CN113174103A - Rubber composition and conveyor belt - Google Patents

Rubber composition and conveyor belt Download PDF

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Publication number
CN113174103A
CN113174103A CN202110022073.0A CN202110022073A CN113174103A CN 113174103 A CN113174103 A CN 113174103A CN 202110022073 A CN202110022073 A CN 202110022073A CN 113174103 A CN113174103 A CN 113174103A
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rubber
mass
content
ethylene
conveyor belt
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CN202110022073.0A
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Inventor
山崎康平
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Yokohama Rubber Co Ltd
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Yokohama Rubber Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Belt Conveyors (AREA)

Abstract

The invention provides a rubber composition capable of forming a conveyor belt excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance, and a conveyor belt. The rubber composition of the present invention comprises: a rubber component containing chlorinated polyethylene and an olefin rubber; antimony trioxide; and a bromine-based flame retardant, wherein the content of antimony trioxide is 1 to 10 parts by mass per 100 parts by mass of the rubber component, and the content of the bromine-based flame retardant is 5 to 40 parts by mass per 100 parts by mass of the rubber component.

Description

Rubber composition and conveyor belt
Technical Field
The present invention relates to a rubber composition and a conveyor belt.
Background
Conventionally, in iron works, chemical plants, and the like, belt conveyors are used to continuously convey conveyed materials such as raw materials. A belt conveyor is generally a device that transports a conveyed object by moving or rotating a belt (conveyor belt) by a driving device such as a roller.
In the iron works or factories as described above, for example, frictional heat is generated in the belt conveyor and the conveyed material is sometimes heated, so that flame retardancy and heat resistance are required for the conveyor belt.
As a rubber composition used for forming a covering rubber layer in such a conveyor belt, for example, patent document 1 discloses a rubber composition containing 1 to 10 parts by mass of antimony trioxide and 10 to 50 parts by mass of a bromine-based flame retardant having a specific structure, based on 100 parts by mass of a rubber component containing at least an ethylene/1-butene copolymer.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6583518
Disclosure of Invention
Problems to be solved by the invention
In recent years, from the viewpoint of improvement in plant operation rate and the like, further improvement in performance has been demanded for conveyor belts, and for example, conveyor belts excellent in flame retardancy, flame retardancy after heat aging (excellent flame retardancy even after long-term exposure to a high-temperature environment), heat resistance, bending resistance and wear resistance have been demanded.
The present inventors have evaluated a rubber composition containing an ethylene/propylene copolymer and an ethylene/1-butene copolymer as rubber components and a brominated flame retardant and antimony trioxide as flame retardants or flame retardant aids, with reference to patent document 1, and found that at least 1 of flame retardancy, bending resistance and abrasion resistance after heat aging has room for improvement, although excellent flame retardancy and heat resistance.
Accordingly, the present invention has an object to provide a rubber composition capable of forming a conveyor belt excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance. The present invention also addresses the problem of providing a conveyor belt having excellent flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance, and wear resistance.
Means for solving the problems
The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have found that a conveyor belt excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance can be obtained by using a rubber composition containing a chlorinated polyethylene as a rubber component and containing predetermined amounts of antimony trioxide and a bromine-based flame retardant, and have completed the present invention.
That is, the present inventors have found that the above problems can be solved by the following configuration.
[1]
A rubber composition comprising:
a rubber component containing chlorinated polyethylene and an olefin rubber;
antimony trioxide; and
a brominated flame retardant which is a mixture of a brominated flame retardant,
the content of antimony trioxide is 1 to 10 parts by mass per 100 parts by mass of the rubber component,
the content of the bromine-based flame retardant is 5 to 40 parts by mass with respect to 100 parts by mass of the rubber component.
[2]
The rubber composition according to item [1], wherein the bromine-based flame retardant contains a bromine-based flame retardant having a melting point of 300 ℃ or higher.
[3]
The rubber composition according to [1] or [2], wherein the bromine-based flame retardant is a compound represented by the following formula (1).
In the formula (1) described later, R represents an aliphatic hydrocarbon group which may contain an unsaturated bond.
[4]
The rubber composition according to any one of [1] to [3], wherein a mass ratio of a content of the chlorinated polyethylene to a content of the brominated flame retardant is 8 or less.
[5]
The rubber composition according to any one of [1] to [4], wherein the rubber component is composed of only the chlorinated polyethylene and the olefin-based rubber,
the content of the chlorinated polyethylene is 1 to 40% by mass based on the total mass of the rubber component,
the content of the olefinic rubber is 60 to 99% by mass based on the total mass of the rubber component.
[6]
The rubber composition according to any one of [1] to [5], wherein the olefin-based rubber comprises an ethylene/propylene copolymer and an ethylene/1-butene copolymer,
the mass ratio of the content of the ethylene/1-butene copolymer to the content of the ethylene/propylene copolymer is 98 or less.
[7]
The rubber composition according to any one of [1] to [6], which is a rubber composition for a conveyor belt.
[8]
A conveyor belt produced using the rubber composition according to any one of [1] to [7 ].
[9]
The conveyor belt according to [8], which comprises a covering rubber formed by using the rubber composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a rubber composition capable of forming a conveyor belt excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance can be provided. Further, according to the present invention, a conveyor belt excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance can be provided.
Drawings
Fig. 1 is a cross-sectional view of an embodiment of a conveyor belt of the present invention.
Fig. 2 is a cross-sectional view of another embodiment of the conveyor belt of the present invention.
Detailed Description
The present invention will be described in detail below.
In the present specification, a numerical range expressed by "to" in the present specification means a range including numerical values described before and after "to" as a lower limit value and an upper limit value.
In the present specification, unless otherwise specified, each component may be used alone or in combination of 2 or more kinds of the substances corresponding to the component. When the component contains 2 or more substances, the content of the component means the total content of the 2 or more substances.
In the present specification, the method for producing each component is not particularly limited as long as it is not particularly specified. For example, a conventionally known method can be used.
In the present specification, the more excellent at least 1 of flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and abrasion resistance may be referred to as more excellent effect of the present invention.
[ rubber composition ]
The rubber composition of the present invention (hereinafter, also simply referred to as "the present composition") contains: a rubber component containing chlorinated polyethylene and an olefin rubber; antimony trioxide; and a brominated flame retardant. The content of antimony trioxide is 1 to 10 parts by mass per 100 parts by mass of the rubber component. The content of the brominated flame retardant is 5 to 40 parts by mass per 100 parts by mass of the rubber component,
the composition can be used to produce a conveyor belt excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance. The details of the reason for this are not clear, but the reason is presumed to be as follows.
It is presumed that the flame retardancy and heat resistance of the conveyor belt can be balanced at a high level by blending predetermined amounts of antimony trioxide and a bromine-based flame retardant in the rubber component.
The present inventors have made extensive studies on the rubber composition described in patent document 1, and as a result, have found that there is room for improvement in flame retardancy, bending resistance and abrasion resistance after heat aging of a conveyor belt. The reason for this is presumably that the bromine-based flame retardant is debrominated by the blending of antimony trioxide and the bromine-based flame retardant, and the deterioration of the rubber is promoted.
In view of this problem, the present inventors have found that if chlorinated polyethylene is used as the rubber component, a conveyor belt excellent in flame retardancy, bending resistance and abrasion resistance after heat aging can be obtained. The reason for this is presumed to be that the use of chlorinated polyethylene makes it difficult for the chlorinated polyethylene to dehalogenate and does not impair the thermal stability of the olefin rubber as compared with a bromine-based flame retardant in the structure of the chlorinated polyethylene.
The components contained in the present composition and components that can be contained in the composition will be described below.
[ rubber component ]
The rubber component in the present composition comprises chlorinated polyethylene and olefin rubber.
The content of the rubber component is preferably 30 to 60% by mass, and particularly preferably 40 to 50% by mass, based on the total mass of the present composition.
From the viewpoint of further improving the effect of the present invention, the total content of the chlorinated polyethylene and the olefinic rubber is more preferably 60 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the total mass of the rubber component.
The rubber component may contain a rubber other than chlorinated polyethylene and olefin-based rubber, but is preferably composed of only chlorinated polyethylene and olefin-based rubber from the viewpoint that the effect of the present invention is more excellent.
In the case where the rubber component is composed of only chlorinated polyethylene and the olefin-based rubber, from the viewpoint of further improving the effect of the present invention, it is preferable that the content of the chlorinated polyethylene is 1 to 40% by mass (more preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass) with respect to the total mass of the rubber component, and the content of the olefin-based rubber is 60 to 99% by mass (more preferably 80 to 99% by mass, particularly preferably 90 to 99% by mass) with respect to the total mass of the rubber component.
< chlorinated polyethylene >
The chlorinated polyethylene is not particularly limited.
In view of further improving the effect of the present invention, the chlorine content of the chlorinated polyethylene is preferably 20 to 50% by mass, and particularly preferably 25 to 40% by mass. Here, the chlorine content refers to a ratio of the chlorine content contained in the chlorinated polyethylene to the chlorinated polyethylene.
In view of the excellence of the present invention, the specific gravity of the chlorinated polyethylene is preferably 1.00 to 1.40g/cm3Particularly preferably 1.15 to 1.25g/cm3. Specific gravity of chlorinated polyethylene according to JIS Z8807: 2012.
In view of further improving the effect of the present invention, the content of the chlorinated polyethylene is preferably 1 to 40% by mass, more preferably 1 to 20% by mass, and particularly preferably 3 to 15% by mass, based on the total mass of the rubber component.
From the viewpoint of further improving the effects of the present invention, the mass ratio of the content of the chlorinated polyethylene to the content of the brominated flame retardant (content of the chlorinated polyethylene/content of the brominated flame retardant) is preferably 8 or less, more preferably 3 or less, further preferably 2 or less, particularly preferably 0.50 or less, and most preferably 0.35 or less. In addition, from the viewpoint of further excellence in the effect (particularly, heat resistance) of the present invention, the lower limit value of the mass ratio (content of chlorinated polyethylene/content of bromine-based flame retardant) is preferably more than 0, more preferably 0.10 or more, further preferably 0.15 or more, and particularly preferably more than 0.20.
From the viewpoint of further improving the effect of the present invention, the mass ratio of the content of the chlorinated polyethylene to the content of the antimony trioxide (content of the chlorinated polyethylene/content of the antimony trioxide) is preferably 0.1 to 10.0, more preferably 0.3 to 6.0, and particularly preferably 0.5 to 2.0.
< olefin-based rubber >
The olefin rubber is not particularly limited.
The chlorine content of the olefin-based rubber is preferably less than 20% by mass, and particularly preferably 10% by mass or less. Here, the chlorine content refers to a ratio of the chlorine content contained in the olefin rubber to the olefin rubber.
From the viewpoint of further improving the effect of the present invention, the specific gravity of the olefin rubber is preferably 0.70g/cm3Above and less than 1.00g/cm3Particularly preferably 0.75 to 0.99g/cm3. The specific gravity of the olefin rubber can be measured by the same method as that for the chlorinated polyethylene.
From the viewpoint of further improving the effect of the present invention, the content of the olefinic rubber is preferably 60 to 99% by mass, more preferably 80 to 99% by mass, and particularly preferably 85 to 99% by mass, based on the total mass of the rubber component.
Specific examples of the olefin-based rubber include an ethylene/propylene copolymer, an ethylene/1-butene copolymer, an ethylene/1-octene copolymer, an ethylene/propylene/diene copolymer, a maleic acid-modified ethylene/propylene copolymer, a maleic anhydride-modified ethylene/α -olefin copolymer, an ethylene/glycidyl methacrylate copolymer, a maleic anhydride-modified ethylene/ethyl acrylate copolymer, a butyl rubber, a copolymer of isobutylene and an aromatic vinyl compound or a diene-based monomer, an acrylic rubber, an ionomer, and the like.
From the viewpoint of further improving the effects of the present invention, the olefin-based rubber preferably contains at least one of an ethylene/propylene copolymer and an ethylene/1-butene copolymer, and particularly preferably consists of an ethylene/propylene copolymer and an ethylene/1-butene copolymer.
(ethylene/propylene copolymer)
The ethylene/propylene copolymer is not particularly limited as long as it is a copolymer of ethylene and propylene, and conventionally known copolymers can be used.
It is exemplified that at least a part or all of the repeating units composed of propylene constituting the ethylene/propylene copolymer is- [ CH (-CH) (-)3)-CH2]As one of the preferred embodiments. In this case, the ethylene/propylene copolymer may have a structure represented by the above-mentioned-CH3The formed branch chain.
An ethylene/propylene copolymer is a preferred embodiment of a copolymer in which the repeating unit constituting the copolymer is only ethylene and propylene.
From the viewpoint of further improving the effect of the present invention, the weight average molecular weight of the ethylene/propylene copolymer is preferably more than 100,000, more preferably 200,000 to 500,000, and particularly preferably 250,000 to 400,000.
The ethylene content of the ethylene/propylene copolymer is preferably 40 to 60% by mass, more preferably 40% by mass or more and less than 60% by mass, and still more preferably 45 to 55% by mass, because the effect (particularly, heat resistance) of the present invention is more excellent.
The ethylene content of the ethylene/propylene copolymer can be calculated based on ASTM D3900.
The content of the ethylene/propylene copolymer is preferably 1 to 99% by mass, more preferably 35 to 85% by mass, and particularly preferably 40 to 70% by mass, based on the total mass of the olefin rubber.
(ethylene/1-butene copolymer)
The ethylene/1-butene copolymer is not particularly limited as long as it is a copolymer of ethylene and 1-butene, and conventionally known copolymers can be used.
An ethylene/1-butene copolymer is a copolymer in which the repeating units constituting the copolymer are only ethylene and 1-butene, and is one of preferable embodiments.
In the ethylene/1-butene copolymer, the mooney viscosity at 125 ℃ of the ethylene/1-butene copolymer is preferably 20 or more, more preferably 30 or more, and particularly preferably 40 or more, from the viewpoint that the effect (particularly, heat resistance) of the present invention is more excellent. The upper limit of the mooney viscosity is not particularly limited, but is preferably 70 or less, and more preferably 55 or less.
The Mooney viscosity at 125 ℃ is a value determined in accordance with JIS K6300-1: 2013, viscosity (ML1+4, 125 ℃ C.) measured using an L-shaped rotor under the conditions of a preheating time of 1 minute, a rotation time of 4 minutes of the rotor, and a test temperature of 125 ℃ (the same applies hereinafter).
The ethylene content of the ethylene/1-butene copolymer is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, based on the ethylene/1-butene copolymer.
The ethylene content of the ethylene/1-butene copolymer can be calculated based on ASTM D3900.
The content of the ethylene/1-butene copolymer is preferably 1 to 99% by mass, more preferably 15 to 65% by mass, and particularly preferably 30 to 60% by mass, based on the total mass of the olefin rubber.
In the case where the olefin-based rubber contains an ethylene/propylene copolymer and an ethylene/1-butene copolymer, the mass ratio of the content of the ethylene/1-butene copolymer to the content of the ethylene/propylene copolymer (content of the ethylene/1-butene copolymer/content of the ethylene/propylene copolymer) is preferably 98 or less, more preferably 5 or less, and particularly preferably 2 or less, from the viewpoint of further excellent effects of the present invention. In addition, from the viewpoint of further improving the effect of the present invention, the lower limit of the mass ratio (the content of the ethylene/1-butene copolymer/the content of the ethylene/propylene copolymer) is more than 0, preferably 0.1 or more, and particularly preferably 0.5 or more.
[ antimony trioxide ]
Antimony trioxide (Sb) contained in the present composition2O3) There is no particular limitation. Antimony trioxide can act as a flame retardant aid for a brominated flame retardant described later.
The content of antimony trioxide is preferably 2.0 to 9.0 parts by mass, more preferably 3.0 to 7.0 parts by mass, and particularly preferably 5.0 to 7.0 parts by mass, from the viewpoint of further improving the effect of the present invention, with respect to 100 parts by mass of the rubber component.
[ bromine-based flame retardant ]
The brominated flame retardant contained in the composition is a flame retardant containing bromine atoms.
Specific examples of the bromine-based flame retardant include compounds represented by the following formula (1), decabromodiphenyl ether, tetradecobromo-1, 4-diphenoxybenzene, octabromodiphenyl ether, tetrabromodiphenyl ether, tetrabromophthalic anhydride, tetrabromophthalate, 1, 2-bis (2,4, 6-tribromophenoxy) ethane, 2,4, 6-tris (2,4, 6-tribromophenoxy) -1,3, 5-triazine, 2, 4-dibromophenol and its polymer, 2, 6-dibromophenol and its polymer, brominated polystyrene and its polymer, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromocyclodecane, hexabromobenzene, and pentabromobenzylacrylate and its polymer. Among them, from the viewpoint of further improving the effects of the present invention, preferred are compounds represented by the following formula (1), decabromodiphenyl ether, and ethylenebistetrabromophthalimide, and particularly preferred are compounds represented by the following formula (1).
From the viewpoint of further improving the effect of the present invention, the bromine-based flame retardant preferably contains a bromine-based flame retardant having a melting point of 300 ℃ or higher, and particularly preferably has a melting point of 300 ℃ or higher.
From the viewpoint of further improving the effect of the present invention, the melting point of the bromine-based flame retardant is preferably 320 ℃ or higher, and particularly preferably 340 ℃ or higher.
Specific examples of the bromine-based flame retardant having a melting point of 300 ℃ or higher include decabromodiphenyl ether (melting point 305 ℃), tetradecylbromine-1, 4-diphenoxybenzene (melting point 380 ℃), ethylenebistetrabromophthalimide (446 ℃), and bis (pentabromophenyl) ethane (melting point 350 ℃) among compounds represented by the following formula (1).
The melting point of the brominated flame retardant is a temperature at an endothermic peak caused by melting measured by a Differential Scanning Calorimetry (DSC) method.
From the viewpoint of further improving the effect of the present invention, the bromine-based flame retardant is preferably a compound represented by the following formula (1).
Figure BDA0002888942470000091
In formula (1), R represents an aliphatic hydrocarbon group that may contain an unsaturated bond.
The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. An appropriate embodiment is a linear one.
The number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited. Can be, for example, 1 to 10. The number of carbon atoms is preferably 2 to 8.
The aliphatic hydrocarbon group may be saturated or unsaturated. Examples of the unsaturated bond include a vinyl group, an ethenylene group, an ethynylene group, and an ethynylene group.
Examples of the hydrocarbon group include a methylene group, an ethylene group, a 1, 3-propylene group, a 1, 2-propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group.
Examples of the compound represented by the formula (1) include bis (pentabromophenyl) ethane.
The compound represented by formula (1) is preferably bis (pentabromophenyl) ethane from the viewpoint of excellent flame retardancy.
The content of the bromine-based flame retardant is preferably 5 to 40 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 5 to 20 parts by mass, based on 100 parts by mass of the rubber component, from the viewpoint of further improving the effect of the present invention.
[ optional ingredients ]
The composition may further contain additives such as carbon black, silica, zinc white (zinc oxide), stearic acid, wax, processing aids, process oils, liquid polymers, vulcanizing agents, vulcanization accelerators, crosslinking agents, anti-aging agents, softening agents, and flame retardants other than the above, in addition to the above components, within a range not to impair the object of the present invention. The content of these additives may be appropriately determined within a range not impairing the object of the present invention.
[ preparation method of rubber composition ]
The method for producing the composition is not particularly limited, and specific examples thereof include a method of kneading the above components using a known apparatus (for example, a banbury mixer, a kneader, a roll, etc.). When the present composition contains a vulcanizing agent, it is preferable that components other than the vulcanizing agent are first mixed at a high temperature (preferably 100 to 160 ℃), cooled, and then mixed with the vulcanizing agent.
The composition may be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.
[ use ]
The use of the present composition is not particularly limited, and examples thereof include tires (particularly pneumatic tires), hoses and conveyor belts. Among these, the present composition is preferably a rubber composition for a conveyor belt.
[ conveyor belt ]
Next, a conveyor belt according to the present invention will be described.
The conveyor belt of the present invention is a conveyor belt produced using the present composition. The shape and manufacturing method are the same as those of a known conveyor belt.
There is no particular limitation on which constituent member in the conveyor belt of the present invention the present composition is applied. So long as all or a part of the rubber constituting the conveyor belt of the present invention is formed of the present composition.
The present composition is excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and abrasion resistance, and therefore, a conveyor belt of the present invention having a covering rubber formed by using the present composition is one of preferable embodiments.
Specific configurations of the conveyor belt of the present invention include, for example, the configurations described below. In addition, the conveyor belt of the present invention is not limited to the attached drawings.
A conveyor belt 1 according to an embodiment of the present invention will be described with reference to fig. 1.
Fig. 1 is a cross-sectional view of an embodiment of a conveyor belt of the present invention. As shown in fig. 1, a conveyor belt 1 according to embodiment 1 of the present invention is a conveyor belt 4 in which a fabric layer 1 is covered with a coating rubber (adhesive rubber) 2 to form a core layer, and the outer periphery thereof is covered with a covering rubber 3. The covering rubber 3 is preferably formed of the present composition.
The conveyor belt 4 shown in fig. 1 has the fabric layer 1 as a core material, and the number of laminated fabric layers 1, the thickness of the covering rubber 3, the belt width, and the like can be appropriately determined depending on the purpose of use.
Examples of the cloth layer include canvas made of a woven fabric of synthetic fibers such as nylon, vinylon, and polyester.
Thickness T of the coating rubber 31、T2In general, the thickness may be about 1.5 to 20 mm.
The coating rubber 2 may be a coating rubber used for a known conveyor belt, and may be a rubber composition containing, for example, Natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), ethylene/propylene rubber (EPM), Ethylene Propylene Diene Monomer (EPDM), or the like as a rubber component.
Next, embodiment 2 of the conveyor belt of the present invention will be described with reference to fig. 2.
Fig. 2 is a cross-sectional view of another embodiment of the conveyor belt of the present invention.
As shown in fig. 2, the 2 nd embodiment of the conveyor belt according to the present invention is a conveyor belt 8 in which a steel cord 5 is covered with a cushion rubber (adhesive rubber) 6 to form a core layer, and the outer periphery thereof is covered with a covering rubber 7. The covering rubber 7 is preferably formed of the present composition.
The conveyor belt 8 can be made into a core material by arranging about 50 to 230 steel cords 5 having a diameter of about 2.0 to 9.5mm, each of which is formed by twisting a plurality of strands having a diameter of about 0.2 to 0.4 mm. Generally, the total thickness T of the conveyor belt 8 may be about 10 to 50 mm.
The cushion rubber 6 may be made of, for example, an adhesive rubber capable of adhering to a galvanized steel cord, which is used for a known steel conveyor belt, and specifically, a rubber composition containing, as a rubber component, Natural Rubber (NR), acrylonitrile butadiene rubber (NBR), Styrene Butadiene Rubber (SBR), Butadiene Rubber (BR), ethylene/propylene rubber (EPM), Ethylene Propylene Diene Monomer (EPDM), or the like.
The conveyor belt of the present invention can be easily manufactured by, for example, interposing a fabric layer or a steel cord as a core material between unvulcanized rubber sheets molded from the present composition and vulcanizing the unvulcanized rubber sheets by heating and pressing according to a conventional method. The vulcanization is usually carried out at about 120 to 180 ℃ and about 0.1 to 4.9MPa for about 10 to 90 minutes.
The conveyor belt of the present invention is excellent in flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance and wear resistance, because the present composition is used.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited thereto.
[ production of composition ]
Each composition was produced by using the components shown in table 1 below in the composition (parts by mass) shown in the table and mixing them in a banbury mixer.
[ evaluation test ]
[ flame retardancy ]
Using each composition, according to JIS K6324: 2013 (flame retardant コンベヤベルト -grade test and test method) "7.2.1 item cloth layer conveyor rubber was used to prepare a sample (the sample had a size of 200mm long side and 25mm short side) for the test sample. In each test sample (flame retardant conveyor belt), the composition described above formed a covering rubber and the fabric layer formed a core material.
Based on JIS K6324: 2013 (flame retardancy コンベヤベルト -grade) and the vent test method (flame retardancy tape-grade and test method) "were evaluated for flame retardancy (flame disappearance time in seconds), and using the test sample, the flame retardancy was evaluated on the following basis. Further, if the evaluation result is "good", the flame retardancy is evaluated to be excellent. The results are shown in table 1.
Good: flame disappearance time of less than 10 seconds
And (delta): the flame disappearance time is 10 to 30 seconds
X: flame disappearance time of more than 30 seconds
[ flame retardancy after Heat aging ]
The test specimens prepared in the same manner as in the "flame retardancy" were left to stand at 180 ℃ for 168 hours and subjected to heat aging treatment, to obtain evaluation specimens after the heat aging treatment. The obtained test specimens (after heat aging treatment) were used to evaluate the flame retardancy after aging by the same test methods and evaluation criteria as those of the above "flame retardancy". Further, if the evaluation result is "good", the flame retardancy is evaluated to be excellent. The results are shown in table 1.
[ Heat resistance ]
The evaluation of heat resistance was performed based on the elongation at break (EB, unit%) before and after the heat aging treatment using a test sample obtained using the rubber composition.
Specifically, each of the compositions was vulcanized for 45 minutes under a pressure of 3.0MPa in a press molding machine at 160 ℃ to prepare a vulcanized sheet having a thickness of 2 mm. From the sheet, a dumbbell test piece of JIS3 was punched out to obtain a test specimen.
Using the obtained test sample (before heat aging treatment), the temperature was measured at room temperature in accordance with JIS K6251: 2017A tensile test was conducted at a tensile rate of 500 mm/min, and the elongation at break (EB, unit%) was measured (hereinafter, also referred to as "initial EB").
The test sample (before heat aging) was left at 180 ℃ for 168 hours and heat aged to obtain a test sample after heat aging. Using the obtained test sample (after heat aging treatment), a tensile test was performed under the same conditions as the test sample before heat aging treatment, and the elongation at break (EB, unit%) (hereinafter, also referred to as "EB after heat aging") was measured.
Based on the values of "initial EB" and "EB after heat aging" obtained in this way, the change rate (%) of elongation at break before and after heat aging treatment was calculated by the following formula. When the change rate was-25% or more, the heat resistance was evaluated to be excellent. When the rate of change was-10% or more, the heat resistance was evaluated to be more excellent. In addition, the thermal aging resistance is more satisfactory as the value of the rate of change is closer to 0% regardless of whether the value is positive or negative. The results are shown in the column "heat resistance" in table 1.
The rate of change in elongation at break (%) before and after heat aging treatment was 100 × { (EB after heat aging) - (initial EB) }/(initial EB)
[ bending resistance ]
According to JIS K6260: 2017 was subjected to a crack growth test caused by repeated bending.
Specifically, each composition was vulcanized for 45 minutes under a pressure of 3.0MPa of surface pressure to prepare JIS K6260: 2017, 5.1. A test piece having a predetermined size in the above-mentioned flexural crack growth test was prepared, and the test piece with a notch formed by a predetermined cutting edge was subjected to a flexural resistance test by an デマチャ flexural tester (temperature: 23 ℃, stroke: 57mm, speed: 300. + -. 10rpm, total number of bending times: 40 ten thousand). After the test, the length of the crack was determined. After the above test, when the test piece did not break, the bending resistance was evaluated as excellent. The smaller the length of the crack, the more excellent the bending resistance was evaluated. After the completion of the test, the test piece was broken to be "x".
[ abrasion resistance ]
The composition was vulcanized for 45 minutes at a pressing temperature of 160 ℃ and a surface pressure of 3.0MPa using a press molding machine, to prepare a test specimen having a diameter of 16mm and a thickness of 6 mm.
According to JIS K6264-2:2005, abrasion test of test specimen at room temperature (method A) using DIN abrasion tester, abrasion amount [ mm [ [ mm ]3]The abrasion resistance was evaluated by the following criteria. Further, if the evaluation result is "good", the evaluation is excellent in abrasion resistance. The results are shown in table 1.
Good: the abrasion loss is less than 150mm3
X: the abrasion loss is 150mm3The above
[ Table 1]
Figure BDA0002888942470000151
The details of each component in table 1 are as follows.
Ethylene/propylene copolymers: the trade name is "KEP-110" (manufactured by KUMLO POLYCHEM Co., Ltd.). The weight average molecular weight of the ethylene/propylene copolymer was 310,000, and the ethylene content thereof was 52 mass%. The ethylene/propylene copolymer (KEP-110) has a weight average molecular weight of more than 100,000 and thus corresponds to the ethylene/propylene copolymer 1. The ethylene/propylene copolymer has at least a part or all of repeating units derived from propylene as-CH (-CH)3)-CH2-, thus having the formula-CH3The formed branch chain.
Ethylene/1-butene copolymer: the trade name "Engage 7487" (manufactured by ダウケミカル Co.). The Mooney viscosity at 125 ℃ of the ethylene/1-butene copolymer was 47, and the ethylene content thereof was 74% by mass.
Chlorinated polyethylene: the product name is "Weipren 6235" (manufactured by Weifang corporation), and the specific gravity is 1.19g/cm3Chlorine content 35. + -.1% by mass
ISAF grade carbon black: trade name "ニテロン # 300" (manufactured by Rizhi カーボン Co., Ltd.)
Zinc oxide: trade name "acidified yellow type 3 mutant" manufactured by Zhenzi chemical industry Co., Ltd
Stearic acid: trade name "ステアリン acid 50S" (manufactured by Qianye fatty acid Co., Ltd.)
Anti-aging agent (ノクラック MMB): trade name "ノクラック MMB" (manufactured by Dai Xinxing chemical industry Co., Ltd.)
Antimony trioxide: trade name "PATOX-M" (manufactured by Japan concentrate Co., Ltd.), flame retardant aid
Bromine flame retardant (SAYTEX 8010): under the trade name "SAYTEX 8010" (manufactured by ALBEMARLE CORPORATION), bis (pentabromophenyl) ethane
Softening agent: trade name "ルーカント HC-3000X" (manufactured by Mitsui chemical Co., Ltd.), weight-average molecular weight 14,000, ethylene/propylene copolymer oil
Crosslinker 1(ハイクロス GT): trade name "ハイクロス GT" (manufactured by Seiko chemical Co., Ltd.)
Crosslinker 2(パーカドックス 14-40): the trade name is "パーカドックス 14-40" (made by Zubuzubu アクゾ)
As shown in table 1, it was confirmed that if a rubber composition in which 1 to 10 parts by mass of antimony trioxide and 5 to 40 parts by mass of a bromine-based flame retardant were added to 100 parts by mass of a rubber component containing an olefin-based rubber and a chlorinated polyethylene, a conveyor belt having excellent flame retardancy, flame retardancy after heat aging, heat resistance, bending resistance, and wear resistance could be obtained (examples 1 to 7).
Further, from the comparison of examples 1 to 7, it was confirmed that if the mass ratio of the content of the chlorinated polyethylene to the content of the brominated flame retardant exceeds 0.20 and is 8 or less (example 1), a conveyor belt having more excellent heat resistance can be obtained.
Further, from the comparison of examples 1 to 7, it was confirmed that if the mass ratio of the content of the chlorinated polyethylene to the content of the antimony trioxide is 0.60 to 10.0 (examples 1 to 4,6, and 7), a conveyor belt having more excellent bending resistance can be obtained.
On the other hand, as shown in table 1, it was confirmed that when the rubber component does not contain chlorinated polyethylene, and/or when the content of at least one of antimony oxide and a brominated flame retardant is outside the above range with respect to 100 parts by mass of the rubber component, at least 1 of the flame retardancy, the flame retardancy after heat aging, the heat resistance, the bending resistance and the wear resistance of the conveyor belt was poor.
Description of the symbols
1: cloth layer
2: coated rubber
3. 7: covering rubber
4. 8: conveying belt
5: steel cord
6: and (3) buffer rubber.

Claims (9)

1. A rubber composition comprising:
a rubber component comprising chlorinated polyethylene and an olefin-based rubber;
antimony trioxide; and
a brominated flame retardant which is a mixture of a brominated flame retardant,
the content of antimony trioxide is 1 to 10 parts by mass relative to 100 parts by mass of the rubber component,
the content of the bromine-based flame retardant is 5 to 40 parts by mass with respect to 100 parts by mass of the rubber component.
2. The rubber composition according to claim 1, wherein the brominated flame retardant comprises a brominated flame retardant having a melting point of 300 ℃ or higher.
3. The rubber composition according to claim 1 or 2, wherein the bromine-based flame retardant is a compound represented by the following formula (1),
Figure FDA0002888942460000011
in formula (1), R represents an aliphatic hydrocarbon group that may contain an unsaturated bond.
4. The rubber composition according to any one of claims 1 to 3, wherein a mass ratio of the content of the chlorinated polyethylene to the content of the brominated flame retardant is 8 or less.
5. The rubber composition according to any one of claims 1 to 4, wherein the rubber component is composed of only the chlorinated polyethylene and the olefin-based rubber,
the content of the chlorinated polyethylene is 1 to 40% by mass based on the total mass of the rubber component,
the content of the olefinic rubber is 60 to 99% by mass based on the total mass of the rubber component.
6. The rubber composition according to any one of claims 1 to 5, wherein the olefin-based rubber comprises an ethylene/propylene copolymer and an ethylene/1-butene copolymer,
the mass ratio of the content of the ethylene/1-butene copolymer to the content of the ethylene/propylene copolymer is 98 or less.
7. The rubber composition according to any one of claims 1 to 6, which is a rubber composition for a conveyor belt.
8. A conveyor belt produced by using the rubber composition according to any one of claims 1 to 7.
9. The conveyor belt of claim 8 having a cover rubber formed using the rubber composition.
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CN102807714A (en) * 2012-07-31 2012-12-05 天津鹏翎胶管股份有限公司 Rubber composition used for outer layer rubber of power-steering low-pressure oil pipe
CN108003540A (en) * 2017-12-19 2018-05-08 江苏通用科技股份有限公司 Improve ethylene propylene diene rubber and the composite material of chlorinated polyethylene rubber compatibility and preparation method thereof
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CN101616982A (en) * 2008-01-16 2009-12-30 横滨橡胶株式会社 Chlorinated rubber composition and flexible pipe
CN102807714A (en) * 2012-07-31 2012-12-05 天津鹏翎胶管股份有限公司 Rubber composition used for outer layer rubber of power-steering low-pressure oil pipe
CN108003540A (en) * 2017-12-19 2018-05-08 江苏通用科技股份有限公司 Improve ethylene propylene diene rubber and the composite material of chlorinated polyethylene rubber compatibility and preparation method thereof
JP6583518B1 (en) * 2018-11-28 2019-10-02 横浜ゴム株式会社 Rubber composition for conveyor belt and conveyor belt

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