CN106536617A - 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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- CN106536617A CN106536617A CN201580033686.7A CN201580033686A CN106536617A CN 106536617 A CN106536617 A CN 106536617A CN 201580033686 A CN201580033686 A CN 201580033686A CN 106536617 A CN106536617 A CN 106536617A
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- rubber
- reclaimed
- thermoplastic resin
- compounding ingredient
- reclaimed rubber
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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)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A regenerated rubber contains, dispersed therein, a compounding thermoplastic-resin material having a maximum particle diameter of 250 Mu[m] or less.
Description
Technical field
The present invention relates to a kind of reclaimed rubber and its manufacture method and use the transmission belt of the reclaimed rubber.
Background technology
Reclaimed rubber is to implement chemical treatment or physical treatment by the crosslinking rubber to used rubber, and
Become the rubber of the state of formable processing again.The use of reclaimed rubber is for the material cost and manufacture of cutting down rubber
Cost is extremely effective.
A kind of manufacture method of reclaimed rubber is Patent Document 1 discloses, under the manufacture method, to being crosslinked rubber reality
Apply 180～350 DEG C and 10～150kg/cm of shear stress of temperature2Condition desulfurization process.
A kind of manufacture method of reclaimed rubber is Patent Document 2 discloses, under the manufacture method, for crosslinking rubber
Apply shear stress under the heating-up temperature more than regeneration temperature for causing the cut-outs such as the crosslinking between the rubber molecule.
A kind of manufacture method of reclaimed rubber is Patent Document 3 discloses, under the manufacture method, by crosslinking rubber
Material powder is mixed with polydiene, applies the maximum shear speed shear stress of more than 300/ second to which.
A kind of manufacture method of reclaimed rubber is Patent Document 4 discloses, under the manufacture method, is applied to being crosslinked rubber
220～350 DEG C and 10～150kg/cm of shear stress of heating degree2Condition desulfurization process.
Patent documentation 1：The flat 9-227724 publications of Japanese Laid-Open Patent Publication Laid-Open
Patent documentation 2：Japanese Laid-Open Patent Publication Laid-Open 2001-30237 publication
Patent documentation 3：Japanese Laid-Open Patent Publication Laid-Open 2003-128843 publication
Patent documentation 4：Japanese Laid-Open Patent Publication Laid-Open 2004-35690 publication
The content of the invention
In the reclaimed rubber of the present invention, it is scattered here and there the thermoplastic containing maximum particle diameter below 250 μm as compounding ingredient
Property resin.
The manufacture method of the reclaimed rubber of the present invention is such, there are the thermoplastic resin as compounding ingredient
In the case of to be crosslinked rubber apply shear stress carry out desulfurization process, the treatment temperature of the desulfurization process 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, then obtains to be scattered here and there as compounding ingredient and contains
There is the reclaimed rubber of thermoplastic resin of the maximum particle diameter below 250 μm.
For the transmission belt of the present invention, band main body is constituted by the rubber composition of the reclaimed rubber using the present invention
At least a portion.
Description of the drawings
Fig. 1 is the partial perspective cross-sectional figure of the infantees V bands involved by first embodiment.
Fig. 2A is the first explanatory diagram of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 2 B are the second explanatory diagrams of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 2 C are the 3rd explanatory diagrams of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 2 D are the 4th explanatory diagrams of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 2 E are the 5th explanatory diagrams of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 2 F are the 6th explanatory diagrams of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 2 G are the 7th explanatory diagrams of the manufacture method for illustrating the infantees V bands involved by embodiment.
Fig. 3 is the belt wheel site plan with traveling testing machine used by embodiment.
Fig. 4 is the photo of the facet of the reclaimed rubber for observing embodiment 2-1.
Specific embodiment
Below, referring to the drawings embodiment is illustrated.
(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
The EPDM that rubber is crossed come sulfur cross-linking of using by oneself, and cause gel fraction higher as which uses sulfur cross-linking, it is 50～85 matter
Amount %, thus for the rubber composition using the reclaimed rubber, caoutchouc elasticity is higher and tan δ are relatively low.It is therefore preferable that：By
Use the rubber composition of the reclaimed rubber involved by first embodiment, composition that the transmission of alternating bending is particularly carried out
At least a portion with main body of band.
Here, from easily being crosslinked 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 first embodiment 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), the test film is immersed in 72 hours in 30 DEG C of toluene makes re-dry after its swelling, by impregnating
Quality (W before toluene0) and impregnate the quality (W after toluene3) calculate gel fraction gw=(W3/W0)×100.It should be noted that
The method is also stated that for example《Rubber experiment method (Japan rubber association of civic organization edits distribution)》In.
Reclaimed rubber involved by first embodiment includes rubber constituent and rubber chemicals in addition.
In the reclaimed rubber involved by 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 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.
The rubber constituent of most preferably 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 first embodiment
Glue composition, can include：For example, beyond the EPDM such as ethylene propylene monomer (EPM) ethene-alpha-olefin elastomer, natural rubber
Glue (NR) etc..
As the rubber chemicals being included in the reclaimed rubber involved by first embodiment, can include：Under
Reinforcing agent, softening agent, processing aid, vulcanization accelerator additive, cross-linking agent, the sulfur such as just include before stating desulfurization process, such as white carbon black
Change accelerator, age resister etc..
For the reclaimed rubber involved by first embodiment, rubber (virgin is mixed into the reclaimed rubber
Rubber) it is used as base rubber material, or the reclaimed rubber is used directly as base rubber material, then coordinates thereto
Various rubber chemicals comprising cross-linking agent, as the rubber for constituting such as rubber such as transmission belt, conveyer belt, tire, flexible pipe
Glue composition.As described above, being particularly well-suited to transmission belt among these.
For the reclaimed rubber involved by first embodiment, can be handed over by taking out from used rubber
Connection rubber (crosslinked rubber composition), recycles prescriptive procedure to carry out desulfurization process to the crosslinking rubber and obtain the regeneration rubber
Glue.Specifically, for the reclaimed rubber involved by first embodiment, can be by advance will be comprising using sulfur cross-linking mistake
EPDM crosslinking rubber pulverizing powdering or granular, then regulation treatment temperature under to becoming powdery or granular
Crosslinking rubber apply shear stress carry out desulfurization process and obtain the reclaimed rubber.Now, can be by place during desulfurization process
The conditions such as reason temperature, shear stress and process time combine, and the gel fraction of reclaimed rubber is controlled.By above-mentioned de-
The reclaimed rubber that sulphuring treatment is obtained is included：What the main chain of the part and EPDM of the crosslinking points of sulfur was cut off and can be crosslinked
The EPDM of EPDM and the gel section that formed by the sulfur cross-linking portion that left behind i.e. as gum elastic.As a result, with only
Compared using the situation of rubber, using the caoutchouc elasticity of the rubber composition of the reclaimed rubber is higher and tan δ are reduced.
Here, as used rubber, such as transmission belt, conveyer belt, tire, flexible pipe etc. can be included.
The mean diameter of powdery or granular crosslinking rubber preferably more than 10 μm, more preferably more than 100 μm, Er Qieyou
Below 5mm is selected in, more preferably in below 3mm.
The treatment temperature of desulfurization process is 150～250 DEG C, the balance between desulfurization and the gel section for being remained
From the point of view of viewpoint, preferably more than 180 DEG C, and preferably below 230 DEG C.It is flat between desulfurization and the gel section for being remained
Weighing apparatus property from the viewpoint of, shear stress during desulfurization process preferably in more than 0.981MPa, more preferably in more than 4MPa, Er Qieyou
Below 20MPa is selected in, more preferably in below 15MPa.
Desulfurization process as described above can be set using the well-known processing such as single screw rod or twin-screw extruder forming machine
It is standby to carry out.
It should be noted that in the reclaimed rubber involved by first embodiment, can be scattered here and there as compounding ingredient
Containing thermoplastic resin of the maximum particle diameter below 250 μm.By as compounding ingredient be scattered here and there containing maximum particle diameter 250 μm with
Under the rubber composition that obtains of reclaimed rubber of thermoplastic resin be low tan δ, even if thus being subject to also can during alternating bending
Suppress heating, therefore suitable for transmission belt etc. by alternating bending rubber.
Can include as the thermoplastic resin of compounding ingredient：For example, polyamide (PA), poly terephthalic acid second
The compounding ingredients such as terephthalate resin (PET), acrylic resin (PP).Can include as polyamide (PA)：For example, Buddhist nun
Dragon 6, nylon66 fiber etc..Both can be made up of a kind of thermoplastic resin as the thermoplastic resin of compounding ingredient, it is also possible to by various
Thermoplastic resin is constituted.Can include as the form of the thermoplastic resin of compounding ingredient：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.
From the sight that suppression is cracked as the interface of the thermoplastic resin of compounding ingredient in resulting reclaimed rubber
Point from the point of view of, as compounding ingredient thermoplastic resin maximum particle diameter preferably below 230 μm, more preferably below 205 μm, enter
One step 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.Shear stress of desulfurization process etc. can be utilized
Control the maximum particle diameter of the thermoplastic resin in the reclaimed rubber as compounding ingredient.And, obtained by can passing through to observe
The surface of reclaimed rubber is measuring the maximum particle diameter of the thermoplastic resin as compounding ingredient.
In reclaimed rubber as compounding ingredient thermoplastic resin content preferably more than 2 mass %, more preferably 8
More than quality %, and preferably below 30 mass %, more preferably below 20 mass %.And, when manufacture comprising it is above-mentioned most
During the reclaimed rubber of big thermoplastic resin of the particle diameter below 250 μm, preferably the treatment temperature of desulfurization process is set to and is compared to
For the temperature of low more than 20 DEG C of the fusing point of the thermoplastic resin of compounding ingredient.
＜ infantees V band B ＞
Fig. 1 illustrates infantees V bands B (transmission belt) involved by first embodiment.Bag involved by the first embodiment
Cloth V band B are used in such as agricultural machinery, industrial machine.Sizes of the infantees V with B involved by first embodiment does not have quilt
Especially it is limited, such as infantees V band B have following sizes, and band 700～5000mm of Zhou Changwei, bandwidth are 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, the band main body 10
Compression rubber layer 11 with band inner circumferential side (pulley contact side), the bonding rubber layer 12 positioned at centre and stretching with outer circumferential side
Rubber layer 13 this three-decker.Heart yearn 14 is embedded with bonding rubber layer 12, the 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.
Compression rubber layer 11, bonding rubber layer 12 and extension rubber layer 13 are all made up of the rubber composition being crosslinked.And
And, at least one of compression rubber layer 11, bonding rubber layer 12 and extension rubber layer 13 are by involved by using first embodiment
And reclaimed rubber and the rubber composition that has been crosslinked constitute.Constitute compression rubber layer 11, bonding rubber layer 12 and uphold rubber
The rubber composition of layer 13 all preferably uses the reclaimed rubber involved by first embodiment, in this case, above-mentioned rubber
Compositionss can also be identical rubber composition.
Here, having used the rubber composition of the 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 to be mixed into rubber as rubber constituent in the reclaimed rubber and
As base rubber material.Rubber optimal ethylene-alpha-olefin elastomer now, wherein more preferably EPDM.In rubber composition
Rubber constituent in rubber content preferably more than 20 mass %, and preferably below 80 mass %, more preferably in 60 matter
Amount below %.
In the rubber composition of the reclaimed rubber used involved by the first embodiment, it 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 to include：For example, the reinforcing agent such as white carbon black, softening agent, processing aid, vulcanization accelerator additive, cross-linking agent,
Vulcanization accelerator, age resister etc..
In the case where the reclaimed rubber involved by first embodiment is comprising reinforcing agent, it is also possible to mismatch reinforcing agent.
On the other hand, it is in the case of in the rubber composition comprising the reclaimed rubber involved by first embodiment comprising rubber, excellent
Reinforcing agent is closed in apolegamy.
Can include as the white carbon black of reinforcing agent：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 Silicon stone.Reinforcing agent both can be made up of a kind of reinforcing agent, it is also possible to be made up of various reinforcing agents.From wear resistance and bending resistance
From the viewpoint of balance between song, preferred reinforcing agent contains relative to 100 mass parts of rubber constituent of rubber composition
Measure as 30～80 mass parts.
Can include as softening agent：For example, petroleum-type softening agent；The mineral oil softeners such as paraffin oil；Oleum Ricini,
The plant oils such as Oleum Gossypii semen, Semen Lini oil, Oleum Brassicae campestriss, Oleum Glycines, Petiolus Trachycarpi oil, Oleum Cocois, Oleum Arachidis hypogaeae semen, haze tallow, Colophonium, Oleum Pini soften
Agent etc..Softening agent both can be made up of a kind of softening agent, it is also possible to be made up of various softening agents.Softening agent is relative to building rubber compound
The content of 100 mass parts of rubber constituent of thing is, for example, 2～30 mass parts.
Can include 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 various processing aids.Rubber of the processing aid relative to rubber composition
The content of 100 mass parts of glue composition is, for example, 0.1～3 mass parts.
Can include as vulcanization accelerator additive：Such as metal-oxide such as magnesium oxide, Zinc Oxide (zinc white), metal carbon
Hydrochlorate, fatty acid and its derivant etc..Vulcanization accelerator additive both can be made up of a kind of vulcanization accelerator additive, it is also possible to by various
Vulcanization accelerator additive is constituted.Vulcanization accelerator additive relative to the content of 100 mass parts of rubber constituent of rubber composition is, for example,
0.5～8 mass parts.
Can include as cross-linking agent：Sulfur and organic peroxide.As cross-linking agent, sulfur can be coordinated, also may be used
To coordinate organic peroxide, sulfur and organic peroxide can also be used together.It is in the case where cross-linking agent is sulfur, excellent
Cross-linking agent is selected to be, for example, 0.5～4.0 mass parts relative to the use level of 100 mass parts of rubber constituent of rubber composition；Handing over
In the case that connection agent is organic peroxide, preferred cross-linking agent is matched somebody with somebody relative to 100 mass parts of rubber constituent of rubber composition
Resultant is, for example, 0.5～8.0 mass parts.
Can include as organic peroxide：For example, the dialkyl such as dicumyl peroxide class organic peroxy
The peroxidating ketones such as the peroxyesters organic peroxide such as compound, peroxide acetic acid butyl ester, two Ketohexamethylene of peroxidating are organic
Peroxide etc..A kind of organic peroxide can both be coordinated, it is also possible to coordinate various organic peroxides.
When cross-linking agent is sulfur, rubber composition is included：The gel section that formed by the sulfur cross-linking portion that left behind,
With the sulfide linkage formed due to the sulfur cross-linking for being added；When cross-linking agent is organic peroxide, rubber composition is included：By
Gel section and the C-C keys formed as organic peroxide is crosslinked that the sulfur cross-linking portion that left behind is formed.Therefore,
By using the reclaimed rubber involved by first embodiment, and it is obtained in that crosslinking points than only using the rubber group of EPDM rubbers
Rubber composition more than compound.
Can include as vulcanization accelerator：For example, thiazoless (such as MBT, MBTS etc.) vulcanization accelerator, thiuram
Class (such as TT, TRA etc.) vulcanization accelerator, sulfenamide (such as CZ etc.) vulcanization accelerator, dithiocarbamatess
(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 various sulfur
Change accelerator to constitute.Particularly when sulfur having been used as cross-linking agent, preferably coordinate vulcanization accelerator, in this case,
It is preferred that use thiazoless vulcanization accelerator and thiurams vulcanization accelerator simultaneously.Vulcanization accelerator is relative to rubber composition
The content of 100 mass parts of rubber constituent is, for example, 2～10 mass parts.
Can include 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 various age resisters.Age resister relative to 100 mass parts of rubber constituent of rubber composition content be, for example, 0～
8 mass parts.
It should be noted that as rubber chemicals, montmorillonite race, Vermiculitum race and Kaolin can also be coordinated in addition
The phyllosilicates such as race.
Form drawing direction (the drawing of the rubber composition of reclaimed rubber involved by first embodiment is used
Direction) the fissipation factor tan δ at upper 100 DEG C more preferably more than 0.06, and preferably exists preferably more than 0.04
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 having carried out to heart yearn 14 before forming
Process is stated, i.e.,：The bonding reheated after the heart yearn is impregnated in RFL (Resorcin-Formaldehyde-Latex) aqueous solution is processed
And/or it is impregnated into the bonding process of rear re-dry in rubber paste.
The woven fabric, knitting for example by made by the yarns such as cotton, Fypro, polyester fiber, aramid fiber of reinforcement cloth 15
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
Following process are carried out, i.e.,：The bonding reheated after the reinforcement cloth 15 is impregnated in RFL aqueous solutions is processed and/or by rubber
Paste is applied to after becoming on the surface with 10 side of main body processes its bonding being dried again.
Below, manufacture methods of the infantees V with B involved by first embodiment is illustrated.
First, prepare compression rubber layer sheet rubber 11 ', bonding rubber layer sheet rubber 12 ', uphold 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
With sheet rubber 12 ' and extension sheet rubber of the rubber layer containing the reclaimed rubber involved by first embodiment in sheet rubber 13 '
Obtained by following methods, the method is by the reclaimed rubber and rubber involved by first embodiment using stack etc.
The uncrosslinked rubber composition processing slabbing of compounding ingredient mixing, 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, compression rubber layer sheet rubber 11 ' is repeatedly wound on sleeve (mantle) 21, then
The rubber layer sheet rubber 12 ' of winding bonding thereon.And then again thereon, as shown in Figure 2 B, spirally wind upper twisting
14’.Rubber layer sheet rubber 12 ' is binded on winding successively as shown in Figure 2 C thereon again and uphold rubber layer sheet rubber 13 '
Afterwards, just produce cylindric laminated structure 10 '.
Then, as shown in Figure 2 D, after cylindric laminated structure 10 ' being cut into the annulus of Rack on sleeve 21,
The annulus is taken off from sleeve 21.
Then, annular lamellar structure 10 ' is winded at into one as outside using 11 ' side of compression rubber layer sheet rubber
To between belt wheel, rotate, on one side as shown in Figure 2 E as by compression rubber layer with the two of the laminate portion of sheet rubber 11 '
Skew back is cut into V-arrangement to adjust volume.
Next, 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
Heated and pressurizeed in putting it into sulfur still.Now, the rubber constituent of annular lamellar structure 10 ' is crosslinked and forms band master
Body 10, and twisting 14 ' is integrated and become heart yearn 14 with band bonding realizations of main body 10, and cloth 15 ' with bind with main body 10
Realize integration and become reinforcement cloth 15, thus just produce the infantees V band B involved by first embodiment.
(second embodiment)
Under the manufacture method of the reclaimed rubber involved by second embodiment, take out from used rubber and hand over
Connection rubber, in the case where there are the thermoplastic resin as compounding ingredient, applying shear stress to the crosslinking rubber is carried out
Desulfurization process.
Here, as used rubber, such as transmission belt, conveyer belt, tire, flexible pipe etc. can be included.
Can include as the rubber constituent being included in crosslinking rubber：For example, natural rubber (NR), ethylene-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..The rubber constituent being crosslinked in rubber was included in both
Can be made up of a kind of rubber constituent, it is also possible to be made up of various rubber constituents.In crosslinking 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 crosslinking rubber, white carbon black, filler, age resister, plasticizer etc. can also be coordinated in addition.
For being crosslinked rubber, rubber constituent is crosslinked, and both can be crosslinked with sulfur, it is also possible to use organic peroxy
Compound is crosslinked.
From from the viewpoint of effectively carrying out desulfurization process, preferably：By the crosslinking rubber pulverizing powdering before desulfurization process
Or it is granular.The mean diameter of powdery or granular crosslinking rubber preferably more than 10 μm, more preferably more than 100 μm, further
It is preferred that more than 200 μm, and preferably in below 5mm, more preferably in below 3mm.
Can include as the thermoplastic resin of compounding ingredient：For example, polyamide (PA), poly terephthalic acid second
The compounding ingredients such as terephthalate resin (PET), acrylic resin (PP).Can include as polyamide (PA)：For example, Buddhist nun
Dragon 6, nylon66 fiber etc..Both can be made up of a kind of thermoplastic resin as the thermoplastic resin of compounding ingredient, it is also possible to by various
Thermoplastic resin is constituted.Can include as the form of the thermoplastic resin of compounding ingredient：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.
It preferably is contained in crosslinking rubber as the thermoplastic resin of compounding ingredient, that is to say, that as compounding ingredient
Thermoplastic resin is preferably in following occasions, i.e.,：Cooperation is scattered here and there in advance in the friendship taken out from used rubber
In connection rubber, and apply the occasion of shear stress to being crosslinked rubber.In this case, as compounding ingredient in crosslinking rubber
Thermoplastic resin content 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 thermoplastic resin as compounding ingredient it is also possible that,
I.e.：It is not included in being crosslinked in rubber, but is present in when desulfurization process are carried out and crosslinking rubber mix, and applies to being crosslinked rubber
Plus the occasion of shear stress.
In the manufacture method of the reclaimed rubber involved by second embodiment, desulfurization process are that one kind is applied to being crosslinked rubber
Plus shear stress makes crosslink part cut-out, the physical treatment of depolymerization.Specifically, can include as desulfuration processing method：
For example, it is right using the Shearing Flow reactive tank (shear flow field reacting tank) with single screw rod or twin screw
The method that crosslinking rubber is carried out continuously desulfurization process.
Also, under the manufacture method of the reclaimed rubber involved by 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 for being used for compounding ingredient.Here, the process temperature of desulfurization process
Degree refers to the temperature of treated object during desulfurization process, for example, refers to using the shearing with single screw rod or twin screw
Design temperature in the groove of Shearing Flow reactive tank in the case of the reactive tank of flow field.
Here, for the fusing point as the thermoplastic resin of compounding ingredient, being polyamide in thermoplastic resin
(PA) in the case of, for example when for nylon 6 when its fusing point be 225～235 DEG C, when for nylon66 fiber when its fusing point be 260～270
℃；In the case where 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.As the thermoplastic resin of compounding ingredient
The fusing point of fat can be by differential scanning calorimeter (DSC：Differential Scanning Calorimeter) measurement.
Specifically, for the treatment temperature of desulfurization process, for example, when as compounding ingredient used fusing point be 225
DEG C nylon 6 when the treatment temperature is set in into less than 205 DEG C, when having used the nylon that fusing point is 260 DEG C as compounding ingredient
The treatment temperature is set in into less than 240 DEG C when 66.From the viewpoint of the physical property deterioration of the reclaimed rubber from obtained by suppressing, take off
The treatment temperature of sulphuring treatment is preferably set to the fusing point than coordinating the thermoplastic resin as compounding ingredient in crosslinking rubber
Low more than 30 DEG C of temperature, is more preferably set to more than 50 DEG C lower than the fusing point of temperature, is further preferably set to more molten than this
The temperature of low more than 60 DEG C of point, and from from the viewpoint of being adapted for desulfurization process, more than 180 DEG C are preferably set to, it is more excellent
Choosing is set in more than 200 DEG C.It should be noted that when there is various thermoplastic resins as compounding ingredient, at desulfurization
The treatment temperature of reason is set to the temperature of low more than 20 DEG C of minimum fusing point in the fusing point than various thermoplastic resins.
From from the viewpoint of being adapted for desulfurization process, the shear stress of desulfurization process is preferably set to more than 1MPa, more
It is preferably set to more than 4MPa, and from from the viewpoint of suppressing the effect as the thermoplastic resin of compounding ingredient insufficient,
The shear stress of desulfurization process is preferably set to below 20MPa, is more preferably set in below 15MPa.
When the thermoplastic resin as compounding ingredient is included in crosslinking rubber, from the manufactured reclaimed rubber of regulation
From the viewpoint of physical property preferably：Under desulfurization process, the thermoplastic resin with the be included as compounding ingredient of crosslinking rubber is made
Other different thermoplastic resins are present in the outside of the crosslinking rubber as compounding ingredient, that is to say, that will be comprising conduct
The crosslinking rubber of the thermoplastic resin of compounding ingredient is mixed with other thermoplastic resins as compounding ingredient.As cooperation
Other thermoplastic resins of material can include above-mentioned cited polyamide (PA) etc., can enumerate as its form
Go out such as powdery, granular, fibrous etc..Can be crosslinked in rubber with being included in as other thermoplastic resins of compounding ingredient
It is identical as the thermoplastic resin of compounding ingredient, it is also possible to be different from.
Under the manufacture method of the reclaimed rubber involved by second embodiment, by desulfurization process shearing cutting off work
Thermoplastic resin for compounding ingredient makes the thermoplastic resin realize small particle and scatter, so as to the just institute after desulfurization process
For the reclaimed rubber for obtaining, in crosslinking rubber identical rubber constituent, it is scattered here and there containing maximum grain as compounding ingredient
Thermoplastic resin of the footpath below 250 μm.Become different as thermoplastic resin of the compounding ingredient maximum particle diameter more than 250 μm
Thing, and it is likely to become the starting point for cracking.From the thermoplasticity suppressed in resulting reclaimed rubber as 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.Being capable of profit
Shear stress with desulfurization process etc. control the reclaimed rubber in as compounding ingredient thermoplastic resin maximum particle diameter.And
And, the maximum grain of the thermoplastic resin as compounding ingredient can be measured by the surface of the reclaimed rubber obtained by observation
Footpath.
In reclaimed rubber, the content of rubber constituent is preferably more than 30 mass %, more preferably more than 40 mass %, and
It is preferred that below 70 mass %, more preferably below 60 mass %.In reclaimed rubber as compounding ingredient thermoplastic resin
Content 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, there will be has as compounding ingredient
The treatment temperature applied when shear stress carries out desulfurization process to being crosslinked rubber 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, acquisition are scattered here and there containing maximum particle diameter as compounding ingredient
The reclaimed rubber of the thermoplastic resin below 250 μm, thus under desulfurization process as compounding ingredient thermoplastic resin simultaneously
Without melt, thus by obtained from resulting reclaimed rubber rubber composition as shown in the test evaluation 2 of following embodiments
As become low tan δ, even if thus be subject to alternating bending when can also suppress heating.Therefore, it is possible to manufacture suitable for transmission
The reclaimed rubber of the rubber with waiting by alternating bending.In general, in the manufacture of reclaimed rubber, being included in as original
The thermoplastic resins such as the chopped fiber as compounding ingredient in the crosslinking rubber of material are normally used as foreign body via screening, air floating table
(air floating table) is separated, but under the manufacture method of the reclaimed rubber involved by second embodiment, is made
For compounding ingredient above-mentioned thermoplastic resin contribute to having used obtained by the rubber composition of reclaimed rubber realize low tan δ
Change.
Under the manufacture method of the reclaimed rubber involved by second embodiment, essence is carried out after desulfurization process as needed
Refining, filtration, tabletting (sheeting).
The reclaimed rubber obtained using the manufacture method of second embodiment can with involved by first embodiment
Reclaimed rubber identical constitute, that is to say, that the reclaimed rubber is can come from comprising the EPDM crossed with sulfur cross-linking
The rubber composition of rubber, and the gel fraction of the reclaimed rubber is 50～85 mass %.
The reclaimed rubber obtained using the manufacture method of second embodiment is identical with first embodiment, to the regeneration rubber
Glue is mixed into and is included in the identical or different rubber of rubber in reclaimed rubber and is used as base rubber material, or the regeneration rubber
Glue is used directly as base rubber material, then coordinates the rubber chemicals comprising cross-linking agent thereto, for example exists as constituting
Rubber of the infantees V in first embodiment shown in Fig. 1 with the rubber such as transmission belt, conveyer belt, tire, flexible pipe as B
Compositionss.For the reclaimed rubber obtained using the manufacture method of second embodiment, due to having used the reclaimed rubber
Rubber composition is low tan δ, even if thus being subject to also suppress heating during alternating bending.It is therefore preferable that：By having used root
The rubber composition of the reclaimed rubber obtained according to the manufacture method of second embodiment, composition to be carried out the transmission belt of alternating bending
At least a portion with main body.
The rubber composition of the reclaimed rubber obtained according to the manufacture method of second embodiment has been used in form drawing
Storage moduluss E on direction at 25 DEG C ' preferably in more than 12MPa, more preferably in more than 15MPa, and preferably 70MPa with
Under, more preferably in below 40MPa.Storage moduluss E at 100 DEG C ' preferably in more than 8MPa, more preferably in more than 10MPa, and
It is preferred that in below 50MPa, more preferably in below 30MPa.Storage moduluss E at 120 DEG C ' preferably in more than 7MPa, more preferably exist
More than 9MPa, and preferably in below 50MPa, more preferably in below 25MPa.
The reclaimed rubber obtained according to the manufacture method of second embodiment 25 DEG C on the form drawing direction at loss
Factor t an δ 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 more preferably more than 0.06, and preferably exists preferably more than 0.04
Less than 0.14, more preferably below 0.11.
Storage moduluss E can be obtained according to JIS K6394 ' and fissipation factor tan δ.
Embodiment
[test evaluation 1]
(rubber composition)
As crosslinking rubber, EPDM composition (the rubber constituent i.e. content of EPDM crossed with sulfur cross-linking is prepared：50 matter
Amount %).Then, by the crosslinking rubber pulverizing make into 150 μm of mean diameter powdery or it is 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 crosslinking rubber applying shear stress carries out desulfurization process, cooled down and prepare reclaimed rubber.Now, utilize
The variable for the treatment of temperature, screw speed (shear stress) and process time is controlled to gel fraction.Specifically, will process
Temperature is set to 200 DEG C, and screw speed is set to 400rpm (shear stress 7MPa), so as to obtain gel fraction for 70 mass %
Reclaimed rubber 1.Treatment temperature is set to into 220 DEG C, and screw speed is set to into 400rpm (shear stress 8MPa), so as to obtain
Gel fraction is the reclaimed rubber 2 of 52 mass %.Treatment temperature is set to into 260 DEG C, and screw speed is set to into 600rpm (shearings
Stress 11MPa), so as to obtain 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.
Using reclaimed rubber 1～3, the uncrosslinked rubber of following embodiments 1-1～1-4 and comparative example 1-1～1-2 is produced
Compositionss.The composition of each uncrosslinked rubber composition is also show 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. are manufactured, 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,
Sulfur (Karuizawa Refinery CO., LTD. are manufactured, 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 thiazoless
(Ouchi Shinko Chemical Ind Co., Ltd. manufactures vulcanization accelerator, trade name：Nocceler DM-P) mixed after 1 mass parts
Refining, has just obtained uncrosslinked rubber composition, using the 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 1 mass parts of stearic acid, 5 mass parts of Zinc Oxide, 20 mass parts of softening agent, organic peroxide (Japanese oils and fatss
Co., Ltd. manufactures, trade name：PERBUTYL P-40,40 mass % of purity) 8 mass parts (3.2 mass parts of effective ingredient) are laggard
Row mixing, has just obtained uncrosslinked rubber composition, using the uncrosslinked rubber composition as embodiment 1-2.
＜ embodiment 1-3 ＞
Will be in addition to having used reclaimed rubber 2, other compositions uncrosslinked rubber composition all same as Example 1 is made
For embodiment 1-3.
＜ embodiment 1-4 ＞
Relative to the reclaimed rubber 1 (as the EPDM50 mass parts of rubber constituent) of 100 mass parts, EPDM rubbers are mixed with
(JSR Corp. manufactures, trade name：EP33) 50 mass parts, relative to 100 mass parts of rubber constituent included in which
Speech, used as rubber chemicals, (TOKAI CARBON CO., LTD. are manufactured, trade name to have coordinated HAF white carbon blacks：SEAST 3) 50 matter
Amount part, 1 mass parts of stearic acid, 5 mass parts of Zinc Oxide, 20 mass parts of softening agent, 3 mass parts of sulfur, thiurams sulfuration promote
Kneaded after 1 mass parts of 2 mass parts of agent and thiazoless vulcanization accelerator, just obtained uncrosslinked rubber composition, should
Uncrosslinked rubber composition is used as embodiment 1-4.
＜ comparative example 1-1 ＞
Will be in addition to having used reclaimed rubber 3, other compositions uncrosslinked rubber composition all same as Example 1 is made
For comparative example 1-1.
＜ comparative example 1-2 ＞
Will be in addition to having used reclaimed rubber 3, other compositions uncrosslinked rubber composition all same as Example 2 is made
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 make these uncrosslinked rubber compositions be crosslinked obtained rubber composition will
The sulfide linkage formed with the gel section formed by the sulfur cross-linking portion that left behind and due to the sulfur cross-linking for being added.
On the other hand, because the rubber composition of embodiment 1-2 and comparative example 1-2 is organic peroxide is crosslinked class rubber composition,
So make these uncrosslinked rubber compositions be crosslinked obtained rubber composition will be with by the sulfur cross-linking that left behind
Gel section and the C-C keys formed as organic peroxide is crosslinked that portion is formed.
(Test model synthetic techniques)
＜ fissipation factor tan δ ＞
Sheet rubber is shaped by embodiment 1-1～1-4 and the respective uncrosslinked rubber compositions of comparative example 1-1～1-2
Vulcanized after piece, and according to JIS K6394, be that 10Hz, dynamic strain (dynamic strain) are in frequency of vibration
Fissipation factor tan δ in the case of 1.0%, when having obtained 100 DEG C on its form drawing direction.
＜ band long duration test ＞
Produce using embodiment 1-1～1-4 and the respective uncrosslinked rubber compositions of comparative example 1-1～1-2 to constitute
The infantees V bands of compression rubber layer, bonding rubber layer and extension rubber layer.It should be noted that with twisting made by polyester fiber
As heart yearn, and with cotton woven fabric as reinforcement cloth.
Fig. 3 illustrates the belt wheel horizontal layout situation with traveling testing machine 30.
With traveling testing machine 30 there are pulley diameters for 80mm driving pulley 31, and be arranged on below the driving pulley 31
Pulley diameters for 80mm driven pulley 32.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 and be hung around on driving pulley 31 and driven pulley 32
Infantees V band B on.
Will be with embodiment 1-1～1-4 and infantees V bands made by the respective uncrosslinked rubber compositions 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 of suspension 80kg on driven pulley 32
On cloth V band B, and rotary load is not applied to driven pulley 32, at normal temperatures, driving pulley 31 is allowed with the rotating speed of 3500rpm
Rotate to allow infantees V band B to carry out traveling, and regularly allow band to stop traveling eyes and confirm either with or without cracking, true
Recognizing the moment for cracking allows end of tape traveling.Also, the band travel time by comparative example 1-1 to cracking is set to
100, the life-span of band is evaluated with its relative value.And, using non-contact surface thermometer, to band during traveling
After temperature is measured, the maximum of its temperature difference between ambient temperature has been obtained.
(test evaluation result)
Result of the test is shown in table 1.
Used gel fraction it is relatively low, for 45 mass % reclaimed rubber 3 sulfur cross-linking class comparative example 1-1 situation
Under, tan δ larger (0.175), and with heating during traveling also more (+44 DEG C), and then just produce in early stage when band traveling
Crackle causes tape lifetime shorter (100).
Using gel fraction be 52 mass %, higher than reclaimed rubber 3 reclaimed rubber 2 sulfur cross-linking class embodiment
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 it is also less (+
29 DEG C), and then tape lifetime also longer (142).
Using the enforcement that gel fraction is 70 mass %, the sulfur cross-linking class of the reclaimed rubber 1 higher 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 it is also less with heating during traveling
(+25 DEG C), and then tape lifetime also longer (149).
The comparative example of class is crosslinked in the organic peroxide for having used gel fraction relatively low, for the reclaimed rubber 3 of 45 mass %
In the case of 1-2, tan δ be 0.159, and with heating during traveling be+38 DEG C, and then tape lifetime be 120, although better than than
Compared with the situation of example 1-1, but can not be referred to as to have obtained significantly improving.
Embodiment 1-2 of class is crosslinked in the organic peroxide using the reclaimed rubber 1 that gel fraction is 70 mass %
In the case of, compared with the situation of embodiment 1-1, tan δ are further reduced (0.089), and are also more entered 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 for mixing reclaimed rubber 2 and EPDM rubbers,
Compared with the situation of comparative example 1-1 and comparative example 1-2, tan δ relatively low (0.119), and with the heating also less (+28 during traveling
DEG C), and then tape lifetime also longer (152).
For with infantees V bands 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
As a result it is can to deduce excellent tape lifetime is obtained in long duration test.And, even if by reclaimed rubber 2 and EPDM
In the case that rubber is mixed, also suitably scatter by the gel section that the sulfur cross-linking portion that left behind is formed and can
Caoutchouc elasticity is obtained, its result is can to deduce excellent tape lifetime is obtained in long duration test.
Reclaimed rubber 1 and reclaimed rubber 2 used in the rubber composition of embodiment 1-1～1-4 is by
The EPDM crossed with sulfur cross-linking carries out desulfurization process and obtains, and can realize the performance more excellent than using EPDM rubbers.
[test evaluation 2]
(reclaimed rubber)
＜ embodiment 2-1 ＞
Following crosslinking rubber are prepared.I.e.：As shown in table 2, by EPDM, (JSR Corp. manufactures, trade name：EP51) make
For crude rubber, relative to 100 mass parts of crude rubber, coordinated HAF white carbon blacks (TOKAI CARBON CO., LTD. are manufactured,
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. are manufactured, trade name for 15 mass parts, sulfur：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, thiazoless 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) sulfur cross-linking is used afterwards, just obtain crosslinking rubber.
[table 2]
| EPDM | 100 |
| HAF white carbon blacks | 50 |
| Stearic acid | 1 |
| Zinc Oxide | 5 |
| Softening agent | 15 |
| Sulfur | 3 |
| Thiurams vulcanization accelerator | 2 |
| Thiazoless vulcanization accelerator | 1 |
| Nylon66 fiber chopped fiber | 23 |
Rubber pulverizing will be crosslinked into mean diameter, after 400 μm, to put 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
Low 60 DEG C 200 DEG C of 260 DEG C of the fusing point of chopped fiber, and screw speed is set as into 600rpm (shear stresses：14MPa), to handing over
Connection rubber apply shear stress carry out desulfurization process, then cooled down, using the reclaimed rubber as
Embodiment 2-1.
With cutter cut off embodiment 2-1 reclaimed rubber, using microscope (micro-scope) (Keyemce company manufacture,
Model：VHX2000 observed after three positions of the section of the reclaimed rubber are amplified to 200 times), it can be seen that Fig. 1 institutes
The form shown, and the external diameter (maximum outside diameter) of the maximum of nylon short fibre is measured using measurement pattern, the external diameter is 148 μm.
And, gel fraction has been obtained using above-mentioned toluene swelling method, the gel fraction is 62 mass %.
<Embodiment 2-2>
Except screw speed is set to 400rpm (shear stresses：8MPa) and to being crosslinked rubber applying shear stress carry out
Beyond desulfurization process, reclaimed rubber is produced according to embodiment 2-1 identical manufacture method, using the reclaimed rubber as enforcement
Example 2-2.
For the reclaimed rubber of embodiment 2-2, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 202 μm.And, gel fraction is 68 mass %.
<Embodiment 2-3>
Except treatment temperature is set to 230 DEG C lower 30 DEG C than 260 DEG C of the fusing point of nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 600rpm (shear stresses：12MPa) apply beyond shear stress carried out desulfurization process to being crosslinked rubber, according to reality
Apply a 2-1 identical manufacture method and produce reclaimed rubber, using the reclaimed rubber as embodiment 2-3.
For the reclaimed rubber of embodiment 2-3, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 151 μm.And, gel fraction is 55 mass %.
<Embodiment 2-4>
Except treatment temperature is set to 200 DEG C lower 60 DEG C than 260 DEG C of the fusing point of nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 200rpm (shear stresses：6MPa) to being crosslinked beyond rubber carried out desulfurization process, according to embodiment 2-1 identical
Manufacture method produces reclaimed rubber, using the reclaimed rubber as embodiment 2-4.
For the reclaimed rubber of embodiment 2-4, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 227 μm.And, gel fraction is 75 mass %.
<Embodiment 2-5>
Except treatment temperature is set to 240 DEG C lower 20 DEG C than 260 DEG C of the fusing point of nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 600rpm (shear stresses：13MPa) apply beyond shear stress carried out desulfurization process to being crosslinked rubber, according to reality
Apply a 2-1 identical manufacture method and produce reclaimed rubber, using the reclaimed rubber as embodiment 2-5.
For the reclaimed rubber of embodiment 2-5, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 155 μm.And, gel fraction is 51 mass %.
＜ comparative example 2-1 ＞
Treatment temperature is set to 200 by the crosslinking rubber except unmated nylon66 fiber chopped fiber has been used as crosslinking rubber
DEG C and screw speed is set to into 400rpm (shear stresses：5MPa) to be crosslinked rubber apply shear stress carried out desulfurization process with
Outward, reclaimed rubber is produced according to embodiment 2-1 identical manufacture method, using the 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 lower 10 DEG C than 260 DEG C of the fusing point of nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 600rpm (shear stresses：10MPa) apply beyond shear stress carried out desulfurization process to being crosslinked rubber, according to reality
Apply a 2-1 identical manufacture method and produce reclaimed rubber, using the reclaimed rubber as comparative example 2-2.
For the reclaimed rubber of comparative example 2-2, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 147 μm.And, gel fraction is 46 mass %.
＜ comparative example 2-3 ＞
Except screw speed is set to 100rpm (shear stresses：5MPa) taken off to being crosslinked rubber applying shear stress
Beyond sulphuring treatment, reclaimed rubber is produced according to embodiment 2-1 identical manufacture method, using the reclaimed rubber as comparative example
2-3。
For the reclaimed rubber of comparative example 2-3, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 311 μm.And, gel fraction is 83 mass %.
＜ comparative example 2-4 ＞
Except treatment temperature is set to 250 DEG C lower 10 DEG C than 260 DEG C of the fusing point of nylon66 fiber chopped fiber, and screw rod is turned
Speed is set to 100rpm (shear stresses：4MPa) apply beyond shear stress carried out desulfurization process to being crosslinked rubber, according to reality
Apply a 2-1 identical manufacture method and produce reclaimed rubber, using the reclaimed rubber as comparative example 2-4.
For the reclaimed rubber of comparative example 2-4, nylon short fibre is measured according to embodiment 2-1 identical method
Maximum outside diameter, the maximum outside diameter are 302 μm.And, gel fraction is 70 mass %.
(Test model synthetic techniques)
Using embodiment 2-1～2-5 and comparative example 2-1～respective reclaimed rubbers of 2-4, following uncrosslinked rubber are prepared
Compositionss, i.e.,：As shown in table 3, relative to 200 mass parts reclaimed rubber (as the EPDM100 mass parts of rubber constituent), matches somebody with somebody
(NOF Corp manufactures, trade name to have closed stearic acid：Beads Stearic Acid " Tsubaki ") 1 mass parts, oxygen
(SAKAI CHEMICAL INDUSTRY CO., LTD. are manufactured, 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, sulfur
(Karuizawa Refinery CO., LTD. are manufactured, oil-treated sulfur) 3 mass parts, thiurams sulfuration promote
(Ouchi Shinko Chemical Ind Co., Ltd. manufactures, trade name for agent：Nocceler TET-G) 2 mass parts and thiazoless sulfuration
Accelerator (Ouchi Shinko Chemical Ind Co., Ltd. manufactures, Nocceler DM-P) 1 mass parts, so as to obtain uncrosslinked rubber
Glue composition.
[table 3]
| Reclaimed rubber | 200 |
| Stearic acid | 1 |
| Zinc Oxide | 5 |
| Softening agent | 15 |
| Sulfur | 3 |
| Thiurams vulcanization accelerator | 2 |
| Thiazoless vulcanization accelerator | 1 |
<Dynamic viscoelastic is tested>
By the uncrosslinked building rubber compound for having used embodiment 2-1～2-5 and comparative example 2-1～respective reclaimed rubbers of 2-4
Thing is vulcanized after shaping sheet rubber piece, and according to JIS K6394, is that 10Hz, dynamic strain are in frequency of vibration
In the case of 1.0%, storage moduluss E when measuring 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 for having used embodiment 2-1～2-5 and comparative example 2-1～respective reclaimed rubbers of 2-4
Glue composition constitutes compression rubber layer, bonding rubber layer and upholds the infantees V bands of rubber layer, and implements and 1 phase of test evaluation
Same band long duration test.Also, the band travel time by comparative example 2-1 to cracking is set to 100, with its relative value couple
The life-span of band is evaluated.
(test evaluation result)
Result of the test is shown 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, comprising nylon66 fiber chopped fiber
Storage moduluss E at the arbitrary temperature of embodiment 2-1～2-5 and comparative example 2-3～2-4 in 25 DEG C, 100 DEG C and 120 DEG C ' all compared with
Height, and fissipation factor tan δ is relatively low, and band 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 moduluss E compared with comparative example 2-1 ' it is higher, and fissipation factor tan δ
It is relatively low, and band excellent in te pins of durability.
For comparative example 2-1, due to not including nylon66 fiber chopped fiber, thus storage moduluss are relatively low and tan δ are relative
Higher, its result can be that heating when deducing bending is more, and degradation is larger.
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：As the treatment temperature of desulfurization process is close to nylon66 fiber chopped fiber
Fusing point, the physical property for thus resulting in nylon66 fiber chopped fiber are reduced.
Can deduce for comparative example 2-3 and 2-4：Due to nylon66 fiber chopped fiber in reclaimed rubber maximum particle diameter compared with
Greatly, thus easily crack at interface.
- industrial applicability-
The present invention is in the technical field of reclaimed rubber and its manufacture method and the transmission belt for having used the reclaimed rubber
It is very useful.
- symbol description-
B infantees V bands
10 band main bodys
11 compression rubber layers
12 bonding rubber layers
13 uphold rubber layer
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 (15)
1. a kind of reclaimed rubber, it is characterised in that：
In the reclaimed rubber, it is scattered here and there the thermoplastic resin containing maximum particle diameter below 250 μm as compounding ingredient.
2. reclaimed rubber according to claim 1, it is characterised in that：
The rubber constituent of the reclaimed rubber is ethene-alpha-olefin elastomer.
3. reclaimed rubber according to claim 1 and 2, it is characterised in that：
The thermoplastic resin is polyamide.
4. reclaimed rubber according to any one of claim 1 to 3, it is characterised in that：
The reclaimed rubber comes the rubber composition of the ethylene propylene diene rubber that self-contained sulfur cross-linking is crossed, and the reclaimed rubber
Gel fraction be 50～85 mass %.
5. a kind of transmission belt, it is characterised in that：
Reclaimed rubber of at least a portion with main body of the transmission belt by any one of having used Claims 1-4
Rubber composition constitute.
6. transmission belt according to claim 5, it is characterised in that：
Rubber is mixed with the rubber composition.
7. transmission belt according to claim 6, it is characterised in that：
The content of rubber described in the rubber constituent of the rubber composition is 20～80 mass %.
8. the transmission belt according to any one of claim 5 to 7, it is characterised in that：
In the rubber composition, sulfur is combined with as cross-linking agent.
9. the transmission belt according to any one of claim 5 to 8, it is characterised in that：
In the rubber composition, organic peroxide is combined with as cross-linking agent.
10. the transmission belt according to any one of claim 5 to 9, it is characterised in that：
The rubber composition 25 DEG C on the form drawing direction at storage moduluss E ' for 12～70MPa, the energy storage at 100 DEG C
Modulus E ' for 8～50MPa, storage moduluss E at 120 DEG C ' is 7～50MPa.
11. transmission belts according to any one of claim 5 to 10, it is characterised in that：
The rubber composition 25 DEG C on the form drawing direction at fissipation factor tan δ be at 0.06～0.20,100 DEG C
It is 0.04～0.14 that fissipation factor tan δ is the fissipation factor tan δ at 0.04～0.15,120 DEG C.
12. a kind of manufacture methods of reclaimed rubber, in the case where there are the thermoplastic resin as compounding ingredient to crosslinking
Rubber applies shear stress carries out desulfurization process, it is characterised in that：
The treatment temperature of the desulfurization process being set to, the fusing point of the thermoplastic resin for being used for compounding ingredient is low 20 DEG C
More than temperature, then obtain and be scattered here and there the thermoplastic resin containing maximum particle diameter below 250 μm as compounding ingredient
Reclaimed rubber.
The manufacture method of 13. reclaimed rubbers according to claim 12, it is characterised in that：
It is threadiness as the thermoplastic resin of compounding ingredient.
The manufacture method of 14. reclaimed rubbers according to claim 12 or 13, it is characterised in that：
It is included in the crosslinking rubber as the thermoplastic resin of compounding ingredient.
The manufacture method of 15. reclaimed rubbers according to claim 14, it is characterised in that：
Under the desulfurization process, its different from the thermoplastic resin of crosslinking the be included as compounding ingredient of rubber is made
Its thermoplastic resin is present in the outside of the crosslinking rubber as compounding ingredient.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014130075 | 2014-06-25 | ||
| JP2014-130075 | 2014-06-25 | ||
| JP2014141232 | 2014-07-09 | ||
| JP2014-141232 | 2014-07-09 | ||
| PCT/JP2015/002834 WO2015198538A1 (en) | 2014-06-25 | 2015-06-04 | Regenerated rubber, process for producing same, and transmission belt including same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106536617A true CN106536617A (en) | 2017-03-22 |
Family
ID=54937649
Family Applications (2)
| 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 |
| CN201580033659.XA Pending CN106459540A (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 |
|---|---|---|---|
| CN201580033659.XA Pending CN106459540A (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) | CN106536617A (en) |
| WO (2) | WO2015198537A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113994123A (en) * | 2019-06-07 | 2022-01-28 | 阪东化学株式会社 | Large V-belt |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108699413B (en) * | 2016-02-24 | 2020-07-24 | 横滨橡胶株式会社 | Rubber composition for adhesive, method for bonding rubber, 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 |
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| US6207723B1 (en) * | 1998-01-26 | 2001-03-27 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Rubber composition and method for producing the same |
| JP2008254300A (en) * | 2007-04-04 | 2008-10-23 | Mitsuboshi Belting Ltd | Power transmission belt |
| CN103154098A (en) * | 2010-07-14 | 2013-06-12 | Ubq材料有限公司 | Composite material from waste and at least one element of vulcanized rubber and tire cords |
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| 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 |
| 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 |
| 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 |
| CN103601984B (en) * | 2013-11-08 | 2015-10-14 | 四川大学 | A kind of desulfurization Ethylene Propylene Terpolymer rubber powder/polypropene blended method preparing thermoplastic sulfurized rubber |
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2015
- 2015-06-04 JP JP2016529009A patent/JPWO2015198537A1/en active Pending
- 2015-06-04 WO PCT/JP2015/002833 patent/WO2015198537A1/en active Application Filing
- 2015-06-04 JP JP2016529010A patent/JPWO2015198538A1/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 CN CN201580033659.XA patent/CN106459540A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207723B1 (en) * | 1998-01-26 | 2001-03-27 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Rubber composition and method for producing the same |
| JP2008254300A (en) * | 2007-04-04 | 2008-10-23 | Mitsuboshi Belting Ltd | Power transmission belt |
| CN103154098A (en) * | 2010-07-14 | 2013-06-12 | Ubq材料有限公司 | Composite material from waste and at least one element of vulcanized rubber and tire cords |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113994123A (en) * | 2019-06-07 | 2022-01-28 | 阪东化学株式会社 | Large V-belt |
| CN113994123B (en) * | 2019-06-07 | 2022-07-15 | 阪东化学株式会社 | Large V-belt |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015198538A1 (en) | 2015-12-30 |
| WO2015198537A1 (en) | 2015-12-30 |
| JPWO2015198538A1 (en) | 2017-04-20 |
| JPWO2015198537A1 (en) | 2017-04-20 |
| CN106459540A (en) | 2017-02-22 |
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