CN100345928C - Adhesive, rubber reinforced cord yarn, driving belt and method for producing driving belt - Google Patents
Adhesive, rubber reinforced cord yarn, driving belt and method for producing driving belt Download PDFInfo
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- CN100345928C CN100345928C CNB03142533XA CN03142533A CN100345928C CN 100345928 C CN100345928 C CN 100345928C CN B03142533X A CNB03142533X A CN B03142533XA CN 03142533 A CN03142533 A CN 03142533A CN 100345928 C CN100345928 C CN 100345928C
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Abstract
The present invention relates to a rubber reinforcement cord yarn for a transmission belt, adhesive for reinforcing the bonding strength of rubber and the rubber reinforcement cord yarn, and a transmission belt containing the rubber reinforcement cord yarn for reinforcing rubber products. The transmission belt comprises a belt body and a rubber reinforcement cord yarn, wherein the belt body and the rubber reinforcement cord yarn are bonded by vulcanization. The rubber reinforcement cord yarn is composed of an S-twisting cord yarn and a Z-twisting cord yarn, wherein the S-twisting cord yarn (or the Z-twisting cord yarn) is provided with cord yarn units and adhesive layers, wherein the surfaces of the cord yarn units are coated by resorcinol-formaldehyde latex compositions; the adhesive layers are formed around the cord yarn units, and are made from the adhesive which contains polymers containing halogen, acrylic resin monomers, epoxy resin, phenolic resin, a crosslinking agent and additives for enhancing heat resistance.
Description
Invention field
The present invention relates to a kind of reinforced rubber goods that are used for, the reinforcing rubber cord of transmission belt for example, the tackiness agent of bond strength and comprise the transmission belt of reinforcing rubber cord between a kind of Reinforced Rubber and the reinforcing rubber cord.
Background technology
Cog belt, vee-belt and many wedges belt or the like are known transmission belts commonly used.Transmission belt is sent to one or more belt pulleys or gear with motivating force by drive pulley or gear driving device.Transmission belt includes the belt body that made by rubber combination, embed the reinforcing rubber cord of belt body and cover the surface fabric on belt body surface.
Recently, because of the miniaturization of engine and energy-conservation, the indoor temperature of engine operation has trend of rising; Therefore, transmission belt need possess very high thermotolerance.Wherein, belt body is to make by the rubber combination sulfuration that will contain hydrogenated nitrile-butadiene rubber, ethylene-propylene copolymer or ethylene-propylene-compositions such as diolefine ter-polymers.The reinforcing rubber cord is made by high strength glass fiber or aramid staple fiber.
The surface of reinforcing rubber cord is covered by resorcinol formaldehyde latex (hereafter " RFL ") composition, to strengthen water-repellancy and snappiness.Around cord, form binder layer, to improve bond strength with component identical with the belt body composition.
Thus, when using above-mentioned material, the thermotolerance of belt body and cord is good, still, is used for adhesive material between belt body and the cord without optimization selection, makes that the thermotolerance of tackiness agent is not fine.Therefore, at high temperature cord is easy to separate from belt body, has shortened the life-span of transmission belt.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of reinforcing rubber cord that possesses the tackiness agent of ultrahigh heat-resistant, a kind of this tackiness agent of application and a kind of transmission belt that possesses good heat resistance when at high temperature operating.
According to the present invention, it provides a kind of tackiness agent, and this tackiness agent is used for the outermost layer of the reinforcing rubber cord that coated by the resorcinol formaldehyde latex composition.This tackiness agent contains chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, resol, linking agent and comprises the additive of at least a following substances: stannic oxide (II), butyl toxilic acid tin compound and butanethiol tin compound.
Thus, binding property and thermotolerance are improved.
According to the present invention, it provides a kind of reinforcing rubber cord.This reinforcing rubber cord comprises the cord unit, and is formed on around the cord unit, sticks to the binder layer on the rubber when sulfuration.This binder layer is made by the tackiness agent that contains chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, linking agent and be used to improve stable on heating additive.
With cord unit harness, be coated with the cord of binder layer around forming.A branch of high strength glass fiber or organic synthetic fibers are twisted to make the cord unit.
Binder layer thickness is 0.01 to 0.03 millimeter., following dry 0.5 to 2 minute at 100 to 150 degrees centigrade then with the adhesive coated cord to form binder layer.
Under 120 degrees centigrade, the reduction of the bond strength between reinforcing rubber cord and rubber is not more than 50% of the bond strength between reinforcing rubber cord and rubber under the room temperature.
Transmission belt comprises belt body, cord unit and is formed at and is used for around the cord unit cord unit is bonded in binder layer on the belt body when sulfuration.Belt body is made by rubber combination.The cord unit embeds belt body, and wraps up with the resorcinol formaldehyde latex composition.This binder layer is made by the tackiness agent that contains chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, resol, linking agent and be used to improve stable on heating additive.
Under 120 degrees centigrade, the minimizing of the stripping strength between cord unit and belt body (pilling strength) is not more than 50% of the stripping strength between cord unit and belt body under the room temperature.
The method of the rubber combination sulfidizing by will mainly containing hydrogenated nitrile-butadiene rubber, ethylene-propylene copolymer or ethylene-propylene-diene terpolymers obtains belt body.
The manufacture method of transmission belt is divided into the first step, second step and the 3rd step.The first step is included in the cord cell surface and covers the resorcinol formaldehyde latex composition.Second step was included in coating adhesive around the cord unit.The 3rd step comprised, embedded rubber by the cord unit that will be coated with tackiness agent and vulcanized then and is shaped the manufacturing transmission belt.
Brief description of drawings
By following description, purpose that the present invention may be better understood and advantage, about appended accompanying drawing, wherein:
Fig. 1 is the skeleton view of part transmission belt;
Fig. 2 is the skeleton view of part reinforcing rubber cord as shown in Figure 1;
Fig. 3 is the synoptic diagram of drive belt manufacturing process;
Fig. 4 is the skeleton view that is used for the sample of cord and rubber combination bond strength assessment experiment;
Fig. 5 is the skeleton view that is connected the sample as shown in Figure 4 on the proofing unit; And
Fig. 6 is the synoptic diagram that transmission belt pulls away the strength test method.
The description of preferred embodiment
Specific embodiments with reference to the accompanying drawings below is described in detail the present invention.
Fig. 1 is the skeleton view of part transmission belt.Transmission belt 10 is a cog belt, and it is provided with belt body 14, and this belt body 14 is formed on the surface of the transmission belt that has sawtooth 12.On the outside surface of sawtooth 12, be coated with surface fabric 18.Transmission belt 10 vertically on the reinforcing rubber cord that extends embed belt body 14.
Preferably, belt body obtains by vulcanizing used rubber combination, this rubber combination mainly contains hydrogenated nitrile-butadiene rubber, ethylene-propylene copolymer, ethylene-propylene-diene terpolymers or above-mentioned three kinds of mixture of polymers, with metallic salts of unsaturated carboxylate.In rubber combination, add when needing such as additives such as vulcanizing agent (for example sulphur or superoxide), vulcanization aid or stiffening agents.This rubber combination is crosslinked by sulfuration.
Preferably, the woven fabric formed by Kevlar or nylon fiber etc. of surface fabric 18.When needing, be used to strengthen the tackiness agent of itself and belt body 14 bond strengths in the surface coated of surface fabric 18.The weavy grain of woven fabric can be tabby weave or twill weave etc., that is to say to have no particular limits.By the vulcanization crosslinking rubber combination, be adhered on the belt body 14 with being about to surface fabric 18.
Reinforcing rubber cord 16 is by obtain reinforcing rubber S-sth. made by twisting cord 160S and the twisting of reinforcing rubber Z-sth. made by twisting cord 160Z volution together.Cord 160S and cord 160Z twist in different directions, and promptly cord 160S is in the twisting of S-direction, and cord 160Z twists in the Z-direction.
Fig. 2 is the skeleton view that part reinforcing rubber S-twists with the fingers cord 160S.Reinforcing rubber S-twists with the fingers cord 160S and comprises cord 167 and binder layer 168.Binder layer 168 is formed at around the cord 167.Cord 167 is produced as follows:
At first, with long filament 162 (every diameter the is 7 microns) harness of 200 little Denier to obtain single line (cord) 164.Then, with three fold yarn 164 harnesses, and on the Z-direction, carry out first twist to obtain first twist yarn 166.At last, with 11 strands of first twist yarn 166 harnesses, and on the S-direction, carry out end and twist with the fingers to obtain cord 167.If line 164 carries out first twist on the S-direction, then yarn 166 carries out whole sth. made by twisting on the Z-direction, to obtain the cord 167 that preparation reinforcing rubber Z-twists with the fingers cord 160Z.
Preferably, long filament 162 is made by high strength glass fiber or organic synthetic fibers.For example, organic synthetic fibers can be Kevlar, polyparaphenylene benzo two azoles fibers, carbon fiber, trevira, polyethylene-2,6-naphthalene ester (naphthalate) fiber or regenerated fiber or the like.Especially, because Kevlar has ultrahigh heat-resistant and fabulous snappiness, so Kevlar is preferred fiber.For example, Kevlar is polyparaphenylene terephthalic acid acid amides (Kevlar (trade(brand)name) du Pont manufacturing), poly-metaphenylene m-phthalic acid acid amides (Conex (trade(brand)name) Teijin Ltd. manufacturing), gathers-3,4 '-oxo diphenylene terephthalic acid acid amides/polyparaphenylene terephthalic acid amide copolymer (Technola (trade(brand)name) Teijin Ltd. manufacturing), poly-p-aminobenzoic acid acid amides, poly-p-aminophenyl hydrazides terephthalic acid acid amides or analogue.
The surface of long filament 162 is coated with RFL.Just before aforementioned first twist, line 164 is immersed RFL solution, dry then and heating makes line 164 (long filament 162) surface be covered by solid RFL.Thus, prevent breaking or splitting of cord 167, and further be, improved the water-repellancy of cord 167.
RFL solution is the first condenses of the latex of formaldehyde/Resorcinol and adding.The ratio of formaldehyde, Resorcinol and latex is a flexibility and changeability.Can in RFL solution, add antioxidant and stablizer when needing.Preferably, if long filament is made up of organic synthetic fibers, then before using the RFL covered filament, be coated with the surface of long filament 162 with Resins, epoxy or isocyanate resin.
For example working as latex is butadiene-styrene-vinyl pyridine terpolymer latex (Nipol-2518FS, Nippon Zeon Corp. makes), during the mixture of butadiene-styrene copolymer latex, butadiene latex, chlorosulfonated polyethylene latex, perbutan latex, hydrogenated butadiene-acrylonitrile copolymer latex, ethylene-propylene copolymer latex, ethylene-propylene-diene terpolymers latex etc. or any two kinds of above-claimed cpds, the latex of RFL solution has extremely strong binding property to binder layer 168.
The binder layer 168 that forms around cord 167 has improved the bounding force between reinforcing rubber cord 16 and the belt body 14.Preferably, the thickness of binder layer 168 is 0.01 to 0.03mm.Binder layer 168 thickness are big more, and the bond strength between cord 16 and the belt body 14 is big more.If thickness is greater than 0.01mm, bond strength is enough strong.If but thickness surpasses 0.03mm, it is almost invariable that bond strength keeps.Therefore, with respect to the amount of adhesive therefor, in order to obtain strong bond strength, the thickness of binder layer 168 should be between 0.01 to 0.03mm.Form the tackiness agent of binder layer 168, it is by polymer containing halogen, acrylic resin monomer, Resins, epoxy, resol, such as filler, the linking agent of carbon black etc. be used to improve stable on heating additive and formed.
Contained polymer containing halogen in the tackiness agent is preferably chlorosulfonated polyethylene, chlorinated rubber, neoprene, chlorinatedpolyethylene, ethylene chloride-propylene copolymer or chlorinated polyvinyl chloride or the like.Especially, chlorosulfonated polyethylene (Hypalon (trade(brand)name) Du Pont Dow Elastomer manufacturing) is preferred.
Contained acrylic resin monomer in the tackiness agent is preferably methacrylic acid, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester or methacrylic tert-butyl acrylate.Especially, methacrylic acid is preferred.
Contained Resins, epoxy in the tackiness agent is preferably the diglycidylether of dihydroxyphenyl propane, the polyglycidyl ether of phenolic novolac (phenolnovolak), polyglycidyl ether, brominated bisphenol category-A Resins, epoxy, cycloaliphatic epoxides or flexible-epoxy of cresols-lacquer resins (cresolnovolak) or the like.Especially, bisphenol A diglycidyl ether is preferred.
Contained carbon black in the tackiness agent is preferably N330, N550 or N762 that Syowa Cabot K.K. makes.But, used carbon black be not limited to top these.
Contained resol in the tackiness agent is preferably novolac resin, thermosetting phenolic varnish resin, thermoset resol, hot active alkyl phenol resin, the active alkyl phenol resin of non-heat or terpene modified resol.Especially, thermosetting phenolic varnish resin (SUMILITE RESIN PR12687 (trade(brand)name) Sumitomo Bakelite Co.Ltd. manufacturing) is preferred.
Contained linking agent in the tackiness agent is preferably p-quinone dioxime, p, p '-dibenzoyl quininie dioxime or tetrachloro-p-benzoquinones.Especially, p-quinone dioxime (Vulnoc GM (trade(brand)name) Ouchishinko chemical industrial Co.Ltd. manufacturing) is preferred.
Contained additive in the tackiness agent is preferably:
(1) compound of carbon group element, for example yellow lead oxide, stannic oxide (II), stannic oxide (IV), tin chloride (II), tin chloride (IV) or lead stearate;
(2) contain the compound of carbon group element, for example the mixture of methyl mercaptan tin compound, butyl tin laurate compound, butyl toxilic acid tin compound, butanethiol tin compound or tin octylate compound;
(3) mixture of the compound of zinc family elements and alkaline earth metal compound, for example barium zn cpds or calcium zn cpds;
(4) mixture of the compound of carbon group element and alkaline earth metal compound, for example calcium tin compound;
(5) mixture of the compound of the compound of carbon group element, alkaline earth metal compound and zinc family elements, for example calcium zinc-tin compound or the like.
Especially, stannic oxide (II), butyl toxilic acid tin compound, butanethiol tin compound or barium zn cpds are preferred.
With reference to Fig. 3, the manufacturing to transmission belt 14 is described hereinafter.
In the first step, the three fold yarn 164 of harness and first twist carries out RFL with first apparatus for coating 100 and handles.The RFL solution that the three fold yarn material 164 that just will be provided by feeding roller 102 imports in first steeping vat 104, and be immersed in the solution so that RFL solution coats this line.Behind line 164 dippings, drying, and in process furnace 106, heat down in predetermined condition (being the preset temperature and the scheduled time), solidify so that be coated on the RFL solution on wire rod 164 surfaces.Thus, the RFL layer forms on fiber 162 (wire rod 164) surface.Then, take out the wire rod 164 of surface coverage RFL by outlet roller 108.
In second step, made the reinforcing rubber cord by the line 164 that RFL coats with the surface.Just to wire rod 164 first twists with twist with the fingers eventually obtaining cord 167, and use second apparatus for coating 110 immediately, cord 167 coating adhesive layers are twisted with the fingers cord 160S (or Z-twists with the fingers cord 160Z) to obtain reinforcing rubber S-.Second apparatus for coating 110 has and first apparatus for coating, 100 identical construction.In second apparatus for coating 110, cord 167 discharging from feeding roller 112 imports second steeping vat 114 and impregnated in the solution, is full of in this groove and contains the above-mentioned tackiness agent and the solution of solvent.Thus, cord is coated by this solution.
Then, in process furnace 116, under predetermined condition (promptly under the preset temperature and the scheduled time), drying also heats cord 167, so that the solvent evaporation in the solution of covering thread 164 makes adhesive coated around cord.Thus, make the reinforcing rubber S-sth. made by twisting cord 160S (or Z-twists with the fingers cord 160Z) that outermost layer is the binder layer of pre-determined thickness.Take out S-by outlet roller 118 and twist with the fingers cord 160S (or 160Z).Between process furnace 116 and outlet roller 118, a fast roller 117 of control is set, the derivation speed of control cord 160S.To be twisted with the fingers cord 160S and one Z-sth. made by twisting cord 160Z by one S-that second apparatus for coating 110 is made, helically twisting is to obtain reinforcing rubber cord 16.
In step, the cylindrical fabric 120 that is used as surface fabric 18 is coated on the cylindrical die 122, has the groove corresponding to the sawtooth on the belt body 14 12 on this mould at the 3rd (a).Roll out with predetermined tension force with being about to reinforcing rubber cord 16, be looped around by around the cylindrical die 122 of cylindrical fabric 120 coverings.Repeatedly be placed on the reinforcing rubber cord 16 vulcanizing the sheet rubber 124 of making belt body 14 then.
In step, cylindrical die 122 integral body that will have sheet rubber 124 grades are placed in the sulfuration sleeve 126, and pressurization is with sulfuration at the 3rd (b).Use steam vulcanization machine 128, and in predetermined condition (promptly at preset temperature and next preset time of pressure) operation down.In this sulfidation, cylindrical fabric 120, sheet rubber 124 and reinforcing rubber cord 16 all are bonded together, some rubber of sheet rubber 124 flow in the interval between reinforcing rubber cord 16 and the cylindrical fabric by the slit between the reinforcing rubber cord 16 simultaneously.Cylindrical fabric 120 is flowed into rubber combination extruding at interval and is stretched, and then, forms the sawtooth 12 of transmission belt.
In the 3rd (c) step, from the steam vulcanization machine, take out the cylindrical band plate 130 that forms by sheet rubber 124 grades in 128, and cut, obtain transmission belt 10.
In second step, further, drying temperature can be set between 100 to 150 degrees centigrade, but preferably sets between 100 to 130 degrees centigrade, so that good bonding and stable between reinforcing rubber cord 16 and the belt body 14.Adjust drying temperature by the temperature in the control process furnace 106.Can be set in time of drying between 0.5 to 2 minute, but preferably set between 0.5 to 1 minute, to obtain good stable bonding effect.Derive the derivation speed of S-sth. made by twisting (or Z-twists with the fingers) cord 160S (160Z) by control and adjust time of drying.
In second step, if drying temperature is lower than 100 degrees centigrade or be shorter than 0.5 minute time of drying, the solvent in the tackiness agent can not evaporate fully.Like this, twisting with the fingers (or Z-twists with the fingers) cord 160S (160Z) by the S-that takes out from process furnace 116 is just coated by the tackiness agent of humidity.Some moist tackiness agents can be bonded on the control speed roller 117 between process furnace 116 and the outlet roller 118, cause the in uneven thickness of binder layer 168.
If drying temperature surpasses 150 degrees centigrade or be longer than time of drying 2 minutes, the reaction that should take place in sulfidation can take place in tackiness agent in second step.This reaction can cause when rubber combination in the 3rd (b) step by sulfuration when crosslinked, reinforcing rubber cord 16 can not be fully bonding with belt body 14.
Characteristics by the transmission belt 10 of aforesaid method manufacturing are binder layers 168, this binder layer 168 strengthens stable on heating additive, for example the tackiness agent manufacturing of stannic oxide (II), butyl toxilic acid tin compound, butanethiol tin compound or barium zn cpds by containing to be useful on.
If tackiness agent does not contain above-mentioned additive, when transmission belt when working long hours (for example in motor car engine) under the hot environment, cord can separate with belt body, or sawtooth rotten fracture in advance because of tackiness agent worsens.Yet, for the transmission belt in this environment 10,, binder layer 168 strengthens stable on heating tackiness agent because of containing, the long-time use, and cord can not separate with belt body in hot environment.Therefore, this transmission belt can be used for hot environment for a long time.
Further, though the transmission belt 10 in the present embodiment is single-face tooth-shaped bands, but the present invention can be used for the transmission belt of other type, and for example the double-sided toothed belt, the belt body cross section that all form on two surfaces of belt body of sawtooth is many wedges belt or the like that the V-arrangement rib of longitudinal extension is arranged on trapezoid vee-belt, the belt body.
Embodiment
To be described in detail four embodiment of the present invention and a Comparative Examples (seeing Table 3) hereinafter, but the present invention is not subjected to the restriction of these embodiment.For ease of explanation, wherein with the explanation of specific embodiments in each identical term of term, all have same implication.
At first, preparation RFL solution.Just with vinyl pyridine-styrene butadiene terpolymer latex (40wt% the solid content) (Nipol-2518FS (trade(brand)name) of 45 parts of weights, NipponZeon Corp. manufacturing), chlorosulfonated polyethylene latex (40wt% the solid content) (Esprene200 (trade(brand)name) of 20 parts of weights, Sumitomo Chemical Co.Ltd. manufacturing), the formaldehyde of 30 parts of weights and the condenses (formaldehyde solid content 8wt%) of Resorcinol, mix with the water of 4 parts of weights, obtain pre-composition.The milky liquid liquid that contains 55wt% mineral oil (as antioxidant) of 1 part of weight and the ammoniacal liquor of 1 part of heavy 25wt% are added in the above-mentioned pre-composition of 100 parts of weights, make RFL solution.
Table 1
| Composition | Component ratio (wt%) |
| SiO 2 | 55-65 |
| Al 2O 3 | 20-26 |
| CaO | 0-10 |
| MgO | 7-12 |
| B 2O 3 | 0-1 |
| R 2O | 0-0.5 |
Next, 200 long filaments 162 (every diameter is 7 microns) are bundled together as the blank (added greige goods) that adds, dry then, make line 164 thus, described fiber 162 is to be made by composition high strength glass fiber as shown in table 1.
Three fold yarn 164 harnesses, and deliver to first apparatus for coating 100 and carry out the RFL processing.Temperature in the process furnace 106 is 290 degrees centigrade, and time of drying, (i.e. passing through the time by process furnace 106) was 1 minute.At this moment, with respect to high strength glass fiber, the solid-state coating levels of RFL is 19wt%.Glass wire 164 harnesses that three stock-traders' know-how RFL handle are also twisted with the fingers its Z-that carries out 2.0 times/25.4mm, obtain first twist yarn 166.Then, 11 strands of first twist yarn 166 harnesses, and, obtain cord 167 to its S-sth. made by twisting that carries out 2.0 times/25.4mm.
Then, be coated with the surface of tackiness agent (embodiment 1-4 is as shown in table 3 respectively), and, binder layer 168 be formed on the outermost layer of reinforcing rubber cord 16 with second apparatus for coating 110 shown in Fig. 3 to cord 167.
Table 2
| Composition A | Composition B | Composition C | Composition D | Composition E | ||
| Polymer containing halogen *1 | 100 | 100 | 100 | 100 | 100 | |
| Carbon black *2 | 5 | 5 | 5 | 5 | 5 | |
| Clay | 15 | 15 | 15 | 15 | 15 | |
| Resol *3 | 8 | 8 | 8 | 8 | 8 | |
| Linking agent *4 | 5 | 5 | 5 | 5 | 5 | |
| Stiffening agent *5 | 1 | 1 | 1 | 1 | 1 | |
| Additive | Stannic oxide (II) | 3 | - | - | - | - |
| Butyl toxilic acid tin *6 | - | 10 | - | - | - | |
| Butanethiol tin | - | - | 10 | - | - | |
| Butyl toxilic acid tin *8 | - | - | - | 10 | - | |
| Amount to | 137 | 144 | 144 | 144 | 134 | |
(unit: by weight part)
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples | |
| Composition A | 100 | - | - | - | - |
| Composition B | - | 100 | - | - | - |
| Composition C | - | - | 100 | - | - |
| Composition D | - | - | - | 100 | - |
| Composition E | - | - | - | - | 100 |
| The acrylic resin monomer *9 | 10 | 10 | 10 | 10 | 10 |
| Resins, epoxy *10 | 10 | 10 | 10 | 10 | 10 |
| | 50 | 50 | 50 | 50 | 50 |
| Toluene | 450 | 450 | 450 | 450 | 450 |
| Amount to | 620 | 620 | 620 | 620 | 620 |
(unit: by weight part)
Table 2 and table 3 are depicted as the binder composition of embodiment 1 to 4 and Comparative Examples 1.In table 2 and table 3, "-" expression does not have added ingredients.As shown in table 2, rubber combination A (in table for be designated as " composition A ") be 100 parts of weights chlorosulfonated polyethylene (as polymer containing halogen) (
*1 Hypalon (trade(brand)name) Du Pont Dow Elastomer makes), the carbon black of 5 parts of weights (
*2 N330 (trade(brand)name) Showa Cabot K.K. makes), the resol of 15 parts of heavy clays, 8 parts of weights (
*3 Sumiliteresin PR12687 (trade(brand)name) SumitomoBakelite Co.Ltd. make), the p-quinone dioxime (as linking agent) of 5 parts of weights (
*4VulnocGM (trade(brand)name) Ouchishinko chemical industrial Co.Ltd. makes), the hardened rosin of 1 part of weight (
*5 Limeresin No.1 (trade(brand)name) Arakawa Chemical Industries Ltd. manufacturing) stannic oxide (II) of (as stiffening agent) and 3 parts of weights (as improving stable on heating additive).Among the above-mentioned rubber combination A that the dihydroxyphenyl propane (* 10) (as resol) and the solvent (toluene of 50 parts of heavy dimethylbenzene and 450 parts of weights) of the methacrylic acid (* 9) (as the acrylic resin monomer) of 10 parts of weights, 10 parts of weights joined 100 parts of weights and mix, make the tackiness agent of embodiment 1.Use the tackiness agent of embodiment 1 to make binder layer 167, make the embodiment cord 1 of twisting with the fingers cord 160S (or Z-twists with the fingers cord 160Z) as S-.
At this, to second apparatus for coating 110, the temperature of process furnace 116 is 100 to 130 degrees centigrade, and be 0.5 to 1 minute time of drying.With respect to embodiment cord 1, the tackiness agent of embodiment cord 1 is for accounting for 4wt%.On 16 points of binder layer 168,, measured its thickness by cross section with submicroscopy embodiment cord 1.The maximum ga(u)ge of binder layer 168 is 0.0238mm, and minimum thickness is 0.0089mm, and mean thickness is 0.0169mm.
The tackiness agent of embodiment 2 has the composition identical with the tackiness agent of embodiment 1, different is to add the dibutyl toxilic acid tin compound (* 6 Gureg T-7052 (trade(brand)name) Dainippon Ink and Chemical Incorporation manufacturing) of 10 parts of weights as butyl toxilic acid tin compound, and the stannic oxide (II) that replaces 3 parts of weights is as strengthening stable on heating additive.Use the tackiness agent of embodiment 2 to make embodiment cord 2.
The tackiness agent of embodiment 3 has the composition identical with the tackiness agent of embodiment 1, and different is that the butanethiol tin compound (* 7Gureg T-186 (trade(brand)name) DainipponInk and Chemical Incorporation manufacturing) that adds 10 parts of weights replaces the stannic oxide (II) of 3 parts of weights as strengthening stable on heating additive.Use the tackiness agent of embodiment 3 to make embodiment cord 3.
The tackiness agent of embodiment 4 has the composition identical with the tackiness agent of embodiment 1, different is to add the dibutyl toxilic acid tin compound (* 8Gureg T-586L (trade(brand)name) Dainippon Ink and Chemical Incorporation manufacturing) of 10 parts of weights as butyl toxilic acid tin compound, and the stannic oxide (II) that replaces 3 parts of weights is as strengthening stable on heating additive.Use the tackiness agent of embodiment 4 to make embodiment cord 4.
The tackiness agent of Comparative Examples 1 has the composition identical with the tackiness agent of embodiment 1, and different is not add to strengthen stable on heating additive.That is to say, in order to make the tackiness agent that is used for Comparative Examples, join the dihydroxyphenyl propane (as Resins, epoxy) of the methacrylic acid (as the acrylic resin monomer) of 10 parts of weights, 10 parts of weights and solvent (toluene of 50 parts of heavy dimethylbenzene and 450 parts of weights) among the rubber combination E as shown in table 2 and mix.Tackiness agent with Comparative Examples makes the Comparative Examples cord.
In order to assess the bond strength of embodiment cord 1-4 and Comparative Examples cord, make the sample of embodiment cord 1-4 and Comparative Examples cord.
Table 4
| Hydrogenated nitrile-butadiene rubber *1 | 100 |
| Stearic acid | 1 |
| | 10 |
| Carbon black *2 | 20 |
| Trimellitic acid ester in the different ninth of the ten Heavenly Stems (trimellitate isonoryl) | 10 |
| Zinc methacrylate | 25 |
| Substituted diphenylamine *3 | 1.5 |
| Trimethylolpropane trimethacrylate | 6 |
| Dicumyl peroxide *4 | 8 |
| Two (t-butylperoxy-sec.-propyl) benzene *5 | 10 |
| Amount to | 191.5 |
(unit: by weight part)
*1: trade(brand)name ZP2010; Nippon Zeon Corp.
*2: trade(brand)name N762; Showa Cabot K.K.
*3: trade(brand)name Naugard 445
*4: trade(brand)name PERCUMYL D-40
*5: trade(brand)name PEROXIMON F-40
Fig. 4 is the skeleton view of the sample 50 of embodiment 1.Rubber compounding shown in the table 4 is mediated, and formed the sheet rubber 52 that a slice 25mm is wide, 120mm is long.28 strands of embodiment 1 cords 54 are set on the surface of sheet rubber 52, then covering fabric 56 on cord 54.By vulcanizing under 150 degrees centigrade with pressing machine and pressurizeing 20 minutes, make the sample 50 of embodiment 1.
The sample structure of embodiment 2-4 and Comparative Examples is identical, and different is that they have different embodiment cords respectively.
Fig. 5 is the skeleton view that is placed on the sample 50 on the trier.In tension test, at first, fabric 56 is peeled off to the degree of determining from sample 50, between the cord 54 of peel tip and sheet rubber 52, do a kerf.The end of cord 54 and the end of sheet rubber 52 are connected on clamp 62 and 64, apply pulling force in one direction, cord 54 and film 52 are cut separation, that is, with the stress rate of 50mm/min cord 54 is pulled to the top among the figure and sheet rubber 52 is pulled to below among the figure.At room temperature (22 degrees centigrade) measure the power (be shown in the table 5, represent with " R.T (A) ") of peeling off cord 54 from sheet rubber 52.Further, sample after placing 30 minutes under 120 degrees centigrade, is tested pulling force (be shown in the table 5, represent with " 120 ℃ (B) ") in 120 degrees centigrade of air.
Table 5
| R.T(A) | 120℃(B) | (B-A)/A(％) | |
| Embodiment 1 | 78.5 | 58.8 | -25.1 |
| Embodiment 2 | 63.7 | 32.4 | -49.1 |
| Embodiment 3 | 58.8 | 36.3 | -38.3 |
| Embodiment 4 | 58.8 | 34.3 | -41.7 |
| Comparative Examples | 61.8 | 27.5 | -55.5 |
(unit: N/25mm)
As shown in table 5, at 120 degrees centigrade, peel off required power, the bond strength of the sample of embodiment 1-4 just is apparently higher than the sample of Comparative Examples.That is to say that at 120 degrees centigrade, have and contain the sample that is useful on the binder layer that improves stable on heating additive, its bond strength is higher than the bond strength that does not contain the Comparative Examples that improves stable on heating additive.
In addition, in embodiment 1-4, under 120 degrees centigrade, the minimizing of bond strength is not more than 50% (be shown in the table 5, represent with (B-A)/A) of bond strength under the room temperature between embodiment cord and the rubber.That is to say that if use the tackiness agent of embodiment 1-4 to make transmission belt, reinforcing rubber cord 16 is not easy to separate with belt body 14, in addition at high temperature bond strength reduction also seldom.
Secondly, 120 degrees centigrade with room temperature under, measure the cord of cog belt and the stripping strength of belt body.Every cog belt all is to make with embodiment cord 1-4 and Comparative Examples cord.
Embodiment band 1 is to use embodiment cord 1 to make as reinforcing rubber cord 16, and the rubber compounding of belt body 14 is shown in the table 4, and its manufacturing processed is as indicated above.The wide of cog belt is 19.1mm.Except that each personal embodiment cord 2-4 and Comparative Examples cord have replaced the embodiment cord 1, embodiment band 2-4 and Comparative Examples band have and embodiment band 1 identical construction.By method as shown in Figure 6, the stripping strength of embodiment band is measured.Just in every embodiment band, at first part 70 places, at some center cords 68 of belt body heart cutting, subsequently, at second section 72 places, the both sides of cutting belt body, with cut side cord 69, rather than center cord 68.First part 70 and second section 72 are at predetermined tooth pitch 71 separately.Then, two of band is terminated on the clamp, band is drawn back with the speed of per minute 50mm.Thus, will draw back from belt body 73 at the center cord 68 at pre-constant pitch 71 places.The required power of cord 68 is drawn back in measurement, and the value of this power is stripping strength.Under room temperature (22 degrees centigrade), measure stripping strength (be shown in the table 6, represent), and descend placement after 30 minutes at 120 degrees centigrade transmission belt with " R.T (C) ", measure its stripping strength (be shown in the table 6, represent) at 120 degrees centigrade with " 120 ℃ (D) ".
Table 6
| R.T(C) | 120℃(D) | (D-C)/C(％) | |
| Embodiment 1 | 743 | 458 | -38.4 |
| Embodiment 2 | 738 | 405 | -45.1 |
| Embodiment 3 | 729 | 412 | -43.5 |
| Embodiment 4 | 725 | 413 | -42.9 |
| Comparative Examples | 757 | 365 | -51.8 |
(unit: N)
Table 6 has been listed the stripping strength of every embodiment band and Comparative Examples band.Clearly, under 120 degrees centigrade, the stripping strength of embodiment band 1-4 is greater than the stripping strength of Comparative Examples band.
In addition, in embodiment 1-4, under 120 degrees centigrade, the reduction of the stripping strength that cord is peeled off from belt body is not more than 50% (be shown in the table 6, represent with (D-C)/C) of the stripping strength that cord under the room temperature peels off from belt body.That is to say that if use the tackiness agent of embodiment 1-4 to make transmission belt, reinforcing rubber cord 16 is limited with separating of belt body 14, even at high temperature the reduction of stripping strength also reduces.
Though specific embodiments of the present invention has been done detailed description by accompanying drawing here, obviously, skilled personnel can do many revisions within the scope of the present invention.
Claims (14)
1. one kind is used for the outermost tackiness agent of reinforcing rubber cord that coated by the resorcinol-formaldehyde latex composition, the additive that it contains chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, resol, linking agent and comprises at least a following substances: stannic oxide (II), butyl toxilic acid tin compound and butanethiol tin compound.
2. reinforcing rubber cord, it comprises:
The cord unit that the surface is coated by the resorcinol-formaldehyde latex composition; And
What form around in described cord unit is used for when sulfuration and the binder layer of rubber adhesion, and described binder layer is by containing chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, resol, linking agent and comprising that the tackiness agent of at least a additive in stannic oxide (II), butyl toxilic acid tin compound and the butanethiol tin compound makes.
3. reinforcing rubber cord as claimed in claim 2, wherein the described cord of harness unit forms the cord that is coated with described binder layer.
4. reinforcing rubber cord as claimed in claim 2 wherein obtains described cord unit by twisting a branch of high strength glass fiber or organic synthetic fibers, and this high strength glass fiber is by the SiO of 55-65wt%
2, the Al of 20-26wt%
2O
3, the CaO of 0-10wt%, the MgO of 7-12wt%, the B of 0-1wt%
2O
3R with 0-0.5wt%
2O forms.
5. reinforcing rubber cord as claimed in claim 2, the thickness of wherein said binder layer are 0.01 to 0.03mm.
6. reinforcing rubber cord as claimed in claim 2 wherein forms described binder layer by the described tackiness agent of coating on described cord unit, under 100-150 ℃ temperature dry 0.5 to 2 minute then.
7. reinforcing rubber cord as claimed in claim 2, the bond strength between wherein said reinforcing rubber cord and the rubber is not more than under the room temperature between this reinforcing rubber cord and rubber 50% of bond strength in the reduction under 120 ℃.
8. transmission belt comprises:
The belt body of making by rubber combination;
The cord unit that embeds described belt body and coated by the resorcinol-formaldehyde latex composition; And
Be used for described cord unit being adhered to the binder layer that forms on the described belt body on described cord unit in when sulfuration,
Described binder layer is by containing chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, resol, linking agent and comprising that the tackiness agent of at least a additive in stannic oxide (II), butyl toxilic acid tin compound and the butanethiol tin compound makes.
9. transmission belt as claimed in claim 8, the stripping strength of wherein said cord unit and described belt body be not more than in the reduction under 120 ℃ described cord and described belt body under the room temperature stripping strength 50%.
10. transmission belt as claimed in claim 8, wherein said cord unit is by twisting obtains to a branch of high strength glass fiber or organic synthetic fibers, and this high strength glass fiber is by the SiO of 55-65wt%
2, the Al of 20-26wt%
2O
3, the CaO of 0-10wt%, the MgO of 7-12wt%, the B of 0-1wt%
2O
3R with 0-0.5wt%
2O forms.
11. transmission belt as claimed in claim 8, wherein said belt body obtains by used rubber is vulcanized, and this rubber mainly contains hydrogenated nitrile-butadiene rubber, ethylene-propylene copolymer or ethylene-propylene-diene terpolymers.
12. transmission belt as claimed in claim 8, wherein the described cord of harness unit forms the cord that is coated with described binder layer.
13. a method of making transmission belt comprises:
The first step comprises with the unitary surface of resorcinol-formaldehyde latex composition wrapped cord;
In second step, be included in coating adhesive around the described cord unit; And
The 3rd step comprised by the described cord unit that will be coated with described tackiness agent embedding rubber, sulfuration and shaping with the acquisition transmission belt,
Described tackiness agent contains chlorosulfonated polyethylene, acrylic resin monomer, Resins, epoxy, resol, linking agent and comprises at least a additive in stannic oxide (II), butyl toxilic acid tin compound and the butanethiol tin compound.
14. the method for manufacturing transmission belt as claimed in claim 13, wherein the described cord of harness unit forms the cord that is coated with described binder layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03142533XA CN100345928C (en) | 2003-06-16 | 2003-06-16 | Adhesive, rubber reinforced cord yarn, driving belt and method for producing driving belt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03142533XA CN100345928C (en) | 2003-06-16 | 2003-06-16 | Adhesive, rubber reinforced cord yarn, driving belt and method for producing driving belt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1566247A CN1566247A (en) | 2005-01-19 |
| CN100345928C true CN100345928C (en) | 2007-10-31 |
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|---|---|---|---|
| CNB03142533XA Expired - Fee Related CN100345928C (en) | 2003-06-16 | 2003-06-16 | Adhesive, rubber reinforced cord yarn, driving belt and method for producing driving belt |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013104757A1 (en) | 2013-05-08 | 2014-11-13 | Contitech Antriebssysteme Gmbh | Method for producing a belt with prepared tension members with a cover layer |
| JP6640921B2 (en) * | 2017-06-20 | 2020-02-05 | 三ツ星ベルト株式会社 | V-ribbed belt and method of manufacturing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58179274A (en) * | 1982-04-15 | 1983-10-20 | Matsushita Electric Works Ltd | Adhesive for bonding plastic and steel |
| JPS58179642A (en) * | 1982-04-15 | 1983-10-20 | 松下電工株式会社 | Building material |
| JPS601860A (en) * | 1983-06-20 | 1985-01-08 | Nec Ic Microcomput Syst Ltd | Semiconductor integrated circuit |
| JPH02221465A (en) * | 1989-02-17 | 1990-09-04 | Asahi Fiber Glass Co Ltd | Fiber for reinforcing rubber and overcoating solution |
| JPH0450144A (en) * | 1990-06-18 | 1992-02-19 | Asahi Fiber Glass Co Ltd | Rubber-reinforcing fiber |
| JPH11158744A (en) * | 1997-11-26 | 1999-06-15 | Nippon Glass Fiber Co Ltd | Glass fiber cord for rubber-reinforcement and rubber belt |
-
2003
- 2003-06-16 CN CNB03142533XA patent/CN100345928C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58179274A (en) * | 1982-04-15 | 1983-10-20 | Matsushita Electric Works Ltd | Adhesive for bonding plastic and steel |
| JPS58179642A (en) * | 1982-04-15 | 1983-10-20 | 松下電工株式会社 | Building material |
| JPS601860A (en) * | 1983-06-20 | 1985-01-08 | Nec Ic Microcomput Syst Ltd | Semiconductor integrated circuit |
| JPH02221465A (en) * | 1989-02-17 | 1990-09-04 | Asahi Fiber Glass Co Ltd | Fiber for reinforcing rubber and overcoating solution |
| JPH0450144A (en) * | 1990-06-18 | 1992-02-19 | Asahi Fiber Glass Co Ltd | Rubber-reinforcing fiber |
| JPH11158744A (en) * | 1997-11-26 | 1999-06-15 | Nippon Glass Fiber Co Ltd | Glass fiber cord for rubber-reinforcement and rubber belt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1566247A (en) | 2005-01-19 |
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