CA2894792C - Rubber composition and conveyor belt - Google Patents

Rubber composition and conveyor belt Download PDF

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Publication number
CA2894792C
CA2894792C CA2894792A CA2894792A CA2894792C CA 2894792 C CA2894792 C CA 2894792C CA 2894792 A CA2894792 A CA 2894792A CA 2894792 A CA2894792 A CA 2894792A CA 2894792 C CA2894792 C CA 2894792C
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Prior art keywords
mass
parts
rubber
rosin
composition
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French (fr)
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CA2894792A1 (en
Inventor
Hidehiro SASAKUMA
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/02Halogenated hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092Polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00Compositions of homopolymers or copolymers of chloroprene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04Rosin
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16GBELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G1/00Driving-belts
    • F16G1/06Driving-belts made of rubber
    • F16G1/08Driving-belts made of rubber with reinforcement bonded by the rubber
    • F16G1/12Driving-belts made of rubber with reinforcement bonded by the rubber with metal reinforcement
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16GBELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
    • F16G5/00V-belts, i.e. belts of tapered cross-section
    • F16G5/04V-belts, i.e. belts of tapered cross-section made of rubber
    • F16G5/06V-belts, i.e. belts of tapered cross-section made of rubber with reinforcement bonded by the rubber
    • F16G5/10V-belts, i.e. belts of tapered cross-section made of rubber with reinforcement bonded by the rubber with metal reinforcement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65GTRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G15/00Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
    • B65G15/30Belts or like endless load-carriers
    • B65G15/32Belts or like endless load-carriers made of rubber or plastics
    • B65G15/38Belts or like endless load-carriers made of rubber or plastics with flame-resistant layers, e.g. of asbestos, glass
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65GTRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G2207/00Indexing codes relating to constructional details, configuration and additional features of a handling device, e.g. Conveyors
    • B65G2207/22Heat or fire protection

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Belt Conveyors (AREA)

Abstract

Provided are: a rubber composition that has excellent adhesiveness to galvanized steel cords and that has improved flame retardancy and cold resistance; and a conveyor belt. This rubber composition is a rubber composition that includes: a rubber component including butadiene rubber, chloroprene rubber, and natural rubber; an organic cobalt salt; rosin or a rosin derivative; and an organochlorine compound. The content of said butadiene rubber is from 5 parts by mass to 20 parts by mass inclusive per 100 parts by mass of said rubber component. The content of said chloroprene rubber is from 20 parts by mass to 65 parts by mass inclusive per 100 parts by mass of said rubber component. The content of said organic cobalt salt is from 0.2 parts by mass to 1.0 part by mass inclusive per 100 parts by mass of said rubber component when the mass of said organic cobalt salt is converted to that of cobalt. The content of said rosin or rosin derivative is from 2 parts by mass to 9 parts by mass inclusive per 100 parts by mass of said rubber component. The content of said organochlorine compound is from 5 parts by mass to 35 parts by mass inclusive per 100 parts by mass of said rubber component.

Description

= CA 02894792 2015-06-11 RUBBER COMPOSITION AND CONVEYOR BELT
TECHNICAL FIELD
[0001]
The present invention relates to a rubber composition and a conveyor belt having flame retardancy and cold resistance.
BACKGROUND
[0002]
Conventionally, a rubber composition containing an organic cobalt salt and a rosin has been used to adhere a galvanized steel cord to a rubber composition (for example, see Patent Document 1). In addition, the idea of adding a flame retardant such as a halogen compound or setting the content of chloroprene rubber (CR), which is a flame retardant rubber, to 100 parts by mass without using a halogen rubber in order to impart flame retardancy to an adhesive rubber is also known (for example, see Patent Document 2).
[0003]
A rubber composition having excellent adhesiveness to galvanized metal materials is described in Patent Document 1. The rubber composition described in Patent Document 1 is a composition containing prescribed amounts of a rosin or rosin derivative, an organic acid cobalt salt, and an organochlorine compound per 100 parts by weight of a sulfur-vulcanizable rubber.
[0004]
A chloroprene-based adhesive rubber composition having excellent flame retardancy and heat resistance is described in Patent Document 2. The adhesive rubber composition described in Patent Document 2 is prepared by blending prescribed amounts of an organic acid cobalt salt, zinc oxide, sulfur, and 2-mercaptoimidazoline per 100 parts by weight of a chloroprene rubber.
PRIOR ART DOCUMENT
Patent Document
[0005]
Patent Document 1: Japanese Unexamined Patent Application Publication No.

Patent Document 2: Japanese Unexamined Patent Application Publication No.

SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0006]
However, although the adhesiveness of the rubber composition described in Patent Document 1, in which a flame retardant is added without using a halogen rubber, is maintained, sufficient consideration is not given to cold resistance or flame retardancy. In addition, in the case of the adhesive rubber composition described in Patent Document 2 containing 100 parts by mass of a chloroprene rubber, adhesiveness is maintained, but cold resistance is not taken into consideration, and there is a concern that the composition may be unusable in cold regions. Therefore, these compositions are insufficient for use in cold regions or usage environments requiring flame retardancy, and there is room for further improvement.
[0007]
Accordingly, there is a demand for a rubber composition for metal adhesion having excellent adhesiveness to galvanized steel cords and having high flame retardancy and excellent cold resistance.
[0008]
In light of the problems described above, an object of the present invention is to provide a rubber composition having excellent adhesiveness to galvanized steel cords and having improved flame retardancy and cold resistance, and a conveyor belt.
Means to Solve the Problem
[0009]
The present invention is described in the following (1) to (3).
(1) A rubber composition comprising a rubber component containing a butadiene rubber, a chloroprene rubber, and a natural rubber; an organic cobalt salt; a rosin or rosin derivative; and an organochlorine compound;
the content of the butadiene rubber being from 5 parts by mass to 20 parts by mass per 100 parts by mass of the rubber component;
the content of the chloroprene rubber being from 20 parts by mass to 65 parts by mass per 100 parts by mass of the rubber component;
the content of the organic cobalt salt being from 0.2 parts by mass to 1.0 parts by mass per 100 parts by mass of the rubber component when the mass of the organic cobalt salt is converted to the mass of cobalt;
the content of the rosin or rosin derivative being from 2 parts by mass to 9 parts by mass per 100 parts by mass of the rubber component; and the content of the organochlorine compound being from 5 parts by mass to 35 parts by mass per 100 parts by mass of the rubber component.
(2) The rubber composition according to (1), wherein a numerical value A calculated by the following formula (1) is at most 83 parts by mass per 100 parts by mass of the rubber component.
[Formula 1]
A= chloroprene rubber (CR) x 0.8 + organochlorine compound x 1.5 + rosin x 2.5 (1) (3) A conveyor belt comprising a composite obtained by vulcanizing a product containing the rubber composition described in (1) or (2) and a galvanized steel cord.
EFFECT OF THE INVENTION
[0010]
The present invention yields excellent adhesiveness to galvanized steel cords and makes it possible to improve flame retardancy and cold resistance.
BRIEF DESCRIPTION OF THE DRAWING
[0011]
FIG. 1 is a cross-sectional perspective view of the conveyor belt of an embodiment of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0012]
The present invention is explained in detail below. However, the present invention is not limited by the embodiments of the invention (hereinafter referred to as the "embodiments") described hereinafter.
Furthermore, the constituents described in the embodiments include constituents that could be easily conceived by a person skilled in the art and constituents that are essentially identical, or, in other words, are equivalent in scope. Moreover, the constituents described in the embodiments can be combined as desired.
[0013]
<Rubber composition>
The rubber composition of this embodiment (called the "composition of this embodiment" hereafter) comprises a rubber component containing a butadiene rubber (BR), a chloroprene rubber (CR), and a natural rubber (NR);
an organic cobalt salt; a rosin or rosin derivative; and an organochlorine compound.
[0014]
(Rubber Component) A sulfur-vulcanizable rubber is used as the rubber component contained in the composition of this embodiment. A sulfur-vulcanizable rubber is a rubber that can be vulcanized using sulfur such as a natural rubber, a synthetic rubber, or a mixture thereof, and examples include diene rubbers and the like. Specific examples of diene rubbers include natural rubbers, isoprene rubbers (IR), various butadiene rubbers (BR), 1,2-butadiene rubbers, various styrene-butadiene copolymer rubbers (SBR), acrylonitrile-butadiene copolymer rubbers (NBR), chloroprene rubbers, butyl rubbers (IIR), and ethylene-propylene-diene rubbers (EPDM). One type of these rubber components may be used alone, or two or more types may be used in combination.
[0015]
Of these rubbers, butadiene rubbers, chloroprene rubbers, and natural rubbers are contained since they have excellent adhesiveness, flame retardancy, and cold resistance.
[0016]
The mass average mrolecular weight (Mw) of the butadiene rubber is preferably at least 400,000 and more preferably at least 450,000. When the mass average molecular weight is within this range, the tensile strength and elongation at break of the rubber composition after vulcanization further improve. The mass average molecular weight is the mass average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC), and tetrahydrofuran (THF) is preferably used as a solvent in the measurement. A commerCially available product may be used as the butadiene rubber, and specific examples include NipolTM BR1220 and NipolTM BR1250H produced by the Zeon Corporation.
[0017]
Examples of chloroprene rubbers include sulfur-modified (G) type rubbers, non-sulfur-modified (W) type rubbers, and high crystalline type rubbers, and various known chloroprene rubbers can be' used. A commercially available product may be used as the chloroprene rubber, and specific examples include NeopreneTM GRT and NeopreneTM
WRT produced by Showa Denko Du Pont and Denka Chloroprene PM-40 and S-41 produced by Denki Kagaku Kogyo K.K.
[0018]
A natural rubber is a polymer having a structure with a head-to-tail linkage of cis-1,4-polyisoprene, and a commonly used natural rubber may be used. A commercially available product may be used as the natural rubber, and specific examples include TSR-20 and RSS#3.
[0019]
The content of the butadiene rubber in the rubber component is from 5 5 parts by mass to 20 parts by mass and preferably from 5 parts by mass to parts by mass per 100 parts by mass of the rubber component of this embodiment. In addition, the content of the chloroprene rubber in the rubber component is from 20 parts by mass to 65 parts by mass and preferably from 25 parts by mass to 60 parts by mass per 100 parts by mass of the rubber component of this embodiment. Furthermore, the content of the natural rubber in the rubber component is the remaining amount determined by subtracting the total content of the butadiene rubber and the chloroprene rubber from 100 parts by mass of the rubber component of this embodiment - that is, from 15 parts by mass to 75 parts by mass and preferably from 25 parts by mass to 70 parts by mass.
[0020]
When the contents of the butadiene rubber, the chloroprene rubber, and the natural rubber are within each of the ranges described above, it is possible to improve flame retardancy and cold resistance while maintaining the adhesiveness of the composition of this embodiment. In addition, the tensile strength and elongation at break, which are physical properties after the vulcanization of the composition of this embodiment, become favorable.
[0021]
<Organic cobalt salt>
The organic cobalt salt contained in the composition of this embodiment is not particularly limited as long as it is a conventionally known substance that is commonly used as a liquid phase oxidation catalyst. The organic cobalt salt can be obtained by a method of performing metathetical precipitation by adding a cobalt acetate solution to an alkali soap aqueous solution of a corresponding organic acid, a method of heating and melting an organic acid and cobalt oxide (II), a method of adding an aqueous solution of cobalt sulfate or cobalt nitrate to a benzene solution of an organic acid, or the like. Specific examples of organic cobalt salts include cobalt naphthenate, cobalt stearate, cobalt neodecanoate, cobalt orthoborate, cobalt octylate, cobalt versatate, cobalt palmitate, cobalt rosinate, cobalt propionate, or cobalt boron complexes. Of these, it is preferable to use cobalt naphthenate, cobalt neodecanoate, a cobalt boron complex, or the like since the adhesiveness improves further. A
commercially available product may be used as the organic cobalt salt, and a specific example is 10% cobalt naphthenate or the like produced by the DIC
Corporation.
[0022]
The content of the organic cobalt salt is from 0.2 parts by mass to 1.0 parts by mass and preferably from 0.3 parts by mass to 0.7 parts by mass per 100 parts by mass of the rubber component when the mass of the organic cobalt salt is converted to the mass of cobalt. When the content of the organic cobalt salt is within the range described above, the adhesiveness to galvanized steel cords (with rubber) becomes favorable. In addition, when the content of the organic cobalt salt is less than 0.2 parts by mass, the adhesiveness to galvanized steel cords and the wet adhesion resistance are diminished, and when the content exceeds 1.0 parts by mass, the aging resistance of the rubber composition is diminished, which is not preferable. In particular, the content of the organic cobalt salt is preferably from 0.2 parts by mass to 1.0 parts by mass from the perspective of simultaneously achieving adhesiveness, wet adhesion resistance, and rubber properties.
[0023]
<Rosin>
The rosin contained in the composition of this embodiment is a type of natural resin also called pine resin. In addition, examples of rosin derivatives include gum rosins extracted from pine wood with a solvent or the like, wood rosins, tall oil rosins, polymers of these rosins, disproportionated rosins, maleated rosins, aldehyde-modified rosins, hydrogenated rosins, and processed products thereof. The rosin or rosin derivative may use a known product that is typically used as a tackifier. A commercially available product may be used as the rosin or rosin derivative, and specific examples include a gum rosin or wood rosin produced by Arakawa Chemical Industries, Ltd., a tall oil rosin produced by Harima Chemicals Group, Inc., and hydrogenated rosin produced by Hercules Co., Ltd.
[0024]
The content of the rosin or rosin derivative is from 2 parts by mass to 9 parts by mass and preferably from 3 parts by mass to 7 parts by mass per 100 parts by mass of the rubber component. When the content of the rosin or rosin derivative is within the range described above, the adhesiveness to galvanized steel cords (with rubber) is favorable, the roll processability is also favorable, and the cold resistance improves. When the content of the rosin or rosin derivative is less than 2 parts by mass, the wet adhesion resistance between the rubber composition and a galvanized steel cord is insufficient, and when the content exceeds 9 parts by mass, the tackiness of the rubber composition increases and the roll processability is diminished. In particular, the content of the rosin or rosin derivative is preferably from 2 parts by mass to 9 parts by mass from the perspective of simultaneously achieving both wet adhesion resistance and practical processability.
[0025]
The composition of this embodiment contains a rosin or a rosin derivative and therefore has excellent adhesiveness to galvanized steel cords and wet adhesion resistance. In addition, a rosin or rosin derivative is typically used as a tackifier, and when the composition of this embodiment contains a rosin or rosin derivative, the tackiness improves, and the tackiness to a roll simultaneously increases. When the tackiness to a roll is too high, the roll processability is diminished. Roll processability refers to the tackiness and processability of the unvulcanized rubber composition material and indicates the characteristic that the substance can be easily molded into the form of a sheet at the time of processing (at the time of rolling at a factory, in particular).
[0026]
<Organochlorine compound>
An organochlorine compound typically used as a chlorine-based flame retardant can be used as the organochlorine compound contained in the composition of this embodiment. A straight-chain organochlorine compound, for example, can be preferably used as the organochlorine compound.
Specific examples of straight-chain organochlorine compounds include chlorinated paraffin and chlorinated polyethylene. Commercially available products can be used for these compounds. For example, there are commercially available chlorinated paraffins with a chlorine content of 40% to 80%, and any of these products may be used. Examples of commercially available products include Toyoparax (chlorine content: 70 mass%, produced by Tosoh Corporation) and Enpara 70S (chlorine content: 70 mass%, produced by the DOVER CHEMICAL COMPANY).
[0027]
The content of the organochlorine compound is from 5 parts by mass to parts by mass and preferably from 5 parts by mass to 30 parts by mass per 35 100 parts by mass of the rubber component. When the content of the organochlorine compound is within the range described above, the flame retardancy of the composition of this embodiment improves. In addition, when the content of the organochlorine compound is less than 5 parts by mass, the adhesion is unstable, and when the content exceeds 35 parts by mass, the tackiness of the composition of this embodiment becomes too high, which makes it difficult to process. In particular, the content of the organochlorine compound is preferably from 5 parts by mass to 35 parts by mass from the perspective of simultaneously achieving both adhesiveness and processability.
[0028]
By containing an organochlorine compound, the adhesiveness - the initial adhesiveness, in particular - of the composition of this embodiment becomes favorable. Furthermore, the organochlorine compound imparts flame retardancy, so by containing the organochlorine compound in an amount within the range described above, the composition of this embodiment demonstrates both excellent flame retardancy and excellent cold resistance. Therefore, a steel cord conveyor belt produced using the composition of this embodiment described below sufficiently satisfies the flame retardancy required for a steel cord conveyor belt used in a mine or the like and can also be used in cold regions.
[0029]
As described above, the composition of this embodiment contains prescribed amounts of a butadiene rubber, a chloroprene rubber, and a natural rubber and further , contains prescribed amounts of an organic cobalt salt, a rosin or rosin derivative, and an organochlorine compound as essential components in 100 parts by mass of the rubber component, which yields excellent adhesiveness to galvanized steel cords and makes it possible to improve flame retardancy and cold resistance.
[0030]
In addition, it is preferable for the composition of this embodiment to contain the six essential components described above and for the numerical value A
calculated by the following formula (1) to be at most 83 parts by mass per 100 parts by mass of the rubber component.

8a
[0031]
[Formula 1]
A= chloroprene rubber (CR) x 0.8 + organochlorine compound x 1.5 + rosin x 2.5 (1)
[0032]
For the three components including a chloroprene rubber, an organochlorine compound, and a rosin, the numerical value A calculated by the above formula (1) is at most 83 parts by mass, preferably from 50 parts by mass to 83 parts by mass, and more preferably from 60 parts by mass to 83 parts by mass. By setting the amounts of the three components including a chloroprene rubber, an organochlorine compound, and a rosin to prescribed compounding ratios satisfying the relation that the numerical value A
calculated by the above formula (1) is at most 83 parts by mass, the composition of this embodiment yields excellent adhesiveness to galvanized steel cords, makes it possible to improve flame retardancy and cold resistance, and to further enhance the roll processability.
[0033]
In addition to the essential components described above, the composition of this embodiment may also contain a phenol resin, a carboxyl group-containing liquid isoprene rubber (prepared by introducing a carboxyl group into an isoprene polymer rubber produced by solution polymerization), and the like within a range that does not diminish the object of the present invention. In addition, the composition may also contain various other additives as necessary. Examples of additives include compounding agents or the like that are ordinarily used, including fillers such as carbon black;
vulcanization accelerator aids such as zinc oxide and stearic acid;
vulcanization accelerators such as dibenzothiazyl-disulfide; antiaging agents such as amine-based, phenol-based or wax-based agents; sulfur; and softeners such as plant oil-based softeners or mineral oil-based softeners. The composition may contain two or more types of these additives. The additives and the like may be kneaded and formed into a composition by a general method and used in vulcanizing or cross-linking. The compounding ratios of these additives may be any conventional standard amount, as long as the objects of this embodiment are not hindered.
[0034]
An example of a method for producing the composition of this embodiment is a method of adding from 5 parts by mass to 20 parts by mass of a butadiene rubber, from 20 parts by mass to 65 parts by mass of a chloroprene rubber, and a prescribed amount of a natural rubber as the remaining rubber component to 100 parts by mass of the rubber component described above, compounding from 0.2 parts by mass to 1.0 parts by mass of an organic cobalt salt per 100 parts by mass of the rubber component when the mass of the organic cobalt salt is converted to the mass of cobalt, from 2 parts by mass to 9 parts by mass of a rosin or rosin derivative per 100 parts by mass of the rubber component, and from 5 parts by mass to 35 parts by mass of an organochlorine compound per 100 parts by mass of the rubber component, appropriately selecting and adding prescribed amounts of the fillers, vulcanization accelerators, antiaging agents, and softeners described above as necessary, and kneading the mixture for a prescribed amount of time at a prescribed temperature using a roll mill, a Banbury mixer, or the like to obtain a rubber composition.
[0035]
5 The rubber composition obtained above can be adhered to a galvanized steel cord and subjected to sulfur vulcanization for a prescribed amount of time at a prescribed temperature so as to form a composite of the rubber and the galvanized steel cord.
[0036]
10 A product obtained by galvanizing a surface-untreated steel cord, for example, can be used as the steel cord to be adhered to the rubber composition described above. Electroplating, hot dip plating, or the like can be applied as a plating method. A galvanized product is preferably used as the steel cord used in a conveyor belt or the like from the perspective of rust prevention and durability. The strand diameter, cord diameter, or the like of the galvanized steel cord can be selected appropriately in accordance with the application when the galvanized steel cord is adhered to the rubber composition of this embodiment to form a composite.
[0037]
As an example of a method of adhering the composition of this embodiment to the galvanized steel cord, the rubber composition may be adhered to the galvanized steel cord with a prescribed thickness, and press vulcanization may be performed for 30 minutes at 150 C to form a composite of the rubber composition and the galvanized steel cord. Since the composition of this embodiment has excellent adhesion to galvanized steel cords, it can be used in products in which a galvanized steel cord is used as a reinforcing material. In addition, the composition can be used not only for steel cords, but also for other galvanized metal materials.
[0038]
The composition of this embodiment is suitably used in the production of a steel cord conveyor belt since it has the excellent characteristics described above, but it can also be suitably used in the production of hoses, crawler belts, marine hoses, tires, and the like.
[0039]
<Conveyor belt>
Next, a case in which the composition of this embodiment is used in a conveyor belt will be described. FIG. 1 is a cross-sectional perspective view of a conveyor belt according to this embodiment (called the "conveyor belt of this embodiment" hereafter). As illustrated in FIG. 1, the conveyor belt 10 has cover rubber layers 11 a and lib, a coating rubber layer 12, and a galvanized steel cord 13. The conveyor belt 10 is a conveyor belt 10 in which a galvanized steel cord 13 coated with the coating rubber layer 12 is provided as a core between the cover rubber layers 11 a and 11 b, for example, and in the conveyor belt 10, the coating rubber layer 12 contains a composite obtained by vulcanizing a product containing the aforementioned rubber composition and the galvanized steel cord 13. The method of forming a composite by vulcanizing a product containing the rubber composition of this embodiment and the galvanized steel cord 13 is as described above.
[0040]
The surface layer of the conveyor belt 10 consists of the two layers of the cover rubber layers 11 a and lib, and the coating rubber layer 12 containing the galvanized steel cord 13 as a core is between the two layers of the cover rubber layers 11 a and lib. The coating rubber layer 12 is obtained by molding the rubber composition of this embodiment into a sheet shape using a roller or the like, adding the galvanized steel cord 13 as a core, and vulcanizing the product. The surfaces of the rubber composition and the galvanized steel cord 13 are then firmly joined to form the coating rubber layer 12. The coating rubber layer 12 serves as an adhesive layer for the galvanized steel cord 13 and the cover rubber 11 as well as a buffering material for the galvanized steel cord 13. A rubber composition containing a component with excellent flame retardancy, heat resistance, cold resistance, oil resistance, abrasion resistance, or weather resistance is preferably used for the cover rubber layer 11 in accordance with the application of the conveyor belt 10.
[0041]
Since the conveyor belt 10 of this embodiment assumes the configuration described above, it has excellent adhesiveness to the galvanized steel cord 13, and the flame retardancy and cold resistance can be improved, so the conveyor belt 10 has excellent durability and long-term reliability. In addition, since the conveyor belt 10 of this embodiment has cold resistance and flame retardancy, it can be used even in cold regions with an outside air temperature of around -30 C, and fires can be prevented in mines.
[0042]
The method of producing the conveyor belt 10 of this embodiment is not particularly limited, and an ordinarily used method or the like can be employed.
A specific example of a method that can be suitably used is a method of kneading the raw materials using a roller, a kneader, a Banbury mixer, or the like, molding the product into a sheet shape for each of the cover rubber layers 11 a and lib using a roller or the like, then laminating each of the resulting layers in a prescribed order so as to sandwich the coating rubber layer (reinforcing layer) 12 obtained as described above, and then applying pressure for 10 to 60 minutes at a temperature of 140 to 170 C.
[0043]
The rubber composition and the conveyor belt of the present invention have been described in detail above, but the present invention should not be limited to the aforementioned examples but should be given the broadest interpretation consistent with the description as a whole.
EXAMPLES
[0044]
The composition of this embodiment will be described in detail hereinafter using working examples. However, the composition of this embodiment is not limited to these working examples.
[0045]
<Preparation of rubber compositions (Working Examples 1 to 6 and Comparative Examples 1 to 8) >
The components shown in Table 1 were compounded at the compounding ratios (parts by mass) shown in the table, and these were kneaded uniformly using a Banbury mixer to prepare the rubber compositions of Working Examples 1 to 6 and Comparative Examples 1 to 8. The compounding ratios of each of the components in the respective working examples and comparative examples are shown in Table 1.
[0046]
Evaluations of adhesiveness, wet adhesion resistance, flame retardancy, cold resistance, and roll processability were performed with the methods shown below for each of the rubber compositions obtained in each of the working examples and comparative examples. The results are shown in Table 1.

12a
[0047]
<Adhesiveness>
Each rubber composition of each working example and comparative example was adhered, with a thickness of 15 mm, to a galvanized steel cord with a diameter of 4.1 mm that was stored in a desiccator and subjected to dust proofing and moisture proofing treatment so as to form a composite of each rubber composition and the steel cord, and this was pressurized and vulcanized for 30 minutes at 150 C to form a test specimen (rubber/galvanized steel cord composite). The steel cord was pulled out of each obtained test specimen, and the adhesiveness was evaluated by the rubber coverage (%). Pulling tests were performed in accordance with DIN22131. The rubber coverage was calculated as the ratio (%) of covering area of the rubber remaining on the steel cord surface after being pulled out with respect to the surface area of the steel cord. The results were assessed as favorable when the rubber coverage was 70% or higher. The evaluation results are shown in Table 1 below. A higher rubber coverage indicates better adhesiveness.
[0048]
<Wet adhesion resistance>
The portions where the steel cord protrudes from the rubber surface of each of the same test specimens as those prepared for the adhesiveness evaluations above were sealed with beeswax and left for three weeks in a thermohygrostat bath with a temperature of 50 C and a relative humidity of 95%. The steel cord was then pulled out of each test specimen, and the wet adhesion resistance was evaluated by the rubber coverage (%). Pulling tests were performed in accordance with DIN22131. The results were assessed as favorable when the rubber coverage was 50% or higher. The evaluation results are shown in Table 1 below. A higher rubber coverage indicates better wet adhesion resistance.
[0049]
<Flame retardancy>
Each rubber composition obtained in each working example and comparative example described above was vulcanized for 30 minutes under a surface pressure of 3.0 MPa using a press molding machine at 150 C to form a vulcanized sheet with a thickness of 2 mm. A test piece (150 mm x 60 mm) was cut out of this sheet, and the oxygen index was measured in accordance with JIS K6269-1998. The results were assessed as favorable when the oxygen index was 32 or higher. The evaluation results are shown in Table 1 below. A higher measured oxygen index indicates higher flame retardancy.
[0050]
<Cold resistance>
A test piece was prepared from vulcanized rubber of each rubber composition in accordance with "Low-temperature brittleness test" of JIS
K6261-2006 "Rubber, vulcanized or thermoplastic - Determination of low-temperature properties." When impact bending was applied to the test pieces under prescribed conditions, the temperature at which 50% of the total number of test pieces broke (brittleness temperature) was measured. The results were assessed as favorable when the brittleness temperature was -35 C or lower.
The evaluation results are shown in Table 1 below. A lower measured brittleness temperature indicates higher cold resistance.
[0051]
<Roll processability>
Each rubber composition obtained in each working example and comparative example described above was passed through rolls heated to 40 C
with a gap of 2.0 mm, and the roll processability was evaluated by visually observing the peeling from the rolls. The roll processability was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1 below.
(Evaluation criteria) : There is no adhesion of the rubber composition to the roll surface 0: Adhesion of the rubber composition to the roll surface is slightly observed, but a sheet can be extracted.
A: Adhesion of the rubber composition to the roll surface is substantially observed, but a sheet can be extracted.
x: Adhesion of the rubber composition to the roll surface is observed, and sheet extraction is difficult.
[0052]
[Table 1]
Working Working Working Working Working Working Comparative Comparative Comparative Comparative Comparative Comparative Comparative Comparative Example Example Example Example Example Example Example Example Example Example Example Example Example Example NR 70.0 40.0 40.0 55.0 25.0 55.0 50.0 90.0 45.0 63.0 - 60.0 70.0 25.0 SBR - - - - - - 50.0 - - -40.0 - - -CR1 - - 45.0 - - - - 10.0 55.0 27.0 45.0 - - -CR2 25.0 45.0 - 30.0 60.0 30.0 _ - -- - 33.0 25.0 50.0 BR 5.0 15.0 15.0 15.0 15.0 15.0 - - -10.0 15.0 7.0 5.0 15.0 Organochlorine 27.0 12.0 12.0 24.0 5.0 24.0 20.0 27.0 27.0 27.0 12.0 38.0 27.0 2.0 compound HAF carbon 40.0 35.0 35.0 35.0 35.0 35.0 50.0 50.0 50.0 50.0 35.0 40.0 40.0 35.0 Rosin 5.0 3.0 3.0 3.0 3.0 3.0 - - _ - 3.0 5.0 10.0 3.5 Organic cobalt salt (metal 0.4 0.4 0.4 0.4 0.4 0.8 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 P
amount) c, Zinc oxide 4.0 4.3 4.3 4.0 4.6 4.0 6.5 6.5 6.5 6.5 4.3 4.0 4.0 4.3 0 Sulfur 3.0 3.5 3.5 3.5 3.5 3.5 3.5 3.0 3.0 3.0 3.5 3.0 3.0 3.5 .
..., u, Value of 73.0 61.5 61.5 67.5 63.0 67.5 30.0 48.5 84.5 62.1 61.5 95.9 85.5 63.0 Formula 1 -u, Adhesiveness c, (rubber 80 95 95 90 85 100 90 15 5 10 , coverage (%)) _ Wet adhesion resistance (rubber coverage (%) after three weeks of moisture proofing) Flame retardancy 32 35 35 33 39 33 28 28 33 33 (oxygen index) Cold resistance (brittleness -36.2 -39 -41.4 -39.8 -37.0 -43.3 -45.8 -33.4 -23.8 -35.8 -41.8 -31.4 -34.6 -37.9 temperature ( C)) Roll 0 0 0 0 0 0 @ 0 x 0 0 x x 0 processability
[0053]
The components shown in Table 1 are as follows.
= NR: Natural rubber, TSR-20 = SBR: styrene-butadiene rubber, trade name "NIPOL 1502", produced by Zeon Corporation = CR1: chloroprene rubber, sulfur-modified chloroprene rubber, trade name "Denka Chloroprene PM-40", produced by Denki Kagaku Kogyo K.K
= CR2: chloroprene rubber, non-sulfur-modified chloroprene rubber, trade name "Denka Chloroprene S-41", produced by Denki Kagaku Kogyo K.K
= BR: butadiene rubber, trade name "Nipol BR1220", produced by Zeon Corporation = Organochlorine compound: chlorinated paraffin, 70% chlorine content, trade name "Enpara 70S", produced by DOVER CHEMICAL
COMPANY
= HAF carbon: carbon black, trade name "Niteron #200", produced by Tokai Carbon Co., Ltd.
= Rosin: gum rosin, produced by Arakawa Chemical Industries, Ltd.
= Organic cobalt salt: cobalt naphthenate, 10% cobalt content, produced by DIC Corporation = Zinc oxide: vulcanization accelerator aid, trade name "Zinc Oxide III", produced by Seido Chemical Industry Co., Ltd.
= Sulfur: vulcanizing agent, oil treatment sulfur, produced by Hosoi Chemical Industry Co., Ltd.
= Value of Formula 1: value of the numerical value A calculated by the following formula [A = chloroprene rubber (CR) x 0.8 + organochlorine compound x 1.5 + rosin x 2.5] with respect to 100 parts by mass of the rubber component
[0054]
It was confirmed from the results shown in Table 1 that Working Examples 1 to 6 all demonstrated excellent adhesiveness, wet adhesion resistance, flame retardancy, cold resistance, and roll processability.
[0055]
In contrast, in Comparative Example 1, it was confirmed that the flame retardancy was poor since the composition did not contain a chloroprene rubber, and the wet adhesion resistance was poor since the composition did not contain a rosin. In addition, in Comparative Example 2, it was confirmed that the cold resistance was poor since the composition did not contain a butadiene rubber, the flame retardancy was poor since the content of the chloroprene =

rubber was insufficient, and the adhesiveness and wet adhesion resistance were poor since the composition did not contain a rosin. Furthermore, in Comparative Example 3, it was confirmed that the cold resistance was poor since the composition did not contain a butadiene rubber, the adhesiveness and wet adhesion resistance were poor since the composition did not contain a rosin, and the roll processability was poor since the value of Formula 1 exceeded 83. In addition, in Comparative Example 4, it was confirmed that the adhesiveness and wet adhesion resistance were poor since the composition did not contain a rosin. Furthermore, in Comparative Example 5, it was confirmed that the wet adhesion resistance was poor since the composition did not contain a natural rubber. In addition, in Comparative Example 6, it was confirmed that the cold resistance was poor since the content of the organochlorine compound was excessive, and the roll processability was poor since the value of Formula 1 exceeded 83. Furthermore, in Comparative Example 7, it was confirmed that the cold resistance was poor since the rosin content was excessive, and the roll processability was poor since the value of Formula 1 exceeded 83. In addition, in Comparative Example 8, it was confirmed that the flame retardancy was poor since the content of the organochlorine compound was insufficient.
[0056]
Accordingly, a rubber composition containing prescribed amounts of a butadiene rubber, a chloroprene rubber, and a natural rubber as the remaining rubber component and prescribed amounts of an organic cobalt salt, a rosin or rosin derivative, and an organochlorine compound in 100 parts by mass of a rubber component yields excellent adhesiveness to galvanized steel cords and makes it possible to improve flame retardancy and cold resistance (see Working Examples 1 to 6).
[0057]
In addition, by containing the six essential components described above and compounding the three components described above so that the numerical value A calculated by the following formula [A = chloroprene rubber x 0.8 +
organochlorine compound x 1.5 + rosin x 2.5] is at most 83 parts by mass per 100 parts by mass of the rubber component, it is possible to further enhance the roll processability (see Working Examples 1 to 6).
[0058]
Accordingly, it was ascertained that the composition of this embodiment can be suitably used in the production or the like of a steel cord conveyor belt from the fact that the composition yields excellent adhesiveness to galvanized steel cords and makes it possible to improve flame retardancy and cold resistance in comparison to conventionally used rubber compositions.
REFERENCE NUMERALS
[0059]
Conveyer belt 11, 11a, 11 b Cover rubber layers 12 Coating rubber layer 13 Steel cord (galvanized steel cord)

Claims (3)

WHAT IS CLAIMED IS:
1. A rubber composition comprising:
a rubber component containing a butadiene rubber, a chloroprene rubber, and a natural rubber;
an organic cobalt salt;
a rosin or a rosin derivative; and an organochlorine compound;
a content of the butadiene rubber being from 5 parts by mass to 20 parts by mass per 100 parts by mass of the rubber component;
a content of the chloroprene rubber being from 20 parts by mass to 65 parts by mass per 100 parts by mass of the rubber component;
a content of the organic cobalt salt being from 0.2 parts by mass to 1.0 parts by mass per 100 parts by mass of the rubber component when the mass of the organic cobalt salt is converted to the mass of cobalt;
a content of the rosin or rosin derivative being from 2 parts by mass to 9 parts by mass per 100 parts by mass of the rubber component; and a content of the organochlorine compound being from 5 parts by mass to 35 parts by mass per 100 parts by mass of the rubber component.
2. The rubber composition according to claim 1, wherein a numerical value A calculated by Formula (1) below is at most 83 parts by mass per 100 parts by mass of the rubber component.
[Formula 1]
A= chloroprene rubber (CR) x 0.8 + organochlorine compound x 1.5 + rosin x 2.5 (1)
3. A conveyor belt comprising a composite obtained by vulcanizing a product containing the rubber composition described in claim 1 or 2 and a galvanized steel cord.
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