulcanization temperature of 180 ℃ to obtain a vulcanized rubber composition.

[ Table 3]

Composition (I)	Proportion (parts by mass)
		SBR	100
CB N234	60
		Processing oil	5
Zinc oxide	4
		Stearic acid	1
Sulfur	1.8
		Accelerator CBS	1.5
Total up to	173.3

Reference example 5 (SBR/epoxy resin-CNF composite)

An epoxy resin-CNF composite-containing unvulcanized rubber composition was prepared by adding the epoxy resin-CNF composite obtained in reference example 3 in terms of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 4 using a 6-inch roll, and a vulcanized rubber composition was obtained in the same manner as in reference example 4.

Example 4(SBR/BPFG-CNF Complex)

An unvulcanized rubber composition containing the BPFG-CNF composite was prepared by adding 3 parts by mass of the BPFG-CNF composite obtained in example 1 in terms of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 4 using a 6-inch roll, and a vulcanized rubber composition was obtained in the same manner as in reference example 4.

Example 5(SBR/BPEF-CNF Complex)

An unvulcanized rubber composition containing the BPEF-CNF composite was prepared by adding 3 parts by mass of the BPEF-CNF composite obtained in example 2 in terms of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 4 using a 6-inch roll, and a vulcanized rubber composition was obtained in the same manner as in reference example 4.

Example 6(SBR/BCF-CNF Complex)

An unvulcanized rubber composition containing a BCF-CNF composite was prepared by adding the BCF-CNF composite obtained in example 3 in terms of solid content to 100 parts by mass of the unvulcanized rubber composition obtained in reference example 4 using a 6-inch roll and obtaining a vulcanized rubber composition in the same manner as in reference example 4.

The evaluation results of the vulcanized rubber compositions obtained in reference examples 4 to 5 and examples 4 to 6 are shown in Table 4.

[ Table 4]

From the results in table 4, it is understood that the vulcanized rubber compositions obtained in the examples are superior in balance between tensile properties and rigidity as compared with the vulcanized rubber compositions obtained in the reference examples.

Reference example 6 (SBS/control)

A dumbbell test piece having a length of 75mm, a width of the parallel portion of 5mm, a length of the parallel portion of 35mm and a thickness of 2mm was prepared from SBS by using an injection molding machine ("C, MOBILE-0813") manufactured by Sellbic.

Reference example 7(SBS/B-CNF)

To 100 parts by mass of SBS, 3 parts by mass of the modified cellulose nanofiber (B-CNF) obtained in reference example 2 was added in terms of solid content, and melt-kneaded at 200 ℃ using a twin-screw extruder (manufactured by Technovel Co., Ltd., 15 mm. phi., L/D. 30) to obtain a composite (compound). The resulting composite was dried at 80 ℃ for 24 hours, and then a test piece was prepared using an injection molding machine ("C, MOBILE-0813" manufactured by Sellbic, Inc.).

Example 7(SBS/BPEF-CNF Complex)

The BPEF-CNF composite obtained in example 2 was added in an amount of 4.5 parts by mass in terms of solid content to 100 parts by mass of SBS, and melt-kneaded at 200 ℃ using a twin-screw extruder (manufactured by Technovel Co., Ltd., 15 mm. phi., L/D. 30) to obtain a composite. The resulting composite was dried at 80 ℃ for 24 hours, and then a test piece was prepared using an injection molding machine ("C, MOBILE-0813" manufactured by Sellbic, Inc.).

Example 8(SBS/BCF-CNF Complex)

To 100 parts by mass of SBS, 4.5 parts by mass of the BCF-CNF composite obtained in example 3 was added in terms of the amount of solid content, and melt-kneaded at 220 ℃ using a twin-screw extruder (manufactured by Technovel Co., Ltd., 15 mm. phi., L/D. 30) to obtain a composite. The resulting composite was dried at 80 ℃ for 24 hours, and then a test piece was prepared using an injection molding machine ("C, MOBILE-0813" manufactured by Sellbic, Inc.).

The evaluation results of the thermoplastic elastomer compositions obtained in reference examples 6 to 7 and examples 7 to 8 are shown in Table 5.

[ Table 5]

From the results in Table 5, it is understood that the thermoplastic elastomer compositions obtained in the examples have higher strength and higher elongation than those of the thermoplastic elastomer compositions obtained in the reference examples.

Industrial applicability

The rubber-like composition of the present invention can be used for various industrial parts (belts such as conveyor belts, rubber covered rollers, gaskets, printing rollers, and conveyor belts, sealing parts such as oil seals, fillers, rubber tube parts such as oil-resistant rubber tubes, and the like), building parts (vibration damping materials such as window frame rubbers and vibration damping rubbers, carpet packaging materials, and the like), transportation equipment parts (belts such as automobile parts, tires, and conveyor belts, and the like), electric and electronic equipment parts (electric wire covering, and the like), and is suitable for sealing parts, rubber tube parts, belts such as tires, conveyor belts, and drive belts, vibration damping rubbers, and the like.