CN106459540A - Regenerated rubber, process for producing same, and transmission belt including same - Google Patents
Regenerated rubber, process for producing same, and transmission belt including same Download PDFInfo
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- CN106459540A CN106459540A CN201580033659.XA CN201580033659A CN106459540A CN 106459540 A CN106459540 A CN 106459540A CN 201580033659 A CN201580033659 A CN 201580033659A CN 106459540 A CN106459540 A CN 106459540A
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- rubber
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- reclaimed rubber
- transmission band
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G1/00—Driving-belts
- F16G1/06—Driving-belts made of rubber
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16G—BELTS, CABLES, OR ROPES, PREDOMINANTLY USED FOR DRIVING PURPOSES; CHAINS; FITTINGS PREDOMINANTLY USED THEREFOR
- F16G5/00—V-belts, i.e. belts of tapered cross-section
- F16G5/04—V-belts, i.e. belts of tapered cross-section made of rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
A regenerated rubber which is derived from a sulfur-crosslinked rubber composition containing ethylene, propylene, and diene monomers and which has a gel content of 50-85 mass%.
Description
Technical field
The present invention relates to a kind of reclaimed rubber and manufacture method thereof and employ the transmission band of this reclaimed rubber.
Background technology
Reclaimed rubber is by implementing chemical treatment or physical treatment to the crosslinked rubber of used rubber, and
Again become the rubber of the state that can form.The use of reclaimed rubber is for the material cost cutting down rubber and manufacture
Cost is extremely effective.
Patent Document 1 discloses the manufacture method of a kind of reclaimed rubber, under this manufacture method, real to crosslinked rubber
Execute temperature 180～350 DEG C and shear stress 10～150kg/cm2The desulfurization process of condition.
Patent Document 2 discloses the manufacture method of a kind of reclaimed rubber, under this manufacture method, for crosslinked rubber
Apply shear stress under heating-up temperature more than the regeneration temperature causing the cut-outs such as the crosslinking between this rubber molecule.
Patent Document 3 discloses the manufacture method of a kind of reclaimed rubber, under this manufacture method, by crosslinked rubber
Material powder mixes with polydiene, applies the maximum shear speed shear stress of more than 300/ second to it.
Patent Document 4 discloses the manufacture method of a kind of reclaimed rubber, under this manufacture method, crosslinked rubber is executed
Degree of heating 220～350 DEG C and shear stress 10～150kg/cm2The desulfurization process of condition.
Patent document 1：Japanese Laid-Open Patent Publication Laid-Open flat 9-227724 publication
Patent document 2：Japanese Laid-Open Patent Publication Laid-Open 2001-30237 publication
Patent document 3：Japanese Laid-Open Patent Publication Laid-Open 2003-128843 publication
Patent document 4：Japanese Laid-Open Patent Publication Laid-Open 2004-35690 publication
Content of the invention
The reclaimed rubber of the present invention is such, i.e.：Comprise ethylene propylene diene rubber as rubber constituent, and gel fraction is
50～85 mass %.
The manufacture method of the reclaimed rubber of the present invention is such, i.e.：To comprising the ethylene-propylene-diene monomer crossed by sulfur cross-linking
After the crosslinked rubber of glue is pulverized, shear stress is applied to chippy described crosslinked rubber and carries out desulfurization process, thus
Obtain the reclaimed rubber that gel fraction is 50～85 mass %.
The transmission band of the present invention is such, i.e.：Constituted by the rubber composition of the reclaimed rubber employing the present invention
At least a portion of the band main body of described transmission band.
Brief description
Fig. 1 is the partial perspective cross-sectional figure of the infantees V band involved by the first embodiment.
Fig. 2 A is the first explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 2 B is the second explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 2 C is the 3rd explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 2 D is the 4th explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 2 E is the 5th explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 2 F is the 6th explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 2 G is the 7th explanatory diagram of the manufacture method illustrating the infantees V band involved by embodiment.
Fig. 3 is the belt wheel floor plan with traveling testing machine that embodiment is used.
Fig. 4 is the photo of the cut surface of the reclaimed rubber observing embodiment 2-1.
Detailed description of the invention
Below, referring to the drawings embodiment is illustrated.
(the first embodiment)
＜ reclaimed rubber ＞
The ethylene propylene diene rubber that the next self-contained sulfur cross-linking of reclaimed rubber involved by first embodiment is crossed is (hereinafter referred to as
Make " EPDM ".) rubber composition, and gel fraction is higher, is 50～85 mass %.Regeneration involved by first embodiment
Rubber is used by oneself the EPDM that sulfur cross-linking is crossed, and owing to it makes gel fraction higher with sulfur cross-linking, is 50～85 matter
Amount %, thus for the rubber composition using this reclaimed rubber, caoutchouc elasticity is higher and tan δ is relatively low.It is therefore preferable that：By
Employ the rubber composition of reclaimed rubber involved by the first embodiment, constitute the transmission of alternating bending particularly to be carried out
At least a portion of the band main body of band.
Here, be crosslinked from carrying out easily again, and physical property deterioration can be suppressed and excellent processability can be obtained
From the viewpoint of, the gel fraction of the reclaimed rubber involved by the first embodiment is preferably more than 50 mass %, more preferably 65
More than quality %, and preferably below 85 mass %, more preferably below 80 mass %.
Gel fraction is tried to achieve by so-called toluene swelling method.Specifically, cut reclaimed rubber test film (such as 20mm ×
The cuboid of 10mm × 2mm), this test film is immersed in the toluene of 30 DEG C 72 hours and is dried again after making its swelling, by impregnating
Quality (W before toluene0) and dipping toluene after quality (W3) calculate gel fraction gw=(W3/W0)×100.It should be noted that
The method also states that for example《Rubber experiment method (Japan rubber association of civic organization edits distribution)》In Deng.
Reclaimed rubber involved by first embodiment comprises rubber constituent and rubber chemicals in addition.
In the reclaimed rubber involved by the first embodiment, the content of rubber constituent is preferably more than 30 mass %, more excellent
It is selected in more than 40 mass %, and preferably below 70 mass %, more preferably below 60 mass %.
In the rubber constituent of the reclaimed rubber involved by the first embodiment the content of EPDM preferably 50 mass % with
On, more preferably more than 70 mass %.In the rubber constituent of reclaimed rubber, the content of EPDM is most preferably 100 mass %, i.e.
Most preferably the rubber constituent of reclaimed rubber is only EPDM.
It should be noted that as the rubber beyond the EPDM in the reclaimed rubber that can be included in involved by the first embodiment
Glue composition, can list：For example, the ethene-alpha-olefin elastomer beyond the EPDM such as EPM (EPM), natural rubber
Glue (NR) etc..
As the rubber chemicals being included in the reclaimed rubber involved by the first embodiment, can list：Under from
State that just comprise before desulfurization is processed, the such as reinforcing agents such as carbon black, softening agent, processing aid, vulcanization accelerator additive, crosslinking agent, sulphur
Change accelerator, age resister etc..
It for the reclaimed rubber involved by the first embodiment, is mixed into rubber (virgin to this reclaimed rubber
Rubber) it is used as base rubber material, or this reclaimed rubber is used directly as base rubber material, then coordinates wherein
Comprise the various rubber chemicals of crosslinking agent, be used as to constitute the rubber of the such as rubbers such as transmission band, conveyer belt, tire, flexible pipe
Glue composition.As described above, be particularly well-suited to transmission band among these.
For the reclaimed rubber involved by the first embodiment, can be handed over by taking out from used rubber
Connection rubber (crosslinked rubber composition), recycling prescriptive procedure carries out desulfurization process to this crosslinking rubber and obtains this regeneration rubber
Glue.Specifically, for the reclaimed rubber involved by the first embodiment, can be by comprising in advance to use sulfur cross-linking mistake
The crosslinked rubber pulverizing powdering of EPDM or granular, then to becoming powdery or granular under the treatment temperature of regulation
Crosslinked rubber apply shear stress carry out desulfurization process and obtain this reclaimed rubber.Now, place when desulfurization can be processed
The conditions such as reason temperature, shear stress and process time combine, and are controlled the gel fraction of reclaimed rubber.Taken off by above-mentioned
The reclaimed rubber that sulphuring treatment obtains comprises：The main chain of a part for the crosslinking points of sulphur and EPDM is cut-off and can carry out crosslinking
EPDM and the gel section that formed by the sulfur cross-linking portion that left behind are i.e. as the EPDM of elastic caoutchouc.As a result, with only
The situation using rubber is compared, and uses the caoutchouc elasticity of the rubber composition of this reclaimed rubber higher and tan δ reduces.
Here, as used rubber, such as transmission band, conveyer belt, tire, flexible pipe etc. can be listed.
The average grain diameter of powdery or granular crosslinked rubber is preferably more than 10 μm, more preferably more than 100 μm, and Er Qieyou
It is selected in below 5mm, more preferably at below 3mm.
The treatment temperature that desulfurization is processed is 150～250 DEG C, from the balance between desulfurization and the gel section being remained
From the point of view of viewpoint, preferably more than 180 DEG C, and preferably below 230 DEG C.From putting down between desulfurization and the gel section being remained
From the viewpoint of weighing apparatus property, shear stress when desulfurization is processed is preferably at more than 0.981MPa, more preferably at more than 4MPa, and Er Qieyou
It is selected in below 20MPa, more preferably at below 15MPa.
Desulfurization as described above processes and single well-known processing such as screw rod or twin-screw extruder forming machine can be used to set
Standby carry out.
It should be noted that in the reclaimed rubber involved by the first embodiment, can be scattered here and there as compounding ingredient
Containing thermoplastic resin below 250 μm for the maximum particle diameter.By as compounding ingredient be scattered here and there containing maximum particle diameter 250 μm with
Under the rubber composition that obtains of the reclaimed rubber of thermoplastic resin be low tan δ, even if thus also can during by alternating bending
Suppression heating, is therefore applicable to the rubber by alternating bending such as transmission band.
Thermoplastic resin as compounding ingredient can list：For example, polyamide (PA), poly terephthalic acid second
The compounding ingredients such as terephthalate resin (PET), acrylic resin (PP).Can list as polyamide (PA)：For example, Buddhist nun
Dragon the 6th, nylon66 fiber etc..Thermoplastic resin as compounding ingredient both can be made up of a kind of thermoplastic resin, it is also possible to by multiple
Thermoplastic resin is constituted.Form as the thermoplastic resin of compounding ingredient can list：For example, powdery, granular, fibrous
Deng.These, it is preferred to fibrous thermoplastic's resin, particularly fibre diameter be 10～30 μm, fibre length be 1～5mm's
Chopped fiber.
The sight cracking as the interface of the thermoplastic resin of compounding ingredient obtained reclaimed rubber from suppression
From the point of view of Dian, as the maximum particle diameter of thermoplastic resin of compounding ingredient preferably below 230 μm, more preferably below 205 μm, enter
One step is preferably below 155 μm, still more preferably below 150 μm, and preferably more than 5 μm, more preferably 20 μm with
On, further preferably more than 50 μm, still more preferably more than 100 μm.The shear stress etc. that desulfurization is processed can be utilized
Control the maximum particle diameter of the thermoplastic resin as compounding ingredient in this reclaimed rubber.And, can by observe obtained by
The maximum particle diameter of the thermoplastic resin as compounding ingredient is measured on the surface of reclaimed rubber.
In reclaimed rubber as the content of thermoplastic resin of compounding ingredient preferably more than 2 mass %, more preferably 8
More than quality %, and preferably below 30 mass %, more preferably below 20 mass %.And, when manufacture comprise above-mentioned
During the reclaimed rubber of big thermoplastic resin less than 250 μm for the particle diameter, preferably the treatment temperature of desulfurization process is set to and is compared to
Temperature for low more than 20 DEG C of the fusing point of the thermoplastic resin of compounding ingredient.
＜ infantees V carries B ＞
Fig. 1 illustrates infantees V band B (transmission band) involved by the first embodiment.This bag involved by the first embodiment
Cloth V band B is in such as agricultural machinery, industrial machine.The size with B for the infantees V involved by first embodiment does not has quilt
Being limited especially, such as this infantees V band B has following size, carries Zhou Changwei 700～5000mm, and bandwidth is 16～17mm,
Tape thickness is 8～10mm.
With B, infantees V involved by first embodiment includes that shape of cross section is trapezoidal band main body 10, this band main body 10
Have that the compression rubber layer of band inner circumferential side (pulley contact side) the 11st, is positioned at centre binds rubber layer 12 and stretching with outer circumferential side
Open this three-decker of rubber layer 13.Being embedded with heart yearn 14 in binding rubber layer 12, this heart yearn 14 is arranged to along bandwidth direction
Form the spiral with pitch.Whole band main body 10 is covered by reinforcement cloth 15.
The 11st, compression rubber layer binds rubber layer 12 and upholds rubber layer 13 and be all made up of crosslinked rubber composition.And
And, the 11st, compression rubber layer binds rubber layer 12 and upholds at least one in rubber layer 13 by using involved by the first embodiment
And reclaimed rubber and crosslinked rubber composition constitute.Constitute compression rubber layer the 11st, binds rubber layer 12 and extension rubber
The rubber composition of layer 13 is all preferably used the reclaimed rubber involved by the first embodiment, in this case, above-mentioned rubber
Composition also can be identical rubber composition.
Here, the rubber composition employing this reclaimed rubber involved by the first embodiment can be by the first embodiment party
Reclaimed rubber involved by formula is used as base rubber material, it is also possible in this reclaimed rubber, be mixed into rubber as rubber constituent and
As base rubber material.Rubber optimal ethylene-alpha-olefin elastomer now, wherein more preferably EPDM.At rubber composition
Rubber constituent in the content of rubber preferably more than 20 mass %, and preferably below 80 mass %, more preferably in 60 matter
Amount below %.
It in the rubber composition of the reclaimed rubber employing involved by this first embodiment, is included in except being combined with
Beyond the rubber chemicals in reclaimed rubber involved by first embodiment, various rubber chemicals are also coordinated.As upper
State rubber chemicals can list：For example, the reinforcing agents such as carbon black, softening agent, processing aid, vulcanization accelerator additive, crosslinking agent,
Vulcanization accelerator, age resister etc..
In the case that the reclaimed rubber involved by the first embodiment comprises reinforcing agent, it is also possible to mismatch reinforcing agent.
On the other hand, in the case of comprising rubber in the rubber composition of the reclaimed rubber comprising involved by the first embodiment, excellent
Reinforcing agent is closed in apolegamy.
Carbon black as reinforcing agent can list：Such as channel black, furnace black, pyrolytic carbon black and acetylene black etc..Furnace black example
If any：Super abrasion furnace black (SAF), medium super abrasion furnace black (ISAF), N-339, high abrasion furnace black (HAF), N-351, in wear-resisting stove
Black (MAF), fast extruding furnace black (FEF), semi-reinforcing furnace black (SRF), general purpose furnace black (GPF), extra conductive furnace black (ECF), N-234
Deng；Pyrolytic carbon black for example has：Fine particle pyrolytic carbon black (FT), middle particle pyrolytic carbon black (MT) etc..Can also arrange as reinforcing agent
Enumerate silica.Reinforcing agent both can be made up of a kind of reinforcing agent, it is also possible to is made up of multiple reinforcing agents.From mar proof and bending resistance
From the viewpoint of balance between song, preferably reinforcing agent containing relative to rubber constituent 100 mass parts of rubber composition
Amount is 30～80 mass parts.
Can list as softening agent：For example, petroleum-type softening agent；The mineral oil softeners such as paraffin oil；Castor oil,
The plant oils such as cottonseed oil, linseed oil, rapeseed oil, soya-bean oil, palm oil, coconut oil, peanut oil, haze tallow, rosin, pine tar soften
Agent etc..Softening agent both can be made up of a kind of softening agent, it is also possible to is made up of multiple softening agents.Softening agent is relative to building rubber compound
Content for example, 2～30 mass parts of rubber constituent 100 mass parts of thing.
Can list as processing aid：For example, stearic acid, Tissuemat E, fatty acid metal salts etc..Processing aid was both
Can be made up of a kind of processing aid, it is also possible to be made up of multiple processing aids.Processing aid is relative to the rubber of rubber composition
Content for example, 0.1～3 mass parts of glue composition 100 mass parts.
Can list as vulcanization accelerator additive：Such as metal oxide, the metal carbon such as magnesia, zinc oxide (zinc white)
Hydrochlorate, aliphatic acid and derivative thereof etc..Vulcanization accelerator additive both can be made up of a kind of vulcanization accelerator additive, it is also possible to by multiple
Vulcanization accelerator additive is constituted.Vulcanization accelerator additive relative to rubber constituent 100 mass parts of rubber composition content for example,
0.5～8 mass parts.
Can list as crosslinking agent：Sulphur and organic peroxide.As crosslinking agent, sulphur can be coordinated, it is possible to
To coordinate organic peroxide, sulphur and organic peroxide can also be used together.In the case that crosslinking agent is sulphur, excellent
Select use level for example, 0.5～4.0 mass parts relative to rubber constituent 100 mass parts of rubber composition for the crosslinking agent；Handing over
In the case that connection agent is organic peroxide, preferably crosslinking agent joining relative to rubber constituent 100 mass parts of rubber composition
Resultant for example, 0.5～8.0 mass parts.
Can list as organic peroxide：For example, the dialkyl class organic peroxies such as dicumyl peroxide
The peroxidating ketones such as the peroxyesters organic peroxide such as compound, peroxide acetic acid butyl ester, peroxidating two cyclohexanone are organic
Peroxide etc..Both a kind of organic peroxide can have been coordinated, it is also possible to coordinate multiple organic peroxide.
When crosslinking agent is sulphur, rubber composition comprises：The gel section that formed by the sulfur cross-linking portion that left behind,
The sulfide linkage being formed with the sulfur cross-linking owing to being added；When crosslinking agent is organic peroxide, rubber composition comprises：By
The gel section of the sulfur cross-linking portion formation that left behind and C-C key that is crosslinked due to organic peroxide and that formed.Therefore,
It by using the reclaimed rubber involved by the first embodiment, and is obtained in that crosslinking points than the rubber group only using EPDM rubber
The many rubber compositions of compound.
Can list as vulcanization accelerator：For example, thiazoles (such as MBT, MBTS etc.) vulcanization accelerator, thiuram
Class (such as TT, TRA etc.) vulcanization accelerator, sulfenamide (such as CZ etc.) vulcanization accelerator, dithiocarbamates
(such as BZ-P etc.) vulcanization accelerator etc..Vulcanization accelerator both can be made up of a kind of vulcanization accelerator, it is also possible to by multiple sulphur
Change accelerator to constitute.Particularly when employing sulphur as crosslinking agent, preferably cooperation vulcanization accelerator, in this case,
Use thiazoles vulcanization accelerator and thiurams vulcanization accelerator preferably simultaneously.Vulcanization accelerator is relative to rubber composition
Content for example, 2～10 mass parts of rubber constituent 100 mass parts.
Can list as age resister：Amine age resister, quinolines age resister, hydroquinone derivative are anti-ageing
Agent, phenols age resister, phosphorous acid esters age resister.Age resister both can be made up of a kind of age resister, it is also possible to
It is made up of multiple age resisters.Age resister relative to rubber constituent 100 mass parts of rubber composition content for example, 0～
8 mass parts.
It should be noted that as rubber chemicals, montmorillonite race, vermiculite race and kaolin can also be coordinated in addition
The phyllosilicates such as race.
Employ the form drawing direction (drawing of the rubber composition of reclaimed rubber involved by the first embodiment
Direction) the fissipation factor tan δ at upper 100 DEG C is preferably more than 0.04, more preferably more than 0.06, and preferably exists
Less than 0.15, more preferably below 0.12.Fissipation factor tan δ can be obtained according to JIS K6394.
Heart yearn 14 is by polyester fiber (PET), polyethylene naphthalate fiber (PEN), aramid fiber, vinylon fibre etc.
Twisting make.In order to give heart yearn 14 relative to the cementability with main body 10, under heart yearn 14 having been carried out before forming
State process, i.e.：The bonding process of reheating after this heart yearn being impregnated in RFL (Resorcin-Formaldehyde-Latex) aqueous solution
And/or the bonding process being dried again after being impregnated in rubber paste.
Reinforcement cloth 15 is for example by thread woven fabrics of yarn such as cotton, Fypro, polyester fiber, aramid fiber, knitting
Cloth, non-woven fabrics etc. are constituted.In order to give reinforcement cloth 15 relative to the cementability with main body 10, to reinforcement cloth 15 before forming
Carry out following process, i.e.：After being impregnated into this reinforcement cloth 15 in the RFL aqueous solution, the bonding of reheating is processed and/or by rubber
Stick with paste to be applied to become after on the surface with main body 10 side and make its bonding process being dried again.
Below, the manufacture method with B for the infantees V involved by the first embodiment illustrates.
First, prepare compression rubber layer sheet rubber 11 ', bind rubber layer sheet rubber 12 ', extension rubber layer rubber
Piece 13 ' and heart yearn twisting 14 ' and reinforcement cloth cloth 15 '.Now, compression rubber layer sheet rubber 11 ', bonding rubber layer
The sheet rubber containing the reclaimed rubber involved by the first embodiment in sheet rubber 13 ' with sheet rubber 12 ' and extension rubber layer
Being obtained by following method, the method is to utilize stack etc. by the reclaimed rubber involved by the first embodiment and rubber
The uncrosslinked rubber composition of compounding ingredient mixing is processed into sheet, has just obtained above-mentioned sheet rubber.Also to heart yearn twisting
14 ' and reinforcement cloth with cloth 15 ' implement bonding process.
Then, as shown in Figure 2 A, sleeve (mantle) 21 is repeatedly wound around compression rubber layer sheet rubber 11 ', then
It is wound around and binds rubber layer sheet rubber 12 '.And then it again on it, as shown in Figure 2 B, is spirally wound around upper twisting
14’.Bind rubber layer sheet rubber 12 ' and uphold rubber layer sheet rubber 13 ' on being wound around successively as shown in Figure 2 C on it again
After, just produce cylindric laminated structure 10 '.
Then, as shown in Figure 2 D, after cylindric laminated structure 10 ' being cut into by sleeve 21 annulus of Rack,
Described annulus is taken off from sleeve 21.
Then, annular lamellar structure 10 ' is winded at one using compression rubber layer sheet rubber 11 ' side as outside
Between belt wheel, rotate, on one side as shown in Figure 2 E as by compression rubber layer the two of the laminate portion of sheet rubber 11 '
Skew back is cut into V-arrangement to regulate volume.
It follows that as shown in Figure 2 F, the periphery of ring-type laminated structure 10 ' is covered with cloth 15 '.
Then, as shown in Figure 2 G, the annular lamellar structure 10 ' wrapped is embedded in the groove 23 of cylinder mould 22, then
Put it into and sulfur still is carried out heat and pressurize.Now, the rubber constituent of annular lamellar structure 10 ' is crosslinked and to form band main
Body 10, and twisting 14 ' is binded with band main body 10 and is realized integrated and become heart yearn 14, and cloth 15 ' binds with band main body 10
Realize that integration becomes reinforcement cloth 15, thus just produce the infantees V band B involved by the first embodiment.
(the second embodiment)
Under the manufacture method of the reclaimed rubber involved by the second embodiment, take out from used rubber and hand over
Connection rubber, in the case of there are the thermoplastic resin as compounding ingredient, applies shear stress to this crosslinking rubber and carries out
Desulfurization process.
Here, as used rubber, such as transmission band, conveyer belt, tire, flexible pipe etc. can be listed.
Can list as the rubber constituent being included in crosslinked rubber：For example, natural rubber (NR), ethene-α-alkene
Olefin elastomer such as EPDM and EPM, neoprene (CR), hydrogenated nitrile-butadiene rubber (H-NBR), isoprene rubber (IR), butadiene-styrene rubber
(SBR), butadiene rubber (BR), nitrile rubber (NBR), butyl rubber (IIR) etc..It both was included in the rubber constituent in crosslinked rubber
Can be made up of a kind of rubber constituent, it is also possible to be made up of multiple rubber constituents.In crosslinked rubber, the content of rubber constituent is excellent
It is selected in more than 30 mass %, more preferably more than 40 mass %, and preferably below 70 mass %, more preferably in 60 mass %
Below.
In crosslinked rubber, carbon black, filler, age resister, plasticizer etc. can also be coordinated in addition.
For crosslinked rubber, rubber constituent crosslinks, and both can carry out crosslinking with sulphur, it is also possible to use organic peroxy
Compound carries out crosslinking.
From the viewpoint of effectively carrying out desulfurization process, preferably：Crosslinked rubber pulverizing powdering before desulfurization is processed
Or it is granular.The average grain diameter of powdery or granular crosslinked rubber is preferably more than 10 μm, more preferably more than 100 μm, further
Preferably more than 200 μm, and preferably at below 5mm, more preferably at below 3mm.
Thermoplastic resin as compounding ingredient can list：For example, polyamide (PA), poly terephthalic acid second
The compounding ingredients such as terephthalate resin (PET), acrylic resin (PP).Can list as polyamide (PA)：For example, Buddhist nun
Dragon the 6th, nylon66 fiber etc..Thermoplastic resin as compounding ingredient both can be made up of a kind of thermoplastic resin, it is also possible to by multiple
Thermoplastic resin is constituted.Form as the thermoplastic resin of compounding ingredient can list：For example, powdery, granular, fibrous
Deng.These, it is preferred to fibrous thermoplastic's resin, particularly fibre diameter be 10～30 μm, fibre length be 1～5mm's
Chopped fiber.
Thermoplastic resin as compounding ingredient preferably is contained in crosslinked rubber, say, that as compounding ingredient
Thermoplastic resin is preferably in following occasion, i.e.：Be scattered here and there friendship in advance that coordinate taking out from used rubber
In connection rubber, and apply the occasion of shear stress to crosslinked rubber.In this case, as compounding ingredient in crosslinked rubber
The content of thermoplastic resin preferably more than 2 mass %, more preferably more than 8 mass %, and preferably 20 mass % with
Under, more preferably below 15 mass %.It should be noted that as compounding ingredient thermoplastic resin it is also possible that,
I.e.：It is not included in crosslinked rubber, and is present in when carrying out desulfurization and processing and crosslinked rubber mix, and crosslinked rubber is executed
Add the occasion of shear stress.
In the manufacture method of the reclaimed rubber involved by the second embodiment, desulfurization is processed is that crosslinked rubber is executed by one
Adding shear stress makes crosslink part cut-out, the physical treatment of depolymerization.Specifically, can list as desulfuration processing method：
For example, use has single screw rod or the Shearing Flow reactive tank (shear flow field reacting tank) of twin-screw is right
Crosslinked rubber is carried out continuously the method that desulfurization is processed.
Further, under the manufacture method of the reclaimed rubber involved by the second embodiment, by the treatment temperature of desulfurization process
It is set to the temperature of low more than 20 DEG C of the fusing point of the thermoplastic resin being used for compounding ingredient.Here, the process temperature that desulfurization is processed
Degree refers to the temperature of treated object when desulfurization is processed, and for example, refers to employing the shearing with single screw rod or twin-screw
In the case of the reactive tank of flow field Shearing Flow reactive tank groove in design temperature.
Here, for the fusing point as the thermoplastic resin of compounding ingredient, be polyamide at thermoplastic resin
(PA), in the case of, for example when for nylon 6, its fusing point is 225～235 DEG C, and when for nylon66 fiber, its fusing point is 260～270
℃；In the case that thermoplastic resin is pet resin (PET), its fusing point is 245～265 DEG C；?
In the case that thermoplastic resin is acrylic resin (PP), its fusing point is 135～180 DEG C.Thermoplastic resin as compounding ingredient
The fusing point of fat can be by differential scanning calorimeter (DSC：Differential Scanning Calorimeter) measurement.
Specifically, it for the treatment temperature that desulfurization is processed, for example, is 225 when employing fusing point as compounding ingredient
DEG C nylon 6 when this treatment temperature is set in less than 205 DEG C, when employing, as compounding ingredient, the nylon that fusing point is 260 DEG C
When 66, this treatment temperature is set in less than 240 DEG C.From the viewpoint of the physical property deterioration of the reclaimed rubber obtained by suppression, de-
The treatment temperature of sulphuring treatment is preferably set to the fusing point than the thermoplastic resin as compounding ingredient coordinating in crosslinked rubber
The temperature of low more than 30 DEG C, is more preferably set to the temperature of lower than this fusing point more than 50 DEG C, is further preferably set to and melts than this
The temperature of low more than 60 DEG C of point, and it from the viewpoint of being adapted for desulfurization process, is preferably set to more than 180 DEG C, more excellent
Choosing is set in more than 200 DEG C.It should be noted that when there is multiple thermoplastic resin as compounding ingredient, at desulfurization
The treatment temperature of reason is set to the temperature than low more than 20 DEG C of the minimum fusing point in the fusing point of multiple thermoplastic resins.
From the viewpoint of being adapted for desulfurization process, the shear stress that desulfurization is processed is preferably set to more than 1MPa, more
It is preferably set to more than 4MPa, and from the viewpoint of suppression is insufficient as the effect of the thermoplastic resin of compounding ingredient,
The shear stress that desulfurization is processed is preferably set to below 20MPa, is more preferably set in below 15MPa.
When the thermoplastic resin as compounding ingredient is included in crosslinked rubber, from the reclaimed rubber manufactured by regulation
From the viewpoint of physical property preferably：Under desulfurization is processed, make the thermoplastic resin with crosslinked the be included as compounding ingredient of rubber
Other different thermoplastic resins are present in the outside of described crosslinked rubber as compounding ingredient, say, that will comprise conduct
The crosslinked rubber of the thermoplastic resin of compounding ingredient mixes with other thermoplastic resins as compounding ingredient.As cooperation
Other thermoplastic resins of material can list above-mentioned cited polyamide (PA) etc., can enumerate as its form
Go out such as powdery, granular, fibrous etc..As compounding ingredient other thermoplastic resins can be included in crosslinked rubber
Thermoplastic resin as compounding ingredient is identical, it is also possible to be different from.
Under the manufacture method of the reclaimed rubber involved by the second embodiment, work is cut off in the shearing processing by desulfurization
Thermoplastic resin for compounding ingredient makes this thermoplastic resin realize small particle and scatter, thus just institute after desulfurization is processed
It for the reclaimed rubber obtaining, in the rubber constituent identical with crosslinked rubber, is scattered here and there containing maximum grain as compounding ingredient
Thermoplastic resin below 250 μm for the footpath.Become different as the thermoplastic resin more than 250 μm for the compounding ingredient maximum particle diameter
Thing, and it is likely to become the starting point cracking.From suppression obtained reclaimed rubber as the thermoplasticity of compounding ingredient
From the viewpoint of the interface of resin cracks, as compounding ingredient thermoplastic resin maximum particle diameter preferably 230 μm with
Under, more preferably below 205 μm, further preferably below 155 μm, still more preferably below 150 μm, and preferably exist
More than 5 μm, more preferably more than 20 μm, further preferably more than 50 μm, still more preferably more than 100 μm.Can profit
Control the maximum particle diameter of the thermoplastic resin as compounding ingredient in this reclaimed rubber with the shear stress etc. that desulfurization is processed.And
And, the maximum grain of the thermoplastic resin as compounding ingredient can be measured by the surface of the reclaimed rubber obtained by observing
Footpath.
In reclaimed rubber, the content of rubber constituent is preferably more than 30 mass %, more preferably more than 40 mass %, and
Preferably below 70 mass %, more preferably below 60 mass %.As the thermoplastic resin of compounding ingredient in reclaimed rubber
Content is preferably more than 2 mass %, more preferably more than 8 mass %, and preferably below 30 mass %, more preferably in 20 matter
Amount below %.
The manufacture method of the reclaimed rubber according to involved by above-mentioned second embodiment, will there are as compounding ingredient
Treatment temperature when carrying out desulfurization process to crosslinked rubber applying shear stress in the case of thermoplastic resin is set to and is used for
The temperature of low more than 20 DEG C of the fusing point of the thermoplastic resin of compounding ingredient, it is thus achieved that be scattered here and there containing maximum particle diameter as compounding ingredient
The reclaimed rubber of the thermoplastic resin below 250 μm, thus desulfurization process under as compounding ingredient thermoplastic resin simultaneously
Not fusing, thus by rubber composition obtained from obtained reclaimed rubber as shown in the test evaluation 2 of following embodiment
As become low tan δ, even if thus by during alternating bending also can suppress heating.It is applicable to transmission therefore, it is possible to manufacture
Reclaimed rubber with waiting rubber by alternating bending.It it is said that in general, in the manufacture of reclaimed rubber, is included in as former
The thermoplastic resins such as the chopped fiber as compounding ingredient in the crosslinked rubber of material are normally used as foreign matter via screening, air floating table
(air floating table) separates, but under the manufacture method of the reclaimed rubber involved by the second embodiment, makees
The rubber composition contributing to employing obtained reclaimed rubber for the above-mentioned thermoplastic resin of compounding ingredient realizes low tan δ
Change.
Under the manufacture method of the reclaimed rubber involved by the second embodiment, after desulfurization is processed, carry out essence as required
Refining, filtration, compressing tablet (sheeting).
The reclaimed rubber utilizing the manufacture method of the second embodiment to obtain can have with involved by the first embodiment
The identical composition of reclaimed rubber, say, that described reclaimed rubber can come from the EPDM comprising to be crossed by sulfur cross-linking
The rubber composition of rubber, and the gel fraction of this reclaimed rubber is 50～85 mass %.
Utilize the reclaimed rubber that the manufacture method of the second embodiment obtains and the first embodiment identical, to this regeneration rubber
Glue is mixed into and is included in the identical or different rubber of the rubber in reclaimed rubber and is used as base rubber material, or this regeneration rubber
Glue is used directly as base rubber material, then coordinates the rubber chemicals comprising crosslinking agent wherein, is used as composition and for example exists
The rubber with the rubbers such as transmission band, conveyer belt, tire, flexible pipe as B for the infantees V shown in Fig. 1 in first embodiment
Composition.For utilizing the reclaimed rubber that the manufacture method of the second embodiment obtains, owing to employing this reclaimed rubber
Rubber composition is low tan δ, even if thus by also suppressing heating during alternating bending.It is therefore preferable that：By employing root
According to the rubber composition of the reclaimed rubber that the manufacture method of the second embodiment obtains, constitute the transmission band of alternating bending to be carried out
At least a portion of band main body.
Employ the rubber composition of the reclaimed rubber obtaining according to the manufacture method of the second embodiment in form drawing
Storage modulus E at 25 DEG C on direction ' preferably at more than 12MPa, more preferably at more than 15MPa, and preferably 70MPa with
Under, more preferably at below 40MPa.Storage modulus E at 100 DEG C ' preferably at more than 8MPa, more preferably at more than 10MPa, and
Preferably at below 50MPa, more preferably at below 30MPa.Storage modulus E at 120 DEG C ' preferably at more than 7MPa, more preferably exist
More than 9MPa, and preferably at below 50MPa, more preferably at below 25MPa.
The reclaimed rubber loss at 25 DEG C on form drawing direction obtaining according to the manufacture method of the second embodiment
Factor t an δ is preferably more than 0.06, more preferably more than 0.08, and preferably below 0.20, more preferably below 0.18.
Fissipation factor tan δ at 100 DEG C is preferably more than 0.04, more preferably more than 0.06, and preferably below 0.15, more excellent
It is selected in less than 0.12.Fissipation factor tan δ at 120 DEG C, preferably more than 0.04, more preferably more than 0.06, and preferably exists
Less than 0.14, more preferably below 0.11.
Storage modulus E can be obtained according to JIS K6394 ' and fissipation factor tan δ.
Embodiment
[test evaluation 1]
(rubber composition)
As crosslinked rubber, prepare EPDM composition (the rubber constituent i.e. content of EPDM crossed by sulfur cross-linking：50 matter
Amount %).Then, this crosslinking rubber powder is broken into average grain diameter 150 μm and make powdery or granular after, put into twin-screw extruder
(Japan Steel Co., Ltd manufactures machine, model：TEX30 α, screw diameter：30mm, spiro rod length：In 1785mm), to powdery
Or after granular crosslinked rubber applying shear stress carries out desulfurization process, cooled down and prepare reclaimed rubber.Now, utilize
Gel fraction is controlled by treatment temperature, screw speed (shear stress) and the variable of process time.Specifically, will process
Temperature is set to 200 DEG C, and screw speed is set to 400rpm (shear stress 7MPa), thus having obtained gel fraction is 70 mass %
Reclaimed rubber 1.Treatment temperature is set to 220 DEG C, and screw speed is set to 400rpm (shear stress 8MPa), thus obtain
Gel fraction is the reclaimed rubber 2 of 52 mass %.Treatment temperature is set to 260 DEG C, and screw speed is set to 600rpm (shearing
Stress 11MPa), thus obtained the reclaimed rubber 3 that gel fraction is 45 mass %.It should be noted that gel fraction is by above-mentioned
Toluene swelling method is tried to achieve.
Utilize reclaimed rubber 1～3, produce following embodiment 1-1～1-4 and the uncrosslinked rubber of comparative example 1-1～1-2
Composition.Also show the composition of each uncrosslinked rubber composition in Table 1.
＜ embodiment 1-1 ＞
For the reclaimed rubber 1 (as the EPDM100 mass parts of rubber constituent) of 200 mass parts, as rubber
Compounding ingredient, (NOF Corp manufactures, trade name to have coordinated stearic acid：Beads Stearic Acid“Tsubaki”)1
(SAKAI CHEMICAL INDUSTRY CO., LTD. manufacture, trade name for mass parts, zinc oxide：Zinc Oxide type
III) (Idemitsu Kosen Co., Ltd. manufactures, trade name for 5 mass parts, softening agent：Diana Process PW-90) 20 mass parts,
Sulphur (Karuizawa Refinery CO., LTD. manufacture, oil-treated sulfur) 3 mass parts, thiurams sulfuration
(Ouchi Shinko Chemical Ind Co., Ltd. manufactures accelerator, trade name：Nocceler TET-G) 2 mass parts and thiazoles
(Ouchi Shinko Chemical Ind Co., Ltd. manufactures vulcanization accelerator, trade name：Nocceler DM-P) mix after 1 mass parts
Refining, has just obtained uncrosslinked rubber composition, using this uncrosslinked rubber composition as embodiment 1-1.
＜ embodiment 1-2 ＞
For the reclaimed rubber 1 (as the EPDM100 mass parts of rubber constituent) of 200 mass parts, as rubber
Compounding ingredient, has coordinated stearic acid 1 mass parts, zinc oxide 5 mass parts, softening agent 20 mass parts, organic peroxide (Japan's grease
Co., Ltd. manufactures, trade name：PERBUTYL P-40, purity 40 mass %) 8 mass parts (active ingredient 3.2 mass parts) are laggard
Row mixing, has just obtained uncrosslinked rubber composition, using this uncrosslinked rubber composition as embodiment 1-2.
＜ embodiment 1-3 ＞
Will be in addition to employing reclaimed rubber 2, other constitute uncrosslinked rubber composition all same as in Example 1 and make
For embodiment 1-3.
＜ embodiment 1-4 ＞
It relative to the reclaimed rubber 1 (as the EPDM50 mass parts of rubber constituent) of 100 mass parts, is mixed with EPDM rubber
(JSR Corp. manufactures, trade name：EP33) 50 mass parts, relative to rubber constituent 100 mass parts included in it
Speech, as rubber chemicals, (TOKAI CARBON CO., LTD. manufacture, trade name to have coordinated HAF carbon black：SEAST 3) 50 matter
Amount part, stearic acid 1 mass parts, zinc oxide 5 mass parts, softening agent 20 mass parts, sulphur 3 mass parts, thiurams sulfuration promote
Knead after agent 2 mass parts and thiazoles vulcanization accelerator 1 mass parts, just obtained uncrosslinked rubber composition, should
Uncrosslinked rubber composition is as embodiment 1-4.
＜ comparative example 1-1 ＞
Will be in addition to employing reclaimed rubber 3, other constitute uncrosslinked rubber composition all same as in Example 1 and make
For comparative example 1-1.
＜ comparative example 1-2 ＞
Will be in addition to employing reclaimed rubber 3, other constitute uncrosslinked rubber composition all same as in Example 2 and make
For comparative example 1-2.
[table 1]
It should be noted that because the building rubber compound of embodiment 1-1, embodiment 1-3, embodiment 1-4 and comparative example 1-1
Thing is sulfur cross-linking class rubber composition, so that the rubber composition that the crosslinking of these uncrosslinked rubber compositions is obtained will
The sulfide linkage that there is the gel section being formed by the sulfur cross-linking portion that left behind and the sulfur cross-linking owing to being added and formed.
On the other hand, because the rubber composition of embodiment 1-2 and comparative example 1-2 is organic peroxide crosslinking class rubber composition,
So that the rubber composition that the crosslinking of these uncrosslinked rubber compositions is obtained will have by the sulfur cross-linking that left behind
The gel section of portion's formation and C-C key that is crosslinked due to organic peroxide and that formed.
(Test model synthetic techniques)
＜ fissipation factor tan δ ＞
Embodiment 1-1～1-4 and the respective uncrosslinked rubber composition of comparative example 1-1～1-2 are shaped sheet rubber
Vulcanized after piece, and according to JIS K6394, be that 10Hz, dynamic strain (dynamic strain) are in vibration frequency
Fissipation factor tan δ in the case of 1.0%, when having obtained on its form drawing direction 100 DEG C.
＜ carries long duration test ＞
Produce and utilize embodiment 1-1～1-4 and the respective uncrosslinked rubber composition of comparative example 1-1～1-2 to constitute
Compression rubber layer, the infantees V band binding rubber layer and extension rubber layer.It should be noted that the twisting made by polyester fiber
As heart yearn, and with cotton woven fabric processed as reinforcement cloth.
Fig. 3 illustrates the belt wheel horizontal layout situation with traveling testing machine 30.
With traveling testing machine 30, there is the driving pulley 31 that pulley diameters is 80mm and be arranged on below this driving pulley 31
Pulley diameters be the driven pulley 32 of 80mm.Driven pulley 32 is configured to movable up and down, and is configured to：By by weight
(constantly acting load) is suspended on driven pulley 32, and can be applied to tension force hang around on driving pulley 31 and driven pulley 32
Infantees V band B on.
The infantees V band will made by embodiment 1-1～1-4 and the respective uncrosslinked rubber composition of comparative example 1-1～1-2
B is winded on driving pulley 31 and driven pulley 32, and tension force is applied to bag by the weight hanging 80kg on driven pulley 32
On cloth V band B, and rotary load is not applied to driven pulley 32, at normal temperatures, allow driving pulley 31 with the rotating speed of 3500rpm
Rotate and allow infantees V band B carry out traveling, and allow band stopping traveling eyes confirm either with or without cracking, really termly
Recognizing the moment cracking allows end of tape traveling.Further, band travel time to cracking for the comparative example 1-1 is set to
100, evaluated by the life-span to band for its relative value.And, use non-contact surface thermometer, to band during traveling
After temperature measures, obtain the maximum of temperature difference between itself and environment temperature.
(test evaluation result)
Show result of the test in Table 1.
Employing the situation that gel fraction is relatively low, be the comparative example 1-1 of the sulfur cross-linking class of the reclaimed rubber 3 of 45 mass %
Under, tan δ is relatively big (0.175), and also more (+44 DEG C) with heating during traveling, and then just produces in early days when carrying traveling
Crackle causes tape lifetime shorter (100).
It is 52 mass %, the embodiment being higher than the sulfur cross-linking class of the reclaimed rubber 2 of reclaimed rubber 3 employing gel fraction
In the case of 1-3, compared with the situation of comparative example 1-1, tan δ relatively low (0.125), and with heating during traveling also less (+
29 DEG C), and then tape lifetime is also longer (142).
The enforcement of the sulfur cross-linking class of higher reclaimed rubber 1 to employ gel fraction be 70 mass %, than reclaimed rubber 2
In the case of example 1-1, compared with the situation of embodiment 1-2, tan δ lower (0.107), and also also less with heating during traveling
(+25 DEG C), and then tape lifetime is also longer (149).
Employing the comparative example that gel fraction is relatively low, be the crosslinked class of organic peroxide of the reclaimed rubber 3 of 45 mass %
In the case of 1-2, tan δ is 0.159, and is+38 DEG C with heating during traveling, and then tape lifetime is 120, although be better than ratio
Compared with the situation of example 1-1, but can not referred to as obtain significantly improving.
Embodiment 1-2 in the crosslinked class of the organic peroxide employing the reclaimed rubber 1 that gel fraction is 70 mass %
In the case of, compared with the situation of embodiment 1-1, tan δ further reduces (0.089), and also more enters with heating during traveling
One step reduces (+21 DEG C), and then tape lifetime also further increases (168).
And, in the case of embodiment 1-4 of the sulfur cross-linking class that reclaimed rubber 2 and EPDM rubber are mixed,
Compared with the situation of comparative example 1-1 and comparative example 1-2, tan δ relatively low (0.119), and with heating during traveling also less (+28
DEG C), and then tape lifetime is also longer (152).
For the infantees V band made by the rubber composition of embodiment 1-1～1-4 because exist by reclaimed rubber 1 and
Appropriate gel section that the sulfur cross-linking portion that left behind in reclaimed rubber 2 is formed and caoutchouc elasticity is maintained, its
Result is can to deduce to obtain excellent tape lifetime in long duration test.And, even if by reclaimed rubber 2 and EPDM
In the case that rubber mixes, the gel section being formed by the sulfur cross-linking portion that left behind also suitably scatter and can
Obtaining caoutchouc elasticity, its result is can to deduce to obtain excellent tape lifetime in long duration test.
Reclaimed rubber 1 used in the rubber composition of embodiment 1-1～1-4 and reclaimed rubber 2 are by
Carry out desulfurization process with the EPDM that sulfur cross-linking is crossed and obtain, be capable of the performance more excellent than using EPDM rubber.
[test evaluation 2]
(reclaimed rubber)
＜ embodiment 2-1 ＞
Prepare following crosslinked rubber.I.e.：As shown in table 2, by EPDM, (JSR Corp. manufactures, trade name：EP51) make
For crude rubber, relative to this crude rubber 100 mass parts, coordinated HAF carbon black (TOKAI CARBON CO., LTD. manufacture,
Trade name：SEAST 3) 50 mass parts, stearic acid (NOF Corp manufacture, trade name：Beads Stearic Acid
" Tsubaki ") 1 mass parts, zinc oxide (SAKAI CHEMICAL INDUSTRY CO., LTD. manufacture, trade name：Zinc
Oxide type III) 5 mass parts, softening agent (Idemitsu Kosen Co., Ltd. manufacture, trade name：Diana Process oil
PW-90) (Karuizawa Refinery CO., LTD. manufacture, trade name for 15 mass parts, sulphur：oil-treated
Sulfur) (Ouchi Shinko Chemical Ind Co., Ltd. manufactures, trade name for 3 mass parts, thiurams vulcanization accelerator：
Nocceler TET-G) 2 mass parts, thiazoles vulcanization accelerator (Ouchi Shinko Chemical Ind Co., Ltd. manufacture, trade name：
Nocceler DM-P) (Asahi Kasei Corporation manufactures, trade name for 1 mass parts and nylon66 fiber chopped fiber：Leona66, fusing point
260 DEG C) use sulfur cross-linking afterwards, just obtain crosslinked rubber.
[table 2]
| EPDM | 100 |
| HAF carbon black | 50 |
| Stearic acid | 1 |
| Zinc oxide | 5 |
| Softening agent | 15 |
| Sulphur | 3 |
| Thiurams vulcanization accelerator | 2 |
| Thiazoles vulcanization accelerator | 1 |
| Nylon66 fiber chopped fiber | 23 |
Crosslinking rubber powder is broken into after average grain diameter is 400 μm, puts into twin (double) screw extruder (JSW's strain formula meeting
Society manufactures, model：TEX30 α, screw diameter：30mm, spiro rod length：In 1785mm), treatment temperature is set to and compares nylon66 fiber
200 DEG C of low 60 DEG C of the fusing point of chopped fiber 260 DEG C, and screw speed is set as 600rpm (shear stress：14MPa), to friendship
Connection rubber apply shear stress carry out desulfurization process, then carry out cooling down just having obtained reclaimed rubber, using this reclaimed rubber as
Embodiment 2-1.
With cutter cut off embodiment 2-1 reclaimed rubber, utilize microscope (micro-scope) (Keyemce company manufacture,
Model：VHX2000) observe after three positions of the section of this reclaimed rubber being amplified to 200 times, it can be seen that Fig. 1 institute
The form shown, and utilize measurement pattern to measure the maximum external diameter (maximum outside diameter) of nylon short fibre, this external diameter is 148 μm.
And, utilize above-mentioned toluene swelling method to obtain gel fraction, this gel fraction is 62 mass %.
<Embodiment 2-2>
Except screw speed is set to 400rpm (shear stress：8MPa) and apply shear stress to crosslinked rubber to carry out
Beyond desulfurization is processed, produce reclaimed rubber according to the manufacture method identical with embodiment 2-1, using this reclaimed rubber as enforcement
Example 2-2.
For the reclaimed rubber of embodiment 2-2, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 202 μm.And, gel fraction is 68 mass %.
<Embodiment 2-3>
Except treatment temperature is set to 230 DEG C of low 30 DEG C of fusing point 260 DEG C than nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 600rpm (shear stress：12MPa) apply shear stress to have carried out beyond desulfurization processes to crosslinked rubber, according to reality
Execute the identical manufacture method of example 2-1 and produce reclaimed rubber, using this reclaimed rubber as embodiment 2-3.
For the reclaimed rubber of embodiment 2-3, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 151 μm.And, gel fraction is 55 mass %.
<Embodiment 2-4>
Except treatment temperature is set to 200 DEG C of low 60 DEG C of fusing point 260 DEG C than nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 200rpm (shear stress：6MPa) crosslinked rubber is carried out beyond desulfurization processes, according to identical with embodiment 2-1
Manufacture method produces reclaimed rubber, using this reclaimed rubber as embodiment 2-4.
For the reclaimed rubber of embodiment 2-4, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 227 μm.And, gel fraction is 75 mass %.
<Embodiment 2-5>
Except treatment temperature is set to 240 DEG C of low 20 DEG C of fusing point 260 DEG C than nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 600rpm (shear stress：13MPa) apply shear stress to have carried out beyond desulfurization processes to crosslinked rubber, according to reality
Execute the identical manufacture method of example 2-1 and produce reclaimed rubber, using this reclaimed rubber as embodiment 2-5.
For the reclaimed rubber of embodiment 2-5, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 155 μm.And, gel fraction is 51 mass %.
＜ comparative example 2-1 ＞
Except employing the crosslinked rubber of unmated nylon66 fiber chopped fiber as crosslinked rubber, treatment temperature is set to 200
DEG C and screw speed is set to 400rpm (shear stress：5MPa) crosslinked rubber is applied shear stress carried out desulfurization process with
Outward, reclaimed rubber is produced according to the manufacture method identical with embodiment 2-1, using this reclaimed rubber as comparative example 2-1.
The gel fraction of the reclaimed rubber of comparative example 2-1 is 78 mass %.
＜ comparative example 2-2 ＞
Except treatment temperature is set to 250 DEG C of low 10 DEG C of fusing point 260 DEG C than nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 600rpm (shear stress：10MPa) apply shear stress to have carried out beyond desulfurization processes to crosslinked rubber, according to reality
Execute the identical manufacture method of example 2-1 and produce reclaimed rubber, using this reclaimed rubber as comparative example 2-2.
For the reclaimed rubber of comparative example 2-2, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 147 μm.And, gel fraction is 46 mass %.
＜ comparative example 2-3 ＞
Except screw speed is set to 100rpm (shear stress：5MPa) apply shear stress to crosslinked rubber to be taken off
Beyond sulphuring treatment, produce reclaimed rubber according to the manufacture method identical with embodiment 2-1, using this reclaimed rubber as comparative example
2-3.
For the reclaimed rubber of comparative example 2-3, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 311 μm.And, gel fraction is 83 mass %.
＜ comparative example 2-4 ＞
Except treatment temperature is set to 250 DEG C of low 10 DEG C of fusing point 260 DEG C than nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 100rpm (shear stress：4MPa) apply shear stress to have carried out beyond desulfurization processes to crosslinked rubber, according to reality
Execute the identical manufacture method of example 2-1 and produce reclaimed rubber, using this reclaimed rubber as comparative example 2-4.
For the reclaimed rubber of comparative example 2-4, measure nylon short fibre according to the method identical with embodiment 2-1
Maximum outside diameter, this maximum outside diameter is 302 μm.And, gel fraction is 70 mass %.
(Test model synthetic techniques)
Utilize embodiment 2-1～2-5 and comparative example 2-1～respective reclaimed rubber of 2-4, prepare following uncrosslinked rubber
Composition, i.e.：As shown in table 3, the reclaimed rubber (as the EPDM100 mass parts of rubber constituent) relative to 200 mass parts, joins
(NOF Corp manufactures, trade name to have closed stearic acid：Beads Stearic Acid " Tsubaki ") 1 mass parts, oxygen
(SAKAI CHEMICAL INDUSTRY CO., LTD. manufacture, trade name to change zinc：Zinc Oxide type III) 5 mass parts,
(Idemitsu Kosen Co., Ltd. manufactures softening agent, trade name：Diana Process oil PW-90) 15 mass parts, sulphur
(Karuizawa Refinery CO., LTD. manufacture, oil-treated sulfur) 3 mass parts, thiurams sulfuration promote
(Ouchi Shinko Chemical Ind Co., Ltd. manufactures, trade name in agent：Nocceler TET-G) 2 mass parts and thiazoles sulfuration
Accelerator (Ouchi Shinko Chemical Ind Co., Ltd. manufactures, Nocceler DM-P) 1 mass parts, thus obtained uncrosslinked rubber
Glue composition.
[table 3]
| Reclaimed rubber | 200 |
| Stearic acid | 1 |
| Zinc oxide | 5 |
| Softening agent | 15 |
| Sulphur | 3 |
| Thiurams vulcanization accelerator | 2 |
| Thiazoles vulcanization accelerator | 1 |
<Dynamic viscoelastic is tested>
By the uncrosslinked building rubber compound employing embodiment 2-1～2-5 and comparative example 2-1～respective reclaimed rubber of 2-4
Thing is vulcanized after shaping sheet rubber piece, and according to JIS K6394, is that 10Hz, dynamic strain are in vibration frequency
In the case of 1.0%, measure storage modulus E when 25 DEG C, 100 DEG C and 120 DEG C on its form drawing direction ' and fissipation factor
tanδ.
<Band long duration test>
Produce by the uncrosslinked rubber employing embodiment 2-1～2-5 and comparative example 2-1～respective reclaimed rubber of 2-4
Glue composition constitutes compression rubber layer, binds rubber layer and upholds the infantees V band of rubber layer, and implements and test evaluation 1 phase
Same band long duration test.Further, band travel time to cracking for the comparative example 2-1 is set to 100, by its relative value pair
The life-span of band is evaluated.
(test evaluation result)
Show result of the test in table 4 and table 5.
[table 4]
[table 5]
According to table 4 and table 5：Compared with the comparative example 2-1 without nylon66 fiber chopped fiber, comprise nylon66 fiber chopped fiber
Storage modulus E under embodiment 2-1～2-5 and arbitrary temperature in 25 DEG C, 100 DEG C and 120 DEG C for the comparative example 2-3～2-4 ' all relatively
Height, and fissipation factor tan δ is relatively low, and carry excellent in te pins of durability.Also know that：Storage for comparative example 2-2, when only 25 DEG C
Energy modulus E ' less than comparative example 2-1, and in addition, storage modulus E compared with comparative example 2-1 ' higher, and fissipation factor tan δ
Relatively low, and carry excellent in te pins of durability.
For comparative example 2-1, owing to not comprising nylon66 fiber chopped fiber, thus storage modulus is relatively low and tan δ is relative
Higher, heating when its result is to deduce bending is more, and degradation is bigger.
Understand：Compared with comparative example 2-1～2-4, the band excellent in te pins of durability of embodiment 2-1～2-5.
Can deduce for comparative example 2-2 and 2-4：Owing to the treatment temperature of desulfurization process is close to nylon66 fiber chopped fiber
Fusing point, the physical property thus resulting in nylon66 fiber chopped fiber reduces.
Can deduce for comparative example 2-3 and 2-4：Due to nylon66 fiber chopped fiber in reclaimed rubber maximum particle diameter relatively
Greatly, thus easily crack at interface.
-industrial applicability-
The present invention is in reclaimed rubber and manufacture method thereof and the technical field of transmission band employing this reclaimed rubber
It is very useful.
-symbol description-
B infantees V carries
10 band main bodys
11 compression rubber layers
12 bonding rubber layers
13 extension rubber layers
14 heart yearns
15 reinforcement cloth
10 ' laminated structures
11 '～13 ' sheet rubbers
14 ' twistings
15 ' cloth
21 sleeves
22 cylinder moulds
23 grooves
30 band traveling testing machines
31 driving pulleys
32 driven pulleys
Claims (14)
1. a reclaimed rubber, it is characterised in that：
Described reclaimed rubber comes the rubber composition of the ethylene propylene diene rubber that self-contained sulfur cross-linking is crossed, and this reclaimed rubber
Gel fraction be 50～85 mass %.
2. reclaimed rubber according to claim 1, it is characterised in that：
The rubber constituent of described reclaimed rubber is only ethylene propylene diene rubber.
3. reclaimed rubber according to claim 1 and 2, it is characterised in that：
The content of the rubber constituent of described reclaimed rubber is 30～70 mass %.
4. a transmission band, it is characterised in that：
At least a portion of the band main body of described transmission band is by the reclaimed rubber employing according to any one of claims 1 to 3
Rubber composition constitute.
5. transmission band according to claim 4, it is characterised in that：
It is mixed with rubber in described rubber composition.
6. transmission band according to claim 5, it is characterised in that：
Described rubber is ethene-alpha-olefin elastomer.
7. the transmission band according to claim 5 or 6, it is characterised in that：
Described in the rubber constituent of described rubber composition, the content of rubber is 20～80 mass %.
8. the transmission band according to according to any one of claim 4 to 7, it is characterised in that：
It in described rubber composition, is combined with sulphur as crosslinking agent.
9. the transmission band according to according to any one of claim 4 to 8, it is characterised in that：
It in described rubber composition, is combined with organic peroxide as crosslinking agent.
10. the transmission band according to according to any one of claim 4 to 9, it is characterised in that：
On the form drawing direction of described rubber composition, the fissipation factor tan δ at 100 DEG C is 0.04～0.15.
The manufacture method of 11. 1 kinds of reclaimed rubbers, it is characterised in that：
After the crosslinked rubber of ethylene propylene diene rubber comprising to be crossed by sulfur cross-linking is pulverized, to chippy described crosslinking
Rubber applies shear stress and carries out desulfurization process, thus obtains the reclaimed rubber that gel fraction is 50～85 mass %.
The manufacture method of 12. reclaimed rubbers according to claim 11, it is characterised in that：
The average grain diameter of chippy described crosslinked rubber is 10 μm～5mm.
The manufacture method of 13. reclaimed rubbers according to claim 11 or 12, it is characterised in that：
The treatment temperature that described desulfurization is processed is set to 150～250 DEG C.
The manufacture method of 14. reclaimed rubbers according to according to any one of claim 11 to 13, it is characterised in that：
Described shear stress is set to 0.981～20MPa.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-130075 | 2014-06-25 | ||
| JP2014130075 | 2014-06-25 | ||
| JP2014141232 | 2014-07-09 | ||
| JP2014-141232 | 2014-07-09 | ||
| PCT/JP2015/002833 WO2015198537A1 (en) | 2014-06-25 | 2015-06-04 | Regenerated rubber, process for producing same, and transmission belt including same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106459540A true CN106459540A (en) | 2017-02-22 |
Family
ID=54937649
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580033659.XA Pending CN106459540A (en) | 2014-06-25 | 2015-06-04 | Regenerated rubber, process for producing same, and transmission belt including same |
| CN201580033686.7A Pending CN106536617A (en) | 2014-06-25 | 2015-06-04 | Regenerated rubber, process for producing same, and transmission belt including same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580033686.7A Pending CN106536617A (en) | 2014-06-25 | 2015-06-04 | Regenerated rubber, process for producing same, and transmission belt including same |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPWO2015198537A1 (en) |
| CN (2) | CN106459540A (en) |
| WO (2) | WO2015198537A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721863A (en) * | 2019-01-23 | 2019-05-07 | 保定华月胶带有限公司 | Application of the fire-retardant reclaimed rubber in fire retarding conveying band |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017145866A1 (en) * | 2016-02-24 | 2017-08-31 | 横浜ゴム株式会社 | Rubber composition for adhesives, bonding method for rubbers, and conveyor belt |
| JP6837920B2 (en) * | 2016-06-14 | 2021-03-03 | 三ツ星ベルト株式会社 | Wrapped V-belt and manufacturing method of wrapped V-belt |
| CN107602965A (en) * | 2017-09-21 | 2018-01-19 | 如皋市嘉好热熔胶有限公司 | A kind of tyre reclaim and preparation method thereof |
| JP6777835B1 (en) * | 2019-06-07 | 2020-10-28 | バンドー化学株式会社 | Large V-belt |
Citations (1)
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| CN103601984A (en) * | 2013-11-08 | 2014-02-26 | 四川大学 | Method for preparing thermoplastic vulcanizate through blending desulfurized ethylene propylene diene monomer (EPDM) rubber powder/polypropylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06179215A (en) * | 1992-12-14 | 1994-06-28 | Furukawa Electric Co Ltd:The | Method for pulverizing vulcanized rubber material |
| JPH10176001A (en) * | 1996-12-18 | 1998-06-30 | Toyota Central Res & Dev Lab Inc | Regeneration of vulcanized rubber |
| DE69928974T2 (en) * | 1998-01-26 | 2006-11-30 | Toyoda Gosei Co., Ltd. | Rubber composition and process for its preparation |
| JP3308484B2 (en) * | 1998-02-19 | 2002-07-29 | 株式会社豊田中央研究所 | Rubber composition |
| JP4104031B2 (en) * | 1998-10-28 | 2008-06-18 | 株式会社ブリヂストン | Recycled rubber |
| JP2008254300A (en) * | 2007-04-04 | 2008-10-23 | Mitsuboshi Belting Ltd | Power transmission belt |
| JP5704782B2 (en) * | 2007-04-17 | 2015-04-22 | 住友ゴム工業株式会社 | Rubber composition for tire tread containing liquid recycled rubber and pneumatic tire having tread using the same |
| EP2593499A1 (en) * | 2010-07-14 | 2013-05-22 | U.B.Q. Materials Ltd. | Composite material from waste and at least one element of vulcanized rubber and tire cords |
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2015
- 2015-06-04 WO PCT/JP2015/002833 patent/WO2015198537A1/en active Application Filing
- 2015-06-04 JP JP2016529009A patent/JPWO2015198537A1/en active Pending
- 2015-06-04 CN CN201580033659.XA patent/CN106459540A/en active Pending
- 2015-06-04 WO PCT/JP2015/002834 patent/WO2015198538A1/en active Application Filing
- 2015-06-04 CN CN201580033686.7A patent/CN106536617A/en active Pending
- 2015-06-04 JP JP2016529010A patent/JPWO2015198538A1/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601984A (en) * | 2013-11-08 | 2014-02-26 | 四川大学 | Method for preparing thermoplastic vulcanizate through blending desulfurized ethylene propylene diene monomer (EPDM) rubber powder/polypropylene |
Non-Patent Citations (1)
| Title |
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| 柳云骐、罗根祥、孙海翔主编: "《材料化学》", 28 February 2013 * |
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|---|---|---|---|---|
| CN109721863A (en) * | 2019-01-23 | 2019-05-07 | 保定华月胶带有限公司 | Application of the fire-retardant reclaimed rubber in fire retarding conveying band |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015198537A1 (en) | 2015-12-30 |
| WO2015198538A1 (en) | 2015-12-30 |
| JPWO2015198537A1 (en) | 2017-04-20 |
| JPWO2015198538A1 (en) | 2017-04-20 |
| CN106536617A (en) | 2017-03-22 |
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Application publication date: 20170222 |