WO2016136902A1 - Additive for rubber composition, and rubber composition - Google Patents

Abstract

Provided are: an additive for rubber compositions which is used for obtaining rubber compositions excellent in terms of moldability, mechanical property, etc.; and a rubber composition excellent in terms of moldability, mechanical property, etc. The additive for rubber compositions comprises powdery cellulose having an average particle diameter of 15-70 µm. Preferably, the powdery cellulose has a degree of polymerization of 150-1,200, a degree of crystallinity of 70-90%, an apparent specific gravity of 0.15-0.6 g/mL, an angle of repose of 45-60º, and a water content of 5% or less. The rubber composition comprises a rubber component, a filler, and powdery cellulose having an average particle diameter of 15-70 µm.

Description

Additive for rubber composition and rubber composition

The present invention relates to an additive for a rubber composition and a rubber composition.

In general, a rubber composition produced by adding carbon black to a rubber component is known.
In Cited Document 1, a rubber composition containing nitrile rubber and carbon black in a predetermined compounding ratio satisfies the muddy water resistance and sealing properties, and can be used as a sealing member for various machines and devices including rolling bearings for automobiles. It is described.
Cited Document 2 describes a rubber composition containing hydrogenated nitrile rubber, carbon black, and / or carbon fiber, and particularly for oil sealing with sliding having a high required level of wear resistance and oil resistance. It is described that it can be used as a member.
On the other hand, in Patent Document 3, a rubber composition containing hydrogenated acrylonitrile-butadiene rubber (hydrogenated NBR), carbon black, and cellulose powder in a predetermined compounding ratio can be used as an oil seal for power steering. Are listed.

JP 2012-97213 A Japanese Patent No. 5158717 JP 2003-336745 A

However, when a filler (eg, carbon black, silica) is added to the rubber component, mechanical strength such as tensile strength and impact resilience are improved, but mechanical property problems (particularly, reduction in elongation) occur. . Further, due to the increase in Mooney viscosity, which is an index of rubber moldability, the fluidity is lowered and the moldability of the rubber molded product is lowered.
In addition, when the rubber composition is used as a member for oil sealing with sliding, which requires a high level of wear resistance and oil resistance, the oil seal (rubber coating layer) of the sliding portion is used in high temperature oil. Wear and may cause oil leakage.
Furthermore, the addition of the filler may increase the specific gravity of the rubber composition, which may reduce the energy efficiency of a machine or the like using the rubber composition.
Therefore, the present invention provides an excellent rubber composition that is superior to one or more selected from 1) moldability, 2) mechanical properties, 3) reduction of rubber wear depth in high-temperature oil (oil leakage suppression), and 4) reduction of specific gravity. It is an object to provide an additive for a rubber composition for obtaining a rubber composition or the rubber composition. Alternatively, an object of the present invention is to provide a rubber composition additive or an oil sealing rubber composition for obtaining a rubber composition for oil sealing.

In order to solve the above-described problems and achieve the object, the present invention provides the following [1] to [15].
[1] An additive for a rubber composition comprising powdery cellulose having an average particle size of 15 to 70 μm.
[2] The additive for rubber composition according to [1], wherein the average particle size of the powdery cellulose is 25 to 70 μm.
[3] Powdery cellulose has a degree of polymerization of 150 to 1200, a crystallinity of 70 to 90%, an apparent specific gravity of 0.15 to 0.6 g / mL, an angle of repose of 45 to 60 °, and a moisture content of 5% or less. The additive for rubber composition according to [1] or [2].
[4] The rubber composition additive according to any one of [1] to [3], wherein the powdery cellulose is a pulverized product of a cellulose raw material treated with an inorganic acid.
[5] The additive for a rubber composition according to any one of [1] to [4], wherein the rubber composition contains 100 parts by mass of a rubber component and 20 to 120 parts by mass of carbon black.
[6] The additive for a rubber composition according to any one of [1] to [5], wherein the rubber composition contains 100 parts by mass of a rubber component and 20 to 60 parts by mass of silica.
[7] The additive for a rubber composition according to any one of [1] to [6], wherein the rubber composition is for oil sealing.
[8] A rubber composition comprising a rubber component, a filler, and powdered cellulose having an average particle size of 15 to 70 μm.
[9] The degree of polymerization of the powdered cellulose is 150 to 1200, the crystallinity is 70 to 90%, the apparent specific gravity is 0.15 to 0.6 g / mL, the angle of repose is 45 to 60 °, and the moisture is 5% or less. The rubber composition according to [8], wherein
[10] The rubber composition according to [8] or [9], comprising 100 parts by mass of a rubber component, 20 to 120 parts by mass of a filler, and 5 to 50 parts by mass of powdered cellulose.
[11] The rubber composition according to any one of [8] to [10], wherein the filler is carbon black or silica.
[12] The rubber composition according to any one of [8] to [11], comprising 20 to 60 parts by mass of a filler.
[13] The rubber composition according to any one of [8] to [12], comprising 10 to 40 parts by mass of powdered cellulose.
[14] The rubber composition according to any one of [8] to [13], which is used for oil sealing.
[15] An oil seal containing the rubber composition according to any one of [8] to [13].

The present invention also provides the following [2-1] to [2-3].
[2-1] A rubber composition containing a rubber component, carbon black, and powdered cellulose, wherein the compounding ratio of the rubber component, carbon black, and powdered cellulose is rubber component: carbon black: powdered cellulose = 100: (50 to 120): (5 to 50) (parts by weight) A rubber composition.
[2-2] The rubber composition according to [2-1], wherein the rubber component is nitrile rubber.
[2-3] The powdery cellulose has an average particle size of 15 to 50 μm, a polymerization degree of 150 to 1200, a crystallinity of 70 to 90, an apparent specific gravity of 0.2 to 0.6 g / ml, and an angle of repose. The rubber composition according to [2-1] or [2-2], which is 45 to 60 ° and has a water content of 5% or less.

The present invention also provides the following [3-1] to [3-2].
[3-1] A rubber composition for oil sealing containing a rubber component, carbon black, and powdered cellulose, wherein the compounding ratio of the rubber component, carbon black, and powdered cellulose is rubber component: carbon black: powder. A rubber composition for oil sealing, in the form of cellulose: 100: (20-60): (5-30) (parts by weight).
[3-2] The rubber composition for oil sealing according to [3-1], wherein the rubber component is nitrile rubber.

The present invention also provides the following [4-1] to [4-3].
[4-1] A rubber composition containing a rubber component, silica, and powdered cellulose, wherein the compounding ratio of the rubber component, silica, and powdered cellulose is rubber component: silica: powdered cellulose = 100 :( 20 to 60): (10 to 40) (parts by mass) A rubber composition for oil sealing.
[4-2] The rubber composition for oil sealing according to [4-1], wherein the rubber component is ethylene propylene diene rubber.
[4-3] The rubber composition for oil sealing according to [4-1] or [4-2], wherein the silica is silica treated with a silane coupling agent.

The present invention also provides the following.
Use of powdered cellulose having an average particle size of 15 to 70 μm as an additive of a rubber composition.
The powdery cellulose has a polymerization degree of 150 to 1200, a crystallinity of 70 to 90%, an apparent specific gravity of 0.15 to 0.6 g / mL, an angle of repose of 45 to 60 °, and a water content of 5% or less. Use above.
The use as described above, wherein the powdery cellulose is a pulverized product of a cellulose raw material treated with an inorganic acid.
The use as described above, wherein the rubber composition comprises 100 parts by mass of a rubber component and 20 to 120 parts by mass of carbon black.
The use as described above, wherein the rubber composition comprises 100 parts by mass of a rubber component and 20 to 60 parts by mass of silica.

According to the present invention, excellent moldability and mechanical properties can be imparted to a rubber composition containing a filler (eg, carbon black, silica). In addition, according to the present invention, it is possible to provide a rubber composition that can be used as an oil seal that has a reduced rubber wear depth (oil leakage suppression property) and / or an excellent rubber specific gravity in high-temperature oil.

1. Additive for rubber composition The additive for rubber composition of the present invention comprises powdery cellulose having an average particle size of 15 to 70 μm. The additive of the present invention may be a composition.

(Powdered cellulose)
The powdery cellulose used in the present invention is not particularly limited as long as the average particle size is 15 to 70 μm. Powdered cellulose is produced by pulverizing cellulose raw materials such as pulp hydrolyzed with mineral acids (ie, inorganic acids) such as hydrochloric acid, sulfuric acid, and nitric acid, or cellulose raw materials such as pulp not subjected to acid hydrolyzing treatment. It can be obtained by grinding. In addition, it is preferable to use the powdery cellulose with few impurities which grind | pulverized the cellulose raw materials, such as pulp which carried out the acid hydrolysis process, as a powdery cellulose used for the additive for rubber compositions of this invention.

The powdery cellulose used in the present invention has an average particle size of 15 μm or more, preferably 22 μm or more, more preferably 25 μm or more, and further preferably 35 μm or more. An average particle diameter is 70 micrometers or less, Preferably it is 55 micrometers or less, More preferably, it is 50 micrometers or less, More preferably, it is 36 micrometers or less. Therefore, the powdery cellulose used in the present invention has an average particle size of 15 to 70 μm, preferably 15 to 50 μm, more preferably 22 to 36 μm, or preferably 25 to 70 μm. More preferably, it is 35 to 55 μm.
When the average particle size is increased, the Mooney viscosity reducing effect is small, the rubber hardness is increased, and the mechanical properties tend to be inferior. On the other hand, when the average particle size is decreased, the Mooney viscosity reducing effect is improved, but the rubber reinforcing effect tends to be decreased.

In the case where the rubber composition additive of the present invention is blended with a rubber composition containing carbon black, the average particle size of the powdery cellulose is preferably 15 to 50 μm, more preferably 22 to 36 μm. When the additive for a rubber composition of the present invention is blended with a rubber composition containing silica, the average particle size of the powdered cellulose is preferably 25 to 70 μm, more preferably 35 to 55 μm.

In addition, in this specification, an average particle diameter means the value when accumulation distribution will be 50%, when it measures using a laser scattering method and represents a particle size distribution as accumulation distribution.

The degree of polymerization of the powdery cellulose used in the present invention is preferably 150 or more, more preferably 250 or more, still more preferably 400 or more, and particularly preferably 600 or more. The degree of polymerization of the powdery cellulose is preferably 1400 or less, more preferably 1200 or less, and still more preferably 800 or less. Accordingly, the degree of polymerization of the powdery cellulose is preferably 150 to 1200, more preferably 400 to 800, or preferably 250 to 1400, more preferably 600 to 1200. When the degree of polymerization is high, the rubber hardness tends to increase. On the other hand, when the degree of polymerization is low, the rubber reinforcing effect tends to be small.

When the rubber composition additive of the present invention is blended with a rubber composition containing carbon black, the degree of polymerization of the powdery cellulose is preferably 150 to 1200, more preferably 400 to 800.

In addition, when the additive for a rubber composition of the present invention is blended with a rubber composition containing silica as a filler, the degree of polymerization of the powdery cellulose is preferably 250 to 1400, more preferably 600 to 1200. is there.

In the present specification, the degree of polymerization of powdery cellulose means a value obtained by a viscosity measurement method using copper ethylenediamine described in the 16th revised Japanese Pharmacopoeia Description, Crystalline Cellulose Confirmation Test (2).

The crystallinity of the powdery cellulose used in the present invention is preferably from 70 to 90, and more preferably from 80 to 90. When the degree of crystallinity is low, the time required for heat vulcanization is long and workability tends to deteriorate. If the crystallinity is 80 or more, the influence on the vulcanization rate is hardly confirmed. In addition, the crystallinity of the powdery cellulose changes due to the production method in addition to the type of pulp used as a raw material, and the powdered cellulose has a high crystallinity by using an acid hydrolyzed cellulose raw material. Can be obtained. In addition, the powdery cellulose manufactured only by the mechanical process, without performing an acid hydrolysis process tends to have a low crystallinity.
In addition, in this specification, the crystallinity degree of powdery cellulose is the value calculated | required by measuring the X-ray diffraction of a sample. The crystallinity is calculated by the method of Segal et al. (L. Segal, JJ Greery, et al, Text. Res. J., 29, 786, 1959) and the method of Kamide et al. (K. Kamide et al. , Polymer J., 17, 909, 1985), and using the diffraction intensity of 2θ = 4 ° to 32 ° of the diffraction diagram obtained from the X-ray diffraction measurement as a baseline, the diffraction intensity of the 002 plane and 2θ = 1 From the diffraction intensity of the amorphous portion at 18.5 °, the following formula is used.
Xc = (I _002C -Ia) / I _002C × 100
Xc: degree of crystallinity of cellulose (%)
I _002C : 2θ = 22.6 °, 002 plane diffraction intensity Ia: 2θ = 18.5 °, diffraction intensity of amorphous part

The apparent specific gravity of the powdery cellulose used in the present invention is preferably 0.15 or more, more preferably 0.18 or more, still more preferably 0.2 or more, and even more preferably 0.3 or more. It is. The apparent specific gravity of the powdery cellulose is preferably 0.6 or less, more preferably 0.5 or less, still more preferably 0.45 or less, and even more preferably 0.35 or less. Therefore, the apparent specific gravity of the powdery cellulose is preferably 0.2 to 0.6, more preferably 0.3 to 0.45, or preferably 0.15 to 0.5, and more preferably Is 0.18 to 0.35. If the apparent specific gravity is small, the powder is bulky, and the dispersibility of the rubber composition in components (eg, rubber, carbon black, silica, etc.) tends to decrease. On the other hand, when the apparent specific gravity is large, since the powder is low in volume and compact, the dispersibility in the components of the rubber composition (eg, rubber, carbon black, silica, etc.) is good. Since the particle diameter is small, the reinforcing effect of rubber tends to be small.

When the rubber composition additive of the present invention is added to a rubber composition containing carbon black, the apparent specific gravity of the powdery cellulose is preferably 0.2 to 0.6, more preferably 0.3 to 0.45.

In addition, when the additive for rubber composition of the present invention is added to a rubber composition containing silica, the apparent specific gravity of the powdery cellulose is preferably 0.15 to 0.5, more preferably 0.18. ~ 0.35.

In this specification, the apparent specific gravity was calculated by putting 10 g of a sample into a 100 ml graduated cylinder, continuously striking the bottom of the graduated cylinder until the height of the sample did not decrease, and reading the scale on the flat surface. Value (g / mL).

The angle of repose of the powdered cellulose used in the present invention is preferably 45 ° or more, more preferably 48 ° or more. The angle of repose of the powdery cellulose is preferably 60 ° or less, more preferably 58 ° or less, and further preferably 56 ° or less. Therefore, the angle of repose of powdered cellulose is preferably 45 to 60 °, more preferably 48 to 56 °, or preferably 48 to 58 °. If the angle of repose is large, the powder fluidity tends to be poor, which may be unfavorable for work. On the other hand, if the angle of repose is small, the powder fluidity is good and the workability is improved, but there is a tendency for powder to be produced.

When the rubber composition additive of the present invention is added to a rubber composition containing carbon black, the angle of repose of powdered cellulose is preferably 45 to 60 °, more preferably 48 to 56 °.

When the additive for rubber composition of the present invention is added to a rubber composition containing silica, the repose angle of the powdered cellulose is preferably 45 to 60 °, more preferably 48 to 58 °.

The water content of the powdered cellulose used in the present invention is preferably 5% or less, more preferably 3% or less. If the moisture is high, it may cause a vulcanization delay when the rubber is heated and vulcanized. In addition, the strength (eg, mechanical properties) of the rubber after molding may be adversely affected. Therefore, the lower the moisture content of the powdery cellulose, the better.

(Production of powdered cellulose: acid hydrolysis / grinding)
As a method for producing powdery cellulose of the present invention, a cellulose raw material preparation step, an acid hydrolysis reaction step, a neutralization / washing / liquid removal step, a drying step, a pulverization step, a classification step, a cellulose raw material A method of performing mechanical pulverization without performing acid hydrolysis treatment can be exemplified.

The following method is mentioned as an example of the manufacturing method of a specific powdery cellulose. First, a dispersion having a pulp concentration of 3 to 10% by weight (in terms of solid content) adjusted to an acid concentration of 0.10 to 1.2 N is subjected to an acid hydrolysis treatment under conditions of a temperature of 80 to 100 ° C. and a time of 30 minutes to 3 hours. I do. Next, it solid-liquid-separates into the pulp and waste acid which were acid-hydrolyzed at the spin-drying | dehydration process, the alkali agent is added to the pulp which performed the acid hydrolyzing process, and it neutralizes and wash | cleans. Thereafter, it is dried with a dryer, and mechanically pulverized and classified to a specified size with a pulverizer to be manufactured.
In addition, when using fluidized pulp from the pulp bleaching process as a raw material, a predetermined amount is added to the reaction tank after concentration with a dehydrator (eg, screw press, belt filter) in order to increase the concentration before being introduced into the hydrolysis reaction tank. May be input. Moreover, when using the dry sheet | seat of a pulp as a raw material, you may throw into a reaction tank, after loosening a pulp with a crusher (for example, roll crusher) etc.

Examples of cellulose raw materials for powdered cellulose include hardwood-derived pulp, softwood-derived pulp, or non-wood pulp, and pulping methods include sulfite cooking, kraft cooking, soda A quinone cooking method, an organosolv cooking method, etc. can be illustrated. Further, the form of the cellulose raw material is not particularly limited, and it can be used in a slurry form or a sheet form.

The acid concentration at the time of oxidative hydrolysis treatment of the cellulose raw material is not particularly limited, but is usually about 0.1 to 1.2 N. If the acid concentration in the acid hydrolysis treatment is lower than 0.1 N, the depolymerization of cellulose due to the acid can be suppressed, so the decrease in the degree of polymerization of the powdered cellulose is reduced, but it is refined due to the inherent toughness of cellulose. It can be very difficult. On the other hand, if the acid concentration is higher than 1.2N, depolymerization of cellulose proceeds and the particle size of powdered cellulose becomes easy to control, and the powder fluidity is improved, but the degree of polymerization is reduced, and There is a tendency for physical properties to decrease.

As a pulverizer, a cutting mill: mesh mill (manufactured by Horai Co., Ltd.), Atoms (manufactured by Yamamoto Hyakuma Mfg. Co., Ltd.), knife mill (manufactured by Palman), cutter mill (manufactured by Tokyo Atomizer Manufacturing Co., Ltd.), CS cutter ( Mitsui Mining Co., Ltd.), rotary cutter mill (manufactured by Nara Machinery Co., Ltd.), pulp crusher (manufactured by Suikou Co., Ltd.), shredder (manufactured by Shinko Pantech Co., Ltd.), hammer type mill: jaw crusher (Makino Co., Ltd.) ), Hammer crusher (manufactured by Hadano Sangyo Co., Ltd.), impact mill: Pulverizer (manufactured by Hosokawa Micron Corporation), fine impact mill (manufactured by Hosokawa Micron Corporation), super micron mill (manufactured by Hosokawa Micron Corporation), Inomizer (Hosokawa Micron Corporation) Made), fine mill Nippon Pneumatic Kogyo Co., Ltd.), CUM type centrifugal mill (Mitsui Mining Co., Ltd.), Ixed Mill (Ogino Sangyo Co., Ltd.), Ultraplex (Ogino Sangyo Co., Ltd.), Contraplex (Ogino Sangyo Co., Ltd.) , Coroplex (manufactured by Hadano Sangyo Co., Ltd.), sample mill (manufactured by Seisin Co., Ltd.), bantam mill (manufactured by Seisin Co., Ltd.), atomizer (manufactured by Seisin Co., Ltd.), tornado mill (manufactured by Nikkiso Co., Ltd.), Neamill (Dalton Co., Ltd.) ), HT type pulverizer (manufactured by Horai Co., Ltd.), free crusher (manufactured by Nara Machinery Co., Ltd.), New Cosmizer (manufactured by Nara Machinery Co., Ltd.), gather mill (manufactured by Nishimura Machinery Co., Ltd.), Spar powder mill (manufactured by Nishimura Machinery Co., Ltd.), blade mill (Nisshin Engineering) Super rotor (Nisshin Engineering Co., Ltd.), Npa crusher (Misho Industry Co., Ltd.), Willet crusher (Miki Seisakusho Co., Ltd.), pulp crusher (Zuiko Co., Ltd.), Jacobson Fine Crusher (manufactured by Shinko Pantech Co., Ltd.), universal mill (manufactured by Tokusu Kosakusho Co., Ltd.), airflow mill: CGS type jet mill (manufactured by Mitsui Mining Co., Ltd.), micron jet (manufactured by Hosokawa Micron Co., Ltd.), counter jet mill (Manufactured by Hosokawa Micron Corporation), cross jet mill (manufactured by Kurimoto Steel Corporation), supersonic jet mill (manufactured by Nippon Pneumatic Industry Co., Ltd.), current jet (manufactured by Nissin Engineering Co., Ltd.), jet mill (Misho) Industry Co., Ltd.), Ebarajet Micronizer (stock) Company Ebara Seisakusho), Ebara Triad Jet (Ebara Seisakusho Co., Ltd.), Selenium Mirror (Masuyuki Sangyo Co., Ltd.), New Micro Cyc Mat (Masuno Seisakusho Co., Ltd.), Kryptron (Kawasaki Heavy Industries Co., Ltd.) , Vertical roller mill: vertical roller mill (manufactured by Shinion Co., Ltd.), vertical roller mill (manufactured by Schaeffler Japan Co., Ltd.), roller mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), VX mill (Kurimoto Steel Corporation) KVM type vertical mill (Earth Technica Co., Ltd.), IS mill (IHI Plant Engineering Co., Ltd.), turbo mill (Freund Sangyo Co., Ltd.) and the like are exemplified. Among these, a tornado mill (made by Nikkiso Co., Ltd.), a blade mill (made by Nisshin Engineering Co., Ltd.), a free crusher (made by Nara Machinery Co., Ltd.), a turbo mill (made by Freund Sangyo Co., Ltd.), which has excellent pulverization properties. ) Is preferably used.

For the purpose of imparting functionality or improving functionality to the powdered cellulose in the present invention, the raw material of powdered cellulose and other organic and / or inorganic components may be mixed singly or in an arbitrary ratio of two or more types, and pulverized. Is possible. Moreover, it is possible to perform a chemical process in the range which does not impair the polymerization degree of the natural cellulose used for a raw material significantly.

(Manufacture of powdered cellulose: pulverization only)
In the case where powder is produced only by mechanical pulverization using the pulp that has not been subjected to acid hydrolysis as a raw material, it is preferable to use a vertical roller mill having a high pulverization property as the pulverizer. In the present invention, the vertical roller mill is a centrifugal vertical mill that belongs to the roller mill, and the vertical roller mill is a pulp that is crushed by a disk-shaped turntable and a vertical roller. Crush. The biggest feature of the vertical roller mill is that it is excellent in fine pulverization. The reason is that the raw material is pulverized by the force of compressing the raw material between the roller and the table and the shearing force generated between the roller and the table. To do. Conventional grinding machines include vertical roller mills (manufactured by Shinion Co., Ltd.), vertical roller mills (manufactured by Schaeffler Japan Co., Ltd.), roller mills (manufactured by Kotobuki Giken Kogyo Co., Ltd.), and VX mills (corporation). Kurimoto Works), KVM type vertical mill (Earth Technica Co., Ltd.), IS mill (IHI Plant Engineering Co., Ltd.) and the like.

The additive for rubber composition of the present invention may contain an optional component in addition to the above powdery cellulose.

The additive for rubber composition of the present invention is added to the rubber composition to improve the moldability and mechanical properties of the rubber composition.
(Rubber composition)
The rubber composition includes a rubber component.

(Rubber component)
In the present invention, natural rubber, synthetic rubber: isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), polyisobutylene (butyl rubber) IIR), ethylene propylene rubber (EPM), ethylene propylene diene rubber (eg, ethylene propylene butadiene rubber) (EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM), fluoro rubber (FKM), epichlorohydrin rubber (CO , ECO), urethane rubber (U), silicone rubber (Q), and the like. Although not particularly limited, nitrile rubber or ethylene propylene diene rubber (eg, ethylene propylene butadiene rubber) is used. Preferred That's right. When the rubber composition further contains carbon black, the rubber component is preferably nitrile rubber. When the rubber composition further contains silica, the rubber component is preferably ethylene propylene diene rubber, more preferably ethylene propylene butadiene rubber. The ethylene propylene diene rubber is preferably obtained by copolymerizing a small amount of various diene components with ethylene and propylene.

As the nitrile rubber, any of medium nitrile (CN: 25 to 30%), medium to high nitrile (CN: 31 to 35%) and high nitrile (CN: 36 to 42%) can be used. Preferably has a medium to high nitrile content.

Further, vulcanization of these rubbers is generally performed by a vulcanization system using a combination of sulfur or a sulfur donating compound and a general-purpose vulcanization accelerator such as a sulfenamide-based compound or a thiuram-based compound. Organic peroxide crosslinking is also possible. Examples of the organic peroxide include tertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, and 1,1-di (tertiary butyl peroxy) -3. , 3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-di (tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, n- Commonly used ones such as butyl-4,4-di (tert-butylperoxy) valerate are used. When crosslinking organic peroxides, multifunctional unsaturated compounds such as triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate, trimethylolpropane trimethacrylate, N, N′-m-phenylenebismaleimide Etc. are preferably used in combination.

The rubber composition to which the additive for rubber composition of the present invention is added preferably contains a filler (eg, carbon black, silica). Carbon black or silica is preferred as the filler. In the rubber composition, only one kind of these fillers may be used, or two or more kinds may be used in combination as long as the effects of the present invention are not impaired.

(Carbon black)
In the present invention, carbon black is carbon fine particles usually having a diameter of about 3 to 500 nm, which are produced by industrial quality control. Carbon black also includes those imparted with properties that are compatible with rubber by controlling the functional groups on the particle surface.

(silica)
The silica is not particularly limited, and examples of silica include natural silica, synthetic silica (precipitated silica, dry silica, wet silica) and the like. As silica, for example, silica used as a tire filler may be used.

By treating the surface of silica with a silane coupling agent, the affinity for various rubbers is improved. Therefore, in the present invention, it is preferable to treat silica with a silane coupling agent. The silane coupling agent is not particularly limited. For example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (4-triethoxysilylbutyl) tetra Sulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, Bis (2-triethoxysilylethyl) trisulfide, bis (4-triethoxysilylbutyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (2-trimethoxysilylethyl) trisulfide, bis ( 4-tri Toxisilylbutyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) disulfide, bis (4-triethoxysilylbutyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide Bis (2-trimethoxysilylethyl) disulfide, bis (4-trimethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N -Dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, Silane cups having sulfide groups such as trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide Ring agent; silane coupling agent having a mercapto group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane; vinyltriethoxysilane, Silane coupling agents having a vinyl group such as vinyltrimethoxysilane; 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Silane, a silane coupling agent having an amino group such as 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane; γ-glycidoxypropyltriethoxysilane, Silane coupling agents having a glycidoxy group such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane; 3-nitropropyltrimethoxysilane, 3 Silane coupling agents having a nitro group such as nitropropyltriethoxysilane; 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, etc. The Silane coupling agents having a B group; and the like. These may be used alone or in combination of two or more.

When the rubber composition contains a filler (eg, carbon black, silica), the filler contained in the rubber composition is preferably 20 parts by mass or more, more preferably 30 parts by mass with respect to 100 parts by mass of the rubber component. As mentioned above, More preferably, it is 50 mass parts or more, More preferably, it is 65 mass parts or more.
The filler contained in the rubber composition is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 60 parts by mass or less, and even more preferably 45 parts by mass with respect to 100 parts by mass of the rubber component. It is as follows.

Therefore, when the rubber composition contains a filler, the filler contained in the rubber composition is preferably 20 to 120 parts by mass, or preferably 50 to 120 parts by mass, more preferably 100 parts by mass of the rubber component. Is 65 to 100 parts by mass, or preferably 20 to 60 parts by mass, more preferably 30 to 45 parts by mass, or preferably 20 to 60 parts by mass.

When the rubber composition contains carbon black, the carbon black contained in the rubber composition is preferably 50 to 120 parts by mass, more preferably 65 to 100 parts by mass, or preferably 100 parts by mass with respect to 100 parts by mass of the rubber component. 20 to 60 parts by mass, more preferably 30 to 45 parts by mass.

When the rubber composition contains carbon black, from the viewpoint of reducing the wear depth of the rubber composition, the carbon black contained in the rubber composition is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the rubber component, More preferred is 30 to 45 parts by mass.

When the rubber composition contains silica, the silica contained in the rubber composition is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the rubber component.

2. Rubber composition The present invention also provides a rubber composition having excellent moldability and mechanical properties. The rubber composition of the present invention includes a rubber component, a filler (eg, carbon black, silica), and powdered cellulose having an average particle size of 15 to 70 μm.

Examples and preferred examples of powdered cellulose contained in the rubber composition of the present invention are the same as the examples and preferred examples already described in the section of the additive for rubber composition.
Examples and preferred examples of the filler contained in the rubber composition of the present invention are the same as the examples and preferred examples already described in the section of additive for rubber composition.
Examples and preferred examples of the rubber component contained in the rubber composition of the present invention are the same as the examples and preferred examples already described in the item of additive for rubber composition.

(Blend cellulose content)
The powdery cellulose contained in the rubber composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the rubber component. The powdery cellulose is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less, particularly preferably 100 parts by mass of the rubber component. 25 parts by mass or less.

Therefore, the powdery cellulose contained in the rubber composition of the present invention is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, or preferably 5 to 30 parts by mass with respect to 100 parts by mass of the rubber component. Part, more preferably 10 to 25 parts by weight, or preferably 10 to 40 parts by weight, more preferably 20 to 35 parts by weight.

When the rubber composition of the present invention contains carbon black, the powdery cellulose contained in the rubber composition of the present invention is preferably 5 to 50 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the rubber component. 30 parts by mass, or preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and particularly from the viewpoint of reducing the wear depth of the rubber composition, preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass.

When the rubber composition of the present invention contains silica, the powdery cellulose contained in the rubber composition of the present invention is preferably 10 to 40 parts by weight, more preferably 20 to 35 parts per 100 parts by weight of the rubber component. Part by mass.

(Amount of filler (eg, carbon black, silica))
The filler contained in the rubber composition of the present invention is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and still more preferably 65 parts by weight with respect to 100 parts by weight of the rubber component. More than part by mass. The filler contained in the rubber composition is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 60 parts by mass or less, and even more preferably 45 parts by mass with respect to 100 parts by mass of the rubber component. Or less.

Therefore, the filler contained in the rubber composition of the present invention is preferably 50 to 120 parts by weight, more preferably 65 to 100 parts by weight, or preferably 20 to 60 parts by weight with respect to 100 parts by weight of the rubber component. More preferably, it is 30 to 45 parts by mass, or preferably 20 to 60 parts by mass.

When the filler is carbon black, the carbon black contained in the rubber composition is preferably 50 to 120 parts by mass, more preferably 65 to 100 parts by mass, or preferably 20 to 100 parts by mass of the rubber component. -60 mass parts, more preferably 30-45 mass parts.
When the filler is carbon black, from the viewpoint of reducing the wear depth of the rubber composition, the carbon black contained in the rubber composition is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the rubber component. The amount is preferably 30 to 45 parts by mass.

When the filler is silica, the silica contained in the rubber composition is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the rubber component.

The rubber composition of the present invention preferably contains 100 parts by mass of a rubber component, 20 to 120 parts by mass of a filler, and 5 to 50 parts by mass of powdered cellulose.

When the rubber composition of the present invention contains a rubber component, carbon black, and powdered cellulose, the compounding ratio of the rubber component, carbon black, and powdered cellulose is preferably rubber component: carbon black: powdered cellulose. = 100: (20 to 120): (5 to 50) (parts by mass). By setting it as the said compounding ratio, the moldability (suppression of a Mooney viscosity rise) of a rubber composition, mechanical characteristics (especially elongation), and vulcanization characteristics (shortening of vulcanization time) are more excellent. In particular, a rubber composition containing carbon black at a high blending ratio of 50 to 120 parts by weight, preferably 65 to 100 parts by weight with respect to 100 parts by weight of the rubber component is particularly moldable for the rubber composition. Excellent mechanical and vulcanizing properties.

In the case where the rubber composition of the present invention contains a rubber component, carbon black, and powdered cellulose, from the viewpoint of improving oil leakage suppression by reducing the wear depth of rubber in high temperature oil. The mixing ratio of rubber component, carbon black, and powdered cellulose is preferably rubber component: carbon black: powdered cellulose = 100: (20-60) :( 5-30) (parts by mass), more preferably rubber Component: Carbon black: Powdered cellulose = 100: (30 to 45): (5 to 30) (parts by mass), more preferably rubber component: Carbon black: Powdered cellulose = 100: (30 to 45): (10 To 20) (parts by mass). The rubber composition having the above compounding ratio is particularly preferable for oil sealing.

When the rubber composition of the present invention is a rubber composition containing a rubber component, silica, and powdered cellulose, the compounding ratio of the rubber component, silica, and powdered cellulose is preferably rubber component: silica: powdered cellulose. = 100: (20 to 60): (10 to 40) (parts by mass). By setting it as the said compounding ratio, the moldability of a rubber composition, mechanical characteristics, and a vulcanization | cure characteristic are more excellent, and the specific gravity of a rubber composition becomes low. The rubber composition having the above compounding ratio is particularly preferable for oil sealing.

The rubber composition of the present invention may contain an optional component in addition to the above components.
Examples of optional components include components that are usually blended in rubber compositions, such as vulcanization accelerators (eg, zinc oxide, stearic acid), dispersants, anti-aging agents, and crosslinking aids. It is done.

Hereinafter, the present invention will be specifically described with reference to examples, but the present application is not limited to the examples. The test method in the Example of this application is shown next.

<Average particle size measurement>
Measurement was performed using a Microtrac particle size analyzer (Spectris Co., Ltd. (Malvern Division). As a measurement principle, a laser scattering method is used, and the particle size distribution is expressed as an accumulation distribution, and a value at which the accumulation distribution is 50% is defined as an average particle diameter.
Specifically, a laser diffraction particle size distribution analyzer (Mastersizer 2000, manufactured by Spectris Co., Ltd. (Malvern Business Division)) was used. A sample used for measurement was collected in a 0.5 g, 100 ml beaker, 60 ml of 0.5% hexametaphosphoric acid solution was added, and Dr. The sample was processed for 2 minutes under the condition of 20% output with an ultrasonic processing apparatus manufactured by Hielscher GmbH, and the processed sample was used for measurement. As a measurement principle, a laser scattering method is used, and the particle size distribution is expressed as an accumulation distribution, and a value at which the accumulation distribution is 50% is defined as an average particle diameter.

<Degree of polymerization>
The cellulose polymerization degree was calculated | required by the viscosity measuring method using the copper ethylenediamine of the 16th revision Japanese Pharmacopoeia commentary and the crystalline cellulose confirmation test (2) description.

<Crystallinity>
The crystallinity was determined by measuring the X-ray diffraction of the sample. For the measurement of X-ray diffraction, an appropriate amount of sample was placed on a glass cell, and an X-ray diffraction measurement apparatus (RAD-2C system, manufactured by Rigaku Corporation) was used. The crystallinity is calculated by the method of Segal et al. (L. Segal, JJ Greery, et al, Text. Res. J., 29, 786, 1959) and the method of Kamide et al. (K. Kamide et al. , Polymer J., 17, 909, 1985), and using the diffraction intensity of 2θ = 4 ° to 32 ° of the diffraction diagram obtained from the X-ray diffraction measurement as a baseline, the diffraction intensity of the 002 plane and 2θ = 1 From the diffraction intensity of the amorphous portion at 18.5 °, the following formula was used.
Xc = (I _002C -Ia) / I _002C × 100
Xc: degree of crystallinity of cellulose (%)
I _002C : 2θ = 22.6 °, 002 plane diffraction intensity Ia: 2θ = 18.5 °, diffraction intensity of amorphous part

<Apparent specific gravity measurement>
According to a conventional method, 10 g of a sample was put into a 100 ml graduated cylinder, the bottom of the graduated cylinder was struck, and continued until the height of the sample was not lowered, and the scale on the flat surface was read and measured. Higher values mean that the powder is more compact.

<Repose angle>
Measurement was performed using a powder tester (PT-N type, manufactured by Hosokawa Micron Corporation), and the angle of repose was taken as the angle of repose as an index of powder flowability. That is, the smaller this value, the better the powder flowability.

<Moisture>
About 5 g of the sample was precisely weighed in a weighing bottle having a known weight, and the weighing bottle containing the sample was dried with a dryer at 100 to 105 ° C. for 2 hours. After 2 hours, the sample was transferred to a desiccator, cooled for 1 hour, weighed with an analytical balance, and calculated from the weight of the sample before and after drying.

<Mooney viscosity (ML (ML _{1 + 4} )>
The values measured with a Mooney viscometer using a Mooney viscometer (SMV-300, manufactured by Shimadzu Corporation) at 100 ° C. for 1 minute preheating and 4 minutes after starting rotation are shown.

<Vulcanization characteristics>
An unvulcanized rubber sheet was prepared as a sample and measured using a curast meter (manufactured by JSR Corporation). A vulcanization curve for 10 minutes was measured at a measurement temperature of 160 ° C., and the torque (N · m) after the lapse of 10 minutes was determined with a graph in which the vertical axis represents torque and the horizontal axis represents time.

<Rubber hardness>
The rubber hardness (Shore A) was measured according to ISO M6518.

<50% tensile stress, 400% tensile stress, 600% tensile stress>
Measured according to ISO M6518.

<Wear depth>
Using a ring-on-disk friction and wear tester (manufactured by Kobe Machinery Co., Ltd.), the test piece was immersed in a designated lubricating oil heated to 100 ° C. (IRM-903, designated in the JIS oil wear test) for 72 hours. At a rotational speed of 250 rpm, a load of 10 kgf was applied per minute from the start of rotation, the load was increased to 40 kgf, and the wear depth of the test piece after 120 minutes was measured by an average of three points. The smaller the wear depth, the higher the resistance to repeated sliding and the less oil leakage.

<Compression set>
In accordance with JIS K6262, the measurement conditions were 70 ° C. and 24 hours.

<Example 1>
Nitrile rubber (KUMHO PETROCHEMICAL, trade name: KNB35L, bound acrylonitrile content 34%, Mooney viscosity 41) 100 parts by weight, carbon black (Sid Richardson, trade name: N550) 75 parts by weight, powdered cellulose ( Manufactured by Nippon Paper Industries Co., Ltd., trade name: W-200Y, average particle size 31 μm, polymerization degree 600, crystallinity 84%, apparent specific gravity 0.36 g / ml, repose angle 51 °, moisture 2.5%) 10 parts by mass, 3 parts by mass of zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.), 6 parts by mass of plasticizer (manufactured by ADEKA, trade name: RS107), 2 parts by mass of anti-aging agent (manufactured by Chemutra), and crosslinking aid (Kawaguchi Chemical Industries) 4.9 parts by mass of a peroxide (manufactured by Kogyo Co., Ltd.) was kneaded with a kneader and an open roll. The kneaded product had a Mooney viscosity of 130 N · m and a vulcanization characteristic of 1.5 N · m. The kneaded product was subjected to press vulcanization at 160 ° C. for 12 minutes to obtain a plate test piece having a rubber hardness of 83 Shore A.

<Example 2>
Example 1 was repeated except that the amount of plasticizer added was changed to 30 parts by mass. The resulting kneaded product had a Mooney viscosity of 54 N · m and a vulcanization characteristic of 1.0 N · m. Further, the rubber hardness of the plate-like test piece was 74 Shore A.

<Example 3>
The same procedure as in Example 1 was performed except that the nitrile rubber was changed to KNB35H (manufactured by KUMHO PETROCHEMICAL, bound acrylonitrile content: 34%, Mooney viscosity: 80). The resulting kneaded product had a Mooney viscosity of 175 N · m and a vulcanization characteristic of 2.2 N · m. Further, the rubber hardness of the plate-like test piece was 87 Shore A.

<Comparative Example 1>
The same procedure as in Example 1 was carried out except that the blending amount of carbon black was 85 parts by mass and powdered cellulose was not blended. The resulting kneaded product had a Mooney viscosity of 140 N · m and a vulcanization characteristic of 1.2 N · m. Further, the rubber hardness of the plate-like test piece was 82 Shore A.

<Comparative Example 2>
The same procedure as in Comparative Example 1 was conducted except that the amount of plasticizer added was changed to 30 parts by mass. The resulting kneaded product had a Mooney viscosity of 62 N · m and a vulcanization characteristic of 0.9 N · m. Further, the rubber hardness of the plate-like test piece was 73 Shore A.

<Comparative Example 3>
Comparative Example 1 was repeated except that the nitrile rubber was changed to KNB35H. The resulting kneaded product had a Mooney viscosity of 200 N · m and a vulcanization characteristic of 1.9 N · m. Further, the rubber hardness of the plate-like test piece was 86 Shore A.

<Example 4>
The powdered cellulose was changed to W-400G (manufactured by Nippon Paper Industries Co., Ltd., average particle size 24 μm, polymerization degree 160, crystallinity 86%, apparent specific gravity 0.48 g / ml, repose angle 49 °, moisture 3.5%). Except for this, the procedure was the same as in Example 1. The resulting kneaded product had a Mooney viscosity of 135 N · m and a vulcanization characteristic of 1.4 N · m. Further, the rubber hardness of the plate-like test piece was 82 Shore A.

<Example 5>
The powdered cellulose was changed to W-100G (manufactured by Nippon Paper Industries Co., Ltd., average particle size 36 μm, polymerization degree 450, crystallinity 85%, apparent specific gravity 0.30 g / ml, repose angle 58 °, moisture 3.6%). Except for this, the procedure was the same as in Example 1. The resulting kneaded product had a Mooney viscosity of 133 N · m and a vulcanization characteristic of 1.4 N · m. Further, the rubber hardness of the plate-like test piece was 83 Shore A.

<Example 6>
The powdery cellulose was changed to W-50 (manufactured by Nippon Paper Industries Co., Ltd., average particle size 42 μm, polymerization degree 1050, crystallinity 83%, apparent specific gravity 0.20 g / ml, repose angle 60 °, moisture 3.1%). Except for this, the procedure was the same as in Example 1. The resulting kneaded product had a Mooney viscosity of 137 N · m and a vulcanization characteristic of 1.3 N · m. Further, the rubber hardness of the plate-like test piece was 84 Shore A.

<Example 7>
The same procedure as in Example 1 was carried out except that the amount of carbon black added was 55 parts by mass and the amount of powdered cellulose was 30 parts by mass. The resulting kneaded product had a Mooney viscosity of 120 N · m and a vulcanization characteristic of 1.6 N · m. Further, the rubber hardness of the plate-like test piece was 86 Shore A.

<Example 8>
The procedure of Example 1 was repeated except that the amount of carbon black added was 100 parts by mass and the amount of powdered cellulose was 20 parts by mass. The resulting kneaded product had a Mooney viscosity of 155 N · m and a vulcanization characteristic of 1.4 N · m. Further, the rubber hardness of the plate-like test piece was 91 Shore A.

<Comparative Example 4>
Powdered cellulose was changed to W-10MG2 (manufactured by Nippon Paper Industries Co., Ltd., average particle size 10 μm, polymerization degree 140, crystallinity 78%, apparent specific gravity 0.38 g / ml, repose angle 47 °, moisture 3.5%). Except for this, the procedure was the same as in Example 1. The resulting kneaded product had a Mooney viscosity of 140 N · m and a vulcanization characteristic of 1.1 N · m. Further, the rubber hardness of the plate-like test piece was 81 Shore A.

<Comparative Example 5>
Using an exposed wood pulp sheet (NDSP, manufactured by Nippon Paper Industries Co., Ltd., average polymerization degree 1600) as a raw material, it is mechanically pulverized using a tornado mill (manufactured by Nikkiso Co., Ltd.), with an average particle diameter of 72.3 μm, average A powdery cellulose having a polymerization degree of 1480 and a crystallinity of 82.3% was obtained.
The same procedure as in Example 1 was conducted except that the powdery cellulose used was changed to the powder described above. The resulting kneaded product had a Mooney viscosity of 145 N · m and a vulcanization characteristic of 1.0 N · m. Further, the rubber hardness of the plate-like test piece was 87 Shore A.

<Comparative Example 6>
The same procedure as in Comparative Example 3 was performed except that the addition amount of carbon black was changed to 120 parts by mass and the addition amount of the plasticizer was changed to 18 parts by mass. The resulting kneaded product had a Mooney viscosity of 153 N · m and a vulcanization characteristic of 1.4 N · m. Further, the rubber hardness of the plate-like test piece was 81 Shore A.

From the results shown in Table 1-1, the rubber compositions of Examples 1 to 3 containing powdered cellulose maintained the rubber hardness as compared with the rubber compositions of Comparative Examples 1 to 3 not containing powdered cellulose. However, it can be seen that the Mooney viscosity is lowered. It can also be seen that the vulcanization characteristics are improved.

From the results of Table 1-2 and Table 1-3, the rubber compositions of Examples 4 to 6 were compared with the rubber compositions of Comparative Examples 4 and 5 where the average particle size of the powdered cellulose was not in the range of 15 to 70 μm. It can be seen that the Mooney viscosity is lowered while the rubber hardness is maintained. It can also be seen that the vulcanization characteristics are improved.

<Example 2-1>
The procedure was the same as Example 1 except that the amount of carbon black was changed to 40 parts by mass. The resulting kneaded product had a Mooney viscosity of 34 N · m and a vulcanization characteristic of 1.4 N · m. The rubber hardness of the plate-like test piece was 72 Shore A, the 50% tensile stress was 29 kgf / cm ² , and the wear depth was 34 μm.

<Example 2-2>
The same procedure as in Example 1 was conducted except that the amount of carbon black was changed to 30 parts by mass and the amount of powdered cellulose was changed to 20 parts by mass. The resulting kneaded product had a Mooney viscosity of 31 N · m and a vulcanization characteristic of 1.5 N · m. Further, the rubber hardness of the plate-like test piece was 73 Shore A, the 50% tensile stress was 34 Kgf / cm ² , and the wear depth was 22 μm.

<Comparative Example 2-1>
The same procedure as in Example 1 was carried out except that the blending amount of carbon black was changed to 50 parts by mass and the powdery cellulose was not blended. The resulting kneaded product had a Mooney viscosity of 37 N · m and a vulcanization characteristic of 1.1 N · m. The rubber hardness of the plate-like test piece was 71 Shore A, the 50% tensile stress was 22 kgf / cm ² , and the wear depth was 84 μm.

<Comparative Example 2-2>
The same procedure as in Example 1 was carried out except that the blending amount of carbon black was changed to 80 parts by mass and the powdery cellulose was not blended. The resulting kneaded product had a Mooney viscosity of 130 N · m and a vulcanization characteristic of 1.3 N · m. The rubber hardness of the plate-like test piece was 82 Shore A, the 50% tensile stress was 26 Kgf / cm ² , and the wear depth was 61 μm.

<Example 2-3>
The powdery cellulose was changed to W-400G (manufactured by Nippon Paper Industries Co., Ltd., average particle size 24 μm, polymerization degree 160, crystallinity 86%, apparent specific gravity 0.48 g / ml, repose angle 49 °, moisture 3.5%). Except for this, the procedure was the same as in Example 2-1. The resulting kneaded product had a Mooney viscosity of 36 N · m and a vulcanization characteristic of 1.4 N · m. The rubber hardness of the plate-like test piece was 71 Shore A, the 50% tensile stress was 25 Kgf / cm ² , and the wear depth was 40 μm.

<Example 2-4>
The powdered cellulose was changed to W-100G (manufactured by Nippon Paper Industries Co., Ltd., average particle size 36 μm, polymerization degree 450, crystallinity 85%, apparent specific gravity 0.30 g / ml, repose angle 58 °, moisture 3.6%). Except for this, the procedure was the same as in Example 2-1. The resulting kneaded product had a Mooney viscosity of 35 N · m and a vulcanization characteristic of 1.4 N · m. The rubber hardness of the plate-like test piece was 72 Shore A, the 50% tensile stress was 28 kgf / cm ² , and the wear depth was 36 μm.

<Example 2-5>
The powdery cellulose was changed to W-50 (manufactured by Nippon Paper Industries Co., Ltd., average particle size 42 μm, polymerization degree 1050, crystallinity 83%, apparent specific gravity 0.20 g / ml, repose angle 60 °, moisture 3.1%). Except for this, the procedure was the same as in Example 2-1. The resulting kneaded product had a Mooney viscosity of 36 N · m and a vulcanization characteristic of 1.3 N · m. The rubber hardness of the plate-like test piece was 73 Shore A, the 50% tensile stress was 23 Kgf / cm ² , and the wear depth was 35 μm.

<Example 2-6>
The procedure was the same as Example 2-1, except that the amount of carbon black added was 20 parts by mass and the amount of powdered cellulose was 5 parts by mass. The resulting kneaded product had a Mooney viscosity of 28 N · m and a vulcanization characteristic of 1.2 N · m. The rubber hardness of the plate-like test piece was 61 Shore A, the 50% tensile stress was 17 kgf / cm ² , and the wear depth was 48 μm.

<Example 2-7>
The same procedure as in Example 2-1 was performed, except that the addition amount of carbon black was 55 parts by mass, and powdered cellulose was 30 parts by mass. The resulting kneaded product had a Mooney viscosity of 120 N · m and a vulcanization characteristic of 1.6 N · m. The rubber hardness of the plate-like test piece was 86 Shore A, the 50% tensile stress was 40 Kgf / cm ² , and the wear depth was 28 μm.

<Example 2-8>
Example 2-1 was performed except that the amount of carbon black added was 100 parts by mass and the amount of powdered cellulose was 20 parts by mass. The resulting kneaded product had a Mooney viscosity of 155 N · m and a vulcanization characteristic of 1.6 N · m. The rubber hardness of the plate-like test piece was 91 Shore A, the 50% tensile stress was 48 kgf / cm ² , and the wear depth was 33 μm.

<Comparative Example 2-3>
Powdered cellulose was changed to W-10MG2 (manufactured by Nippon Paper Industries Co., Ltd., average particle size 10 μm, polymerization degree 140, crystallinity 78%, apparent specific gravity 0.38 g / ml, repose angle 47 °, moisture 3.5%). Except for this, the procedure was the same as in Example 2-1. The resulting kneaded product had a Mooney viscosity of 37 N · m and a vulcanization characteristic of 1.1 N · m. The rubber hardness of the plate-like test piece was 71 Shore A, the 50% tensile stress was 22 kgf / cm ² , and the wear depth was 62 μm.

<Comparative Example 2-4>
Using an exposed wood pulp sheet (NDSP, manufactured by Nippon Paper Industries Co., Ltd., average polymerization degree 1600) as a raw material, it is mechanically pulverized using a tornado mill (manufactured by Nikkiso Co., Ltd.), with an average particle diameter of 72.3 μm, average A powdery cellulose having a polymerization degree of 1480 and a crystallinity of 82.3% was obtained.
Example 2-1 was carried out except that the powdery cellulose used was changed to the above powder. The resulting kneaded product had a Mooney viscosity of 40 N · m and a vulcanization characteristic of 1.0 N · m. The rubber hardness of the plate-like test piece was 77 Shore A, the 50% tensile stress was 19 Kgf / cm ² , and the wear depth was 56 μm.

<Comparative Example 2-5>
The same procedure as in Comparative Example 2-2 was performed except that the addition amount of carbon black was changed to 120 parts by mass and the addition amount of the plasticizer was changed to 18 parts by mass. The resulting kneaded product had a Mooney viscosity of 153 N · m and a vulcanization characteristic of 1.4 N · m. The rubber hardness of the plate-like test piece was 81 Shore A, the 50% tensile stress was 39 Kgf / cm ² , and the wear depth was 60 μm.

From the results of Table 2-1, the rubber compositions of Example 2-1 and Example 2-1 were compared with the rubber compositions of Comparative Example 2-1 and Comparative Example 2-2 that did not contain powdered cellulose. It can be seen that the wear depth is significantly reduced. It can also be seen that the vulcanization characteristics are improved.

From the results shown in Table 2-2 and Table 2-4, it was found that Examples were compared with the rubber compositions of Comparative Example 2-3 and Comparative Example 2-4 where the average particle size of the powdered cellulose was not in the range of 15 to 70 μm. It can be seen that the rubber compositions of 2-3 to Example 2-5 have a significantly reduced wear depth. It can also be seen that the vulcanization characteristics are improved.
Further, the results of Examples 2-6 to 2-8 show that the wear depth is reduced even when the blending ratio of carbon black and powdered cellulose is changed.

<Example 3-1>
Using ethylene propylene diene rubber (EPDM) (manufactured by KUMHO PETROCHEMICAL, product name: KEP570P (Mooney viscosity 53)), silica (manufactured by Rhodia, product name: Z-175) is added to 100 parts by weight of ethylene propylene diene rubber. 40 parts by weight, powdered cellulose (manufactured by Nippon Paper Industries Co., Ltd., product name: W-50 (average particle size 43 μm, polymerization degree 1100, crystallinity 83%, apparent specific gravity 0.20 g / ml, repose angle 58 °, moisture) 2.5%)) 10 parts by weight, zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., zinc oxide for rubber) 5 parts by weight, silane coupling agent (Evonik Degussa, product name: Dynasylan Si-69) 4 Parts by weight, 4 parts by weight of polyethylene glycol (Toho Chemical Industries, product name: PEG 4000), stearin 1 part by weight of acid (manufactured by CMB), 2 parts by weight of anti-aging agent (manufactured by Chemutra, product name: Naugard 445), 3.6 parts by weight of crosslinking aid (manufactured by Kawaguchi Chemical Industry, product name: trialic) The Mooney viscosity of the kneaded product kneaded with a kneader and an open roll was 52 N · m, and the vulcanization characteristic was 1.6 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.08, a rubber hardness of 76 Shore A, a 400% tensile stress of 65 kgf / cm ² , a 600% tensile stress of 150 kgf / cm ² and a compression set of 33%.

<Example 3-2>
Using ethylene propylene diene rubber (manufactured by KUMHO PETROCHEMICAL, product name: KEP570P (Mooney viscosity 53))), 30 parts by weight of silica (manufactured by Rhodia, product name: Z-175) per 100 parts by weight of ethylene propylene diene rubber Parts, powdered cellulose (manufactured by Nippon Paper Industries Co., Ltd., product name: W-50 (average particle size 43 μm, polymerization degree 1100, crystallinity 83%, apparent specific gravity 0.20 g / ml, repose angle 58 °, moisture 2. 5%)) 20 parts by weight, zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., zinc oxide for rubber) 5 parts by weight, silane coupling agent (Evonik Degussa, product name: Dynasylan Si-69) 3.2 Parts by weight, 3.2 parts by weight of polyethylene glycol (manufactured by Toho Chemical Co., Ltd., product name: PEG 4000), stearic acid 1 part by weight (manufactured by CMB), 2 parts by weight of anti-aging agent (manufactured by Chemutra, product name: Naugard 445), and 3.6 parts by weight of crosslinking aid (manufactured by Kawaguchi Chemical Industry Co., Ltd., product name: trialic) The kneaded product kneaded with a kneader and an open roll had a Mooney viscosity of 46 N · m and a vulcanization characteristic of 1.9 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.06, a rubber hardness of 77 Shore A, a 400% tensile stress of 80 kgf / cm ² , a 600% tensile stress of 170 kgf / cm ² and a compression set of 31%.

<Comparative Example 3-1>
Using ethylene propylene diene rubber (manufactured by KUMHO PETROCHEMICAL, product name: KEP570P (Mooney viscosity 53)), 30 parts by weight of silica (manufactured by Rhodia, product name: Z-175) with respect to 100 parts by weight of ethylene propylene diene rubber , 5 parts by weight of zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., zinc oxide for rubber), 2.4 parts by weight of silane coupling agent (manufactured by Evonik Degussa, product name: Dynasylan Si-69), polyethylene glycol (Toho Chemical) Kogyo Co., Ltd., product name: PEG 4000) 2.4 parts by weight, stearic acid (CMB) 1 part by weight, anti-aging agent (Chemutra, product name: Naugard 445) 2 parts by weight, cross-linked 3.6 parts by weight of auxiliary agent (product name: Trialic, manufactured by Kawaguchi Chemical Industry Co., Ltd.) The kneaded product kneaded with an open roll had a Mooney viscosity of 43 N · m and a vulcanization characteristic of 1.1 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.00, rubber hardness of 66 Shore A, 400% tensile stress of 52 Kgf / cm ² , 600% tensile stress of 125 Kgf / cm ² , and compression set of 35%.

<Comparative Example 3-2>
Using ethylene propylene diene rubber (manufactured by KUMHO PETROCHEMICAL, product name: KEP570P (Mooney viscosity 53)), 50 parts by weight of silica (manufactured by Rhodia, product name: Z-175) with respect to 100 parts by weight of ethylene propylene diene rubber , 5 parts by weight of zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., zinc oxide for rubber), 4 parts by weight of silane coupling agent (manufactured by Evonik Degussa, product name: Dynasylan Si-69), polyethylene glycol (Toho Chemical Co., Ltd.) 4 parts by weight of product manufactured by company, product name: PEG 4000), 1 part by weight of stearic acid (manufactured by CMB), 2 parts by weight of anti-aging agent (manufactured by Chemutra, product name: Naugard 445), crosslinking aid (Kawaguchi) 3.6 parts by weight of chemical industry, product name: Trialic), kneader and orange The Mooney viscosity of the kneaded material kneaded with the open roll was 55 N · m, and the vulcanization characteristic was 1.3 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.10, a rubber hardness of 75 Shore A, a 400% tensile stress of 62 kgf / cm ² , a 600% tensile stress of 140 kgf / cm ² and a compression set of 37%.

<Example 3-3>
The powdery cellulose was changed to W-400G (manufactured by Nippon Paper Industries Co., Ltd., average particle size 24 μm, polymerization degree 160, crystallinity 86%, apparent specific gravity 0.48 g / ml, repose angle 49 °, moisture 3.5%). Except for this, the procedure was the same as in Example 3-1. The resulting kneaded product had a Mooney viscosity of 54 N · m and a vulcanization characteristic of 1.4 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.08, a rubber hardness of 75 Shore A, a 400% tensile stress of 62 kgf / cm ² , a 600% tensile stress of 142 kgf / cm ² and a compression set of 34%.

<Example 3-4>
The powdered cellulose was changed to W-100G (manufactured by Nippon Paper Industries Co., Ltd., average particle size 36 μm, polymerization degree 450, crystallinity 85%, apparent specific gravity 0.30 g / ml, repose angle 58 °, moisture 3.6%). Except for this, the procedure was the same as in Example 3-1. The resulting kneaded product had a Mooney viscosity of 53 N · m and a vulcanization characteristic of 1.4 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.08, a rubber hardness of 76 Shore A, a 400% tensile stress of 63 Kgf / cm ² , a 600% tensile stress of 145 Kgf / cm ² and a compression set of 33%.

<Comparative Example 3-3>
Powdered cellulose was changed to W-10MG2 (manufactured by Nippon Paper Industries Co., Ltd., average particle size 10 μm, polymerization degree 140, crystallinity 78%, apparent specific gravity 0.38 g / ml, repose angle 47 °, moisture 3.5%). Except for this, the procedure was the same as in Example 3-1. The resulting kneaded product had a Mooney viscosity of 55 N · m and a vulcanization characteristic of 1.1 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.08, a rubber hardness of 75 Shore A, a 400% tensile stress of 61 kgf / cm ² , a 600% tensile stress of 138 kgf / cm ² and a compression set of 36%.

<Comparative Example 3-4>
Using an exposed wood pulp sheet (NDSP, manufactured by Nippon Paper Industries Co., Ltd., average polymerization degree 1600) as a raw material, it is mechanically pulverized using a tornado mill (manufactured by Nikkiso Co., Ltd.), with an average particle diameter of 72.3 μm, average A powdery cellulose having a polymerization degree of 1480 and a crystallinity of 82.3% was obtained.
The same procedure as in Example 3-1 was conducted, except that the powdery cellulose used was changed to the powder described above. The resulting kneaded product had a Mooney viscosity of 57 N · m and a vulcanization characteristic of 1.0 N · m. The kneaded product was press-vulcanized at 160 ° C. for 12 minutes to obtain a plate-shaped test piece. The obtained specimen had a specific gravity of 1.08, a rubber hardness of 79 Shore A, a 400% tensile stress of 59 Kgf / cm ² , a 600% tensile stress of 132 Kgf / cm ² , and a compression set of 37%.

From the results shown in Table 3-1, the specific gravity of the rubber composition of Example 3-1 was reduced and the rubber hardness was not reduced as compared with the rubber composition of Comparative Example 3-2 not containing powdered cellulose. It can be seen that the Mooney viscosity decreases. It can also be seen that the vulcanization characteristics are also improved.

From the results shown in Table 3-2, Example 3-3 and Example 3 were compared with the rubber compositions of Comparative Example 3-3 and Comparative Example 3-4 where the average particle size of the powdered cellulose was not in the range of 15 to 70 μm. It can be seen that the rubber composition of Example 3-4 has a high 600% tensile stress and excellent mechanical properties. It can also be seen that the vulcanization characteristics are improved.

Claims (15)

1. An additive for rubber composition containing powdered cellulose having an average particle size of 15 to 70 μm.
2. The additive for rubber composition according to claim 1, wherein the average particle size of the powdery cellulose is 25 to 70 µm.
3. The powdery cellulose has a polymerization degree of 150 to 1200, a crystallinity of 70 to 90%, an apparent specific gravity of 0.15 to 0.6 g / mL, an angle of repose of 45 to 60 °, and a water content of 5% or less. The additive for rubber compositions according to claim 1 or 2.
4. The additive for a rubber composition according to any one of claims 1 to 3, wherein the powdery cellulose is a pulverized product of a cellulose raw material treated with an inorganic acid.
5. The additive for a rubber composition according to any one of claims 1 to 4, wherein the rubber composition comprises 100 parts by mass of a rubber component and 20 to 120 parts by mass of carbon black.
6. The rubber composition additive according to any one of claims 1 to 5, wherein the rubber composition comprises 100 parts by mass of a rubber component and 20 to 60 parts by mass of silica.
7. The rubber composition additive according to any one of claims 1 to 6, wherein the rubber composition is used for oil sealing.
8. Rubber composition comprising a rubber component, a filler, and powdered cellulose having an average particle size of 15 to 70 μm.
9. The powdery cellulose has a polymerization degree of 150 to 1200, a crystallinity of 70 to 90%, an apparent specific gravity of 0.15 to 0.6 g / mL, an angle of repose of 45 to 60 °, and a water content of 5% or less. The rubber composition according to claim 8.
10. The rubber composition according to claim 8 or 9, comprising 100 parts by mass of a rubber component, 20 to 120 parts by mass of a filler, and 5 to 50 parts by mass of powdered cellulose.
11. The rubber composition according to any one of claims 8 to 10, wherein the filler is carbon black or silica.
12. The rubber composition according to any one of claims 8 to 11, comprising 20 to 60 parts by mass of a filler.
13. The rubber composition according to any one of claims 8 to 12, comprising 10 to 40 parts by mass of powdered cellulose.
14. The rubber composition according to any one of claims 8 to 13, which is used for oil sealing.
15. An oil seal comprising the rubber composition according to any one of claims 8 to 13.