CN85106873A - Vulcanized rubber article and production method thereof - Google Patents
Vulcanized rubber article and production method thereof Download PDFInfo
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- CN85106873A CN85106873A CN85106873.1A CN85106873A CN85106873A CN 85106873 A CN85106873 A CN 85106873A CN 85106873 A CN85106873 A CN 85106873A CN 85106873 A CN85106873 A CN 85106873A
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Abstract
The present invention relates to vulcanized rubber product and production method, this goods by one deck vulcanized rubber and one deck or which floor atresia heat uniformly thermoplastic polyurethane form, be 0.02 to 1.0 millimeter at the average thickness of at least one lip-deep that layer polyurethane of vulcanized rubber layer.This layer of polyurethane is whole fusing together with vulcanized rubber, and the peel strength between rubber layer and the layer of polyurethane is at least 1.2 kilograms per centimeter, this goods have been simplified the production technology of footwear and have been made production technology control easily, and provide fabulous flexibility for finished product, resistance to bend(ing), rub resistance, performances such as oil resistivity and resistance to ozone cracking.
Description
The present invention relates to vulcanized rubber article.In more detail, rubber involved in the present invention is to semi-hard polyurethane, and synthetic resin article, leather and fur products etc. have fabulous caking property, can be effective as sole, be in the past always ready made vamp is sticked with glue that agent bonds to or by heat welded to the vulcanized rubber sole.But in such footwear, the bonding quality of vulcanized rubber and vamp is very poor.Therefore, aspect the improvement of the adhesive bonding method of vulcanized rubber and vamp, once the someone advised, for example, vamp is put in the desired mould, and the sizing material liquation that will contain the polyurethane of blowing agent then is poured into and makes vamp be stained with foamed glue in the mould, whereby, in the time of with the sole mold pressing, vamp just is combined into an integral body (referring to Japanese patent publication number: 3698/1970 and 1680/1982) with sole.In this well-known method, in order to make the contact-making surface that lands, promptly toe cap and front portion have wearability, in above-mentioned sole foaming and mold pressing, just vulcanized rubber material are put into mould usually, then with carrying out integral die at the bottom of the mold pressing of foaming.But the shortcoming of this method is, this foamed moulded footwear, and a little less than the cementation between vulcanized rubber and the semi-hard polyurethane, and sole is not durable yet.
In order to improve at the bottom of the vulcanized rubber polyurethane with semi-rigid; the bond properties of the material of vamps such as synthetic resin article; once adopted such complicated technology; promptly the surface finish at the bottom of the vulcanizate that need be bonding is become coarse surface; carry out then that chlorination is handled and with a kind of polyurethane-type primer processing of acryloyl group modification; and then coat the adhesive of types such as polyurethane, then place it in Mo Nei and inject the polyurethane of semi-rigid or other synthetic resin articles or the like.Yet, because used rubber-sole adhesive surface is not smooth in the sole, or, before bonding, to be the adhesive surface polishing difficult therefore because the bottom surface is a thin slice or small pieces, the more impossible matsurface that is polished into equably.
Because various before the adhesion process give processing can't be even, the coating of adhesive simultaneously also can not be evenly, so when this article of footwear is subjected to flexural fatigue,, for example often peel off between semihard layer of polyurethane or the vamp at vulcanized rubber layer and synthetic resin article.
For the peel strength between improving at the bottom of synthetic resin layer (as polyurethane) and the vulcanized rubber, someone advises inserting between at the bottom of synthetic resin layer (as polyurethane) and the vulcanized rubber a kind of adhesive phase of heat cross-linking, and the heating pressurization makes them be combined into integral body (Japanese Patent Application Publication 8241/1981).Therefore, in this method, earlier a kind of heat cross-linking adhesive is coated onto on the polyurethane film that (scribbling releasing agent on the mould enters to prevent adhesive) formed in mould, put half finished rubber then, at last, under high temperature and high pressure, carry out the hot pressing mold pressing, a shortcoming is arranged like this, Zhong Jian adhesive is uneven in integral body exactly, or enter into the air in the mould or the volatile materials that produces in the rubber composition in sulfidation this all can cause the local area bond effect poor.
In the art, people require always cancellation avoid at the bottom of the vulcanized rubber with synthetic resin article (as the polyurethane of semi-rigid etc.) between the giving treatment process and require further raising adhesion strength of traditional complexity.
Therefore, an object of the present invention is to simplify the production technology of sole and improve at the bottom of the vulcanized rubber and between the synthetic resin froth bed at the bottom of the vulcanized rubber with the supatex fabric of fibrous supatex fabric or impregnated synthetic resin (as thermoplastic polyurethane) or synthetic resin article (as the semi-rigid polyurathamc) adhesion strength during at integral die.
Another object of the present invention provides the vulcanized rubber article and the production method thereof of shoemaking, adopts the fabulous counter-bending fatigue performance that has of footwear that this method produces, and is comfortable and easy to wear, and can not make the synthetic resin foam sole lose flexibility.
Vulcanized rubber article provided by the present invention is by one deck vulcanized rubber, which floor form with thermoplastic polyurethane one deck or atresia, uniform, at least the average thickness of that layer polyurethane is the 0.02-1.0 millimeter on a surface of vulcanized rubber layer, this layer of polyurethane and vulcanized rubber integrally fuse together, and the peel strength between rubber layer and the layer of polyurethane is 1.2 kilograms per centimeter at least.
The present invention also provides the vulcanized rubber article production method, and this method comprises:
A unvulcanized rubber is put in the mould in order to being shaped,
At least on a surface of half finished rubber, put the thermoplastic polyurethane film of lastblock porous, the fusing point of this polyurethane should be high than rubber sulfurizing temp 30 to 100 ℃ and have tangible gas permeability, fusion pressurization mold pressing then, vulcanize cure time (T simultaneously
2Minute) be (T hardening time
1Minute) 1 to 4 times, can make vulcanized rubber article thus, one deck thermoplastic polyurethane film is arranged in this rubber, this film disappears owing to fusing makes pore, its average thickness is 0.02 to 1.0 millimeter, and it is to get at least one surface that is laminated to the vulcanized rubber layer.And the peel strength between rubber and the polyurethane thin layer is 1.2 kilograms per centimeter at least.
Vulcanized rubber article of the present invention has good caking property to other materials, thereby can make and provide for various good goods.
Brief Description Of Drawings is as follows:
Fig. 1 is the cross sectional representation of vulcanized rubber article of the present invention.Fig. 2 and Fig. 3 are the sectional schematic diagrams of producing the concrete mould of vulcanized rubber article of the present invention.Fig. 4 is that explanation production technology of the present invention and prior art technology compare flow chart.
The used rubber of the present invention is generally in shoemaking or be similar to used rubber in other moulding material of footwear material, and be at least a half finished rubber that from following rubber, chooses: natural rubber (NR) and synthetic rubber, as butadiene-styrene rubber (SBR) acrylonitrile-butadiene rubber (NBR) isoprene rubber (IR), butadiene rubber (BR) etc.
Rubber is used relatively good with the form of half finished rubber sizing material, contain calcium carbonate in this sizing material; Calcium carbonate or the magnesium carbonate crossed with silane or fatty acid treatment; Hydrosilicate is as alumina silicate; Filler is as titanium dioxide, zinc oxide; Crosslinking agent (ionic); Age resistor; Softening agent; Pigment etc.In the half finished rubber sizing material, the content range of rubber be 20-90%(by weight).In order to make fabulous cementation is arranged between rubber and the thermoplastic polyurethane, the content of rubber can change, and this will depend on the kind of used rubber.For example, for the hot rubber in sky, used rubber content 30-85%(is by weight) just enough, and for butadiene-styrene rubber, its consumption is no more than 50%(by weight) just enough.
In addition, because the kind and the content of filler are also influential to the adhesive property of rubber, therefore, reasonable way is to determine the prescription of sizing material and the mold pressing parameter of rubber, make the peel strength between polyurethane thin layer and the vulcanized rubber layer reach 1.2 kilograms per centimeter at least, this can confirm by experiment to mix whether the adhesive property of this two interlayer reaches above-mentioned requirements before a certain specific filler in rubber.
The porous thermoplastic polyurethane film that is laminated on the half finished rubber sizing material of the present invention is 250 kilograms of %/2.5 centimetre according to the measured toughness of the L-1069 of Japanese Industrial Standards (JIS) method, the air permeability of being measured with Type B Curley densometer by the method for JIS P-811 regulation is not more than 500 fens/and 100 milliliters, preferably be not more than 200 fens/100 milliliters, and the thickness of formed polyurethane thin layer is 0.02 to 1.00 millimeter, is advisable with 0.05 to 0.5 millimeter.
Because polyurethane need stand the sulfuration and the mold pressing parameter of HTHP, so its fusing point is advisable to be not less than about 160 ℃, preferably 180 ℃ to 240 ℃, this temperature is higher 30 ℃ than curing temperature and molding temperature, even high 30 ℃ to 100 ℃.
The used thermoplastic polyurethane of the present invention is to be 500 to 3000 dihydroxylic alcohols polymer by mean molecule quantity, and organically PIC and cahin extension agent are key component, makes with required ratio reaction.These components are as follows:
(1) dihydroxylic alcohols polymer
The normally used dihydroxylic alcohols polymer of the present invention has: poly-dihydric alcohol ester class, poly-dihydric alcohol ethers, poly-dihydric alcohol carbonates etc. or its mixture.
The suitable example of poly-dihydric alcohol ester has: the inferior own ethyl ester of poly-adipic acid, poly-adipic acid ethylene propylene ester, poly-adipic acid butylidene ester, polyhexamethylene adipate, poly-dihydric alcohol caproic acid lactone etc.
The suitable example of poly-dihydric alcohol ethers has: poly-ethyleneether, polytrimethylene ether, polybutylene ether, polyhexamethylene ether, poly-ethylene propylene ether etc.
The suitable example of poly-dihydric alcohol carbonic ester has: polyester family dihydroxylic alcohols carbonic ether, its representative are to gather 1, and 6-hexylene glycol carbonic ester is polycarbonate-based with the dihydroxylic alcohols that contains aromatic ring.
(2) organic PIC
The used organic PIC of the present invention has: the toluylene group diisocyanate, diphenyl diisocyanate, diphenyl-methane-4,4 '-vulcabond, the severe group diisocyanate of inferior diformazan, naphthalene diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, the dicyclohexyl vulcabond, 1,6-hexylidene diisocyanate, IPDI etc.These vulcabond can use separately or wherein two kinds or multiple mixing use.
(3) cahin extension agent
The used cahin extension agent of the present invention has: have the low-molecular-weight dihydroxylic alcohols of two reactive hydrogen atoms, low-molecular-weight diamine, low-molecular-weight hydroxylamine etc.These cahin extension agents also can use separately or wherein two kinds or multiple mixing use.
The present invention can adopt any common method to prepare.
The preparation of polyurethane can be carried out in following one or more solvents: dimethyl formamide, DEF, dimethyl sulfoxide (DMSO), dimethylacetylamide, oxolane etc.
Used specially suitable thermoplastic polyurethane comprises by dihydroxylic alcohols polymer (being soft chain segment) and making among the present invention, thermoplastic polyurethane, in this dihydroxylic alcohols polymer, the content of dihydroxylic alcohols polyether segment should be no less than 15%(by weight), preferably be no less than 25%(by weight).When this polyurethane and half finished rubber vulcanize, under the state of fusion, has fabulous performance in mould.In addition, adopt this polyurethane, integrally the thin polyurethane rete and the peel strength between the vulcanized rubber layer of the rubber of fusion are higher after the sulfuration, and have fabulous counter-bending fatigue performance, therefore, vulcanized rubber article of the present invention has its advantage as sole.
The used thermoplastic polyurethane porous membrane of the present invention is solution or the suspension by polyurethane, or is poured on a certain support by the liquid polyurethane sizing material that contains blowing agent, coagulation regulator etc., then, carries out xeothermic solidify or wet solidifying makes.
The polyurethane film of some porous has significant gas permeability.On the other hand, though other polyurethane also have fine and closely woven loose structure, because the method or the condition of solidifying, or owing to the characteristic of polyurethane itself makes that its gas permeability is very poor or do not have gas permeability at all.
Before a kind of cellular polyurethane can adopt, this is as having adopted among the present invention.But a kind of film in back must be by acupuncture, and punching processing, plasma treatment etc. make it have air-vent, so that make the porous membrane of formation have significant gas permeability.
The another kind of method of preparation perforated membrane is that the polyurethane compositions that contains fine material is made film, and this speck matter can be dissolved in the non-solvent of polyurethane, then the film that generates is carried out wash-out and handles, so that wash-out goes out this this fine material.
In addition, the porous membrane with remarkable gas permeability also can prepare by following method.For example do not have the sheet of polyurethane of porosity with the preparation of fusion system embrane method earlier at all, and then carry out acupuncture, punching processing, plasma treatment etc.
Because the working condition of polyurethane film, the ventilative of different perforated membranes such as punching condition will definitely marked change.Polyurethane has best gas permeability is advisable with 500 minutes/100 milliliters according to the basic air penetrability of the regulation polyurethane of the P-8111 of Japanese Industrial Standards (JIS), preferably is not more than 200 minutes/100 milliliters.Polyurethane porous membrane with above-mentioned air penetrability can be removed the air in the mould fully or remove the volatile materials that is produced during the sulfuration of half finished rubber and fusion, so that make the vulcanized rubber layer contact and be combined into integral body, thereby make this higher degree of peeling off be arranged between two-layer with the polyurethane thin layer.
In addition, the toughness of thermoplastic polyurethane porous membrane preferably is at least 250 kilograms of %/2.5 centimetre, because in the time of on being laminated to vulcanized rubber and during the hot pressing mold pressing, in mould, need to keep predetermined shape, want to withstand the expansion force of vulcanized rubber at least in the early stage.
According to the present invention, the sizing material of half finished rubber and thermoplastic polyurethane porous membrane carried out lamination before sulfuration and mold pressing, and the condition of sulfuration and mold pressing then depends on the kind and the prescription of rubber, shape of curing temperature, requirement or the like.Sulfidation normally under 140 ℃ to 180 ℃ temperature the pressure at model surface be 20 to 100 kilograms per centimeter
2Condition under carry out, pressure is 30 to 40 kilograms per centimeter
2Then better.
According to the present invention, sulfidation is at T
2=T
1-4T
1Carry out T in the formula under the condition
1(minute) be the hardening time of polyurethane under a certain predetermined curing temperature of rubber, and T
2(minute) be the time of finishing sulfuration and mold pressing.
If cure time T
2Too short, then the adhesive property between rubber layer and the polyurethane thin layer improves few, on the other hand, if cure time is oversize, then can cause the degraded of polyurethane, and can reduce the cementation between polyurethane and other material, even the cementation between rubber layer and the layer of polyurethane also is such when enough strong.
At the sulfurating stage initial stage, the half finished rubber sizing material flows in mould with molten condition, and the air-vent of the polyurethane film of porous can make air and the volatile materials in rubber size in the mould overflow.
Along with the carrying out of the vulcanization of rubber, sheet of polyurethane also melts gradually and begins to flow, thereby has destroyed the structure of porous or porose polyurethane, makes it become atresia polyurethane thin layer.
The prepared vulcanized rubber article of the present invention is bonded to such as synthetic resin article, just can obtains various products on other desirable materials such as cloth, leather.
The vulcanized rubber article of producing by method of the present invention has improved the peel strength between vulcanized rubber layer and the polyurethane film greatly, and for sole, its peel strength is at least 1.2 kilograms per centimeter or is at least 2.5 kilograms per centimeter.
Also come to illustrate in further detail the present invention with reference to the accompanying drawings below by instantiation:
Fig. 1 is the cross sectional representation of an object lesson of explanation vulcanized rubber article of the present invention, and wherein vulcanized rubber layer 1 and polyurethane thin layer 2 are to merge mutually to form complete lamination.
Fig. 2 illustrates the production method of vulcanized rubber article shown in Figure 1, sticks the polyurethane thin layer on the surface of this goods by rubber layer and makes.Referring to Fig. 2, on a warmed-up mould (former) 3, the half finished rubber sizing material 4 of packing into is put the thermoplastic polyurethane film 5 of porous thereon again.Then, put mould (formpiston) again, and pressurization makes rubber layer sulfuration and in aggregates with the layer of polyurethane fusion.
Fig. 3 illustrates the production method of vulcanized rubber article, and this goods are combined and make with the vulcanized rubber upper and lower faces by the polyurethane thin layer.With reference to figure 3, a half finished rubber 4 is placed between two thermoplastic polyurethane porous thin slices (5,5 '), with pressurization to be heated.
Fig. 4 is sole is produced in explanation according to method of the present invention technology and a prior art technology process chart relatively.
With regard to vulcanized rubber article of the present invention, it is whole that thermoplastic polyurethane thin layer wherein is that a surface with the vulcanized rubber layer fuses at least.This just can simplify the sort of rubber that makes earlier and combine the formation sole with the semi-rigid foam layer of polyurethane, sole is adhered to the multiple assorted shoe-making process that vamp gets on again.
According to the present invention, shoe-making process is controlled easily, and its sole of the product of making and vamp bonding firmly, and is flexible good, anti-bending.
Vulcanized rubber article of the present invention can be applied in the adhesive tape of line with rubber, and sebific duct on the goods such as adhesive plaster, and can be bonded on natural leather and the synthetic leather effectively, and resulting like this goods have fabulous rub resistance, oil resistivity, resistance to ozone cracking.
The present invention can illustrate with following several examples, but should not think that the present invention is only limited to these examples.Various performances in the example are then fixed by the following method.
(1) gas permeability
Method by Japanese industrial standard (JIS) P8111 defined.Measure with Type B Curly densometer.
(2) toughness
Measure the percentage elongation and the tensile strength of 2.5 centimetres of wide samples by the method for Japanese industrial standard JIS L1096 defined.
(3) peel strength
Measure the peel strength of 2.5 centimetres sample by the method for Japanese industrial standard JIS K6301 defined.
In each example, the polyalcohol in the raw material, PIC class and cahin extension agent, and the solvent abbreviation is as follows:
The abbreviation compound
PCL poly-dihydric alcohol caproic acid lactone
PTMG polybutylene ether
MDI P, P '-'-diphenylmethane diisocyanate
EC ethylene glycol
The DMF dimethyl formamide
The preparation method of the thermoplastic polyurethane film of porous is as follows:
(a) A type film
To make mean molecule quantity be 2000 PCL and MDI and react as the ethylene glycol of cahin extension agent, can obtain PAUR.Resulting polyurethane be dissolved into its weight concentration of polyurethane solutions that can obtain containing the loose structure conditioning agent among the DMF be 15% with this solution casting on polyethylene sheets, and be immersed in the moisture DMF solution, solidify to carry out wet method.Then, with resulting cellular polyurethane film washing, oven dry, can obtain a kind of film, its weight is 72 gram/rice
2, thickness is 0.34 millimeter, apparent density is 0.21 gram per centimeter
3This polyurethane film has loose structure, and most of pore all is to extend along the direction of film thickness, and these pores see through another surface from a surperficial break-through of film.
(b) Type B film
Make the PCL of mean molecule quantity 2100 and MDI and EC reaction by top (a) is described with quadrat method, generate the polyester type polyurethane, and it is dissolved among the DMF.This solution casting on polyethylene sheets, and is immersed in the moisture DMF solution, solidifies to carry out wet method.Then, with resulting polyurethane film washing oven dry, the weight of gained film is 88 gram/rice
2, thickness is that 0.33 millimeter, apparent density are 0.27 gram per centimeter
3This polyurethane film has loose structure and one deck top layer is arranged on film surface.
(c) C type film
Making mean molecule quantity is that 1000 PTMC and MDI and EG reaction generate EU.With the EU that produced (30%, by weight) and the PAUR of A type (70%, mix by weight), in DMF, form polyurethane solutions (20%, by weight).This solution casting on sheet of polyurethane, and is immersed in and carries out wet method in the moisture DMF solution and solidify.Then, with resulting polyurethane film washing, oven dry, the weight of the film of gained is 129 gram/rice
2, thickness is that 0.28 millimeter, apparent density are 0.46 gram per centimeter
3Resulting polyurethane film has the structure of porous and one deck top layer is arranged on film surface.
(d) D type
Making mean molecule quantity is that 1000 PTMC and MDI and EC are reacted into EU.Be cast in the solution (18% weight) of polyurethane in DMF on the polyethylene film and be immersed in and carry out wet method in the moisture DMF solution and solidify.Then, resulting polyurethane film film water is washed oven dry, the weight of gained film is 79 gram/rice
2, thickness is that 0.22 millimeter, apparent density are 0.36 gram per centimeter
3The endoporus that resulting polyurethane film has loose structure and relatively thinner top layer arranged and extend along the sheet thickness direction.
The performance of gained porous membrane is shown in table 1.
Table 1
The preparation method of rubber size is as follows:
165 ℃ of hardening times is that 4 minutes rubber size is as follows:
Sizing material composition weight portion
Natural rubber 50,000
Butadiene rubber (butadiene rubber) 25,000
Butadiene-styrene rubber 25,000
Sulfur 1,700
Zinc oxide 5,000
Stearic acid 1,000
Vulcanization accelerator 1,550
White carbon black 50,000
Activator 3,500
Age resistor 1,000
Calcium carbonate 15,000
Titanium dioxide 6,000
Add up to 184,750
(gum content 54.1%)
Example 1 to 8 and reference example 1 to 4
With method shown in Figure 2, the such rubber size and the polyurethane film of above-mentioned porous are to be that 165 ℃ of pressure are 50 kilograms per centimeter in temperature
2Condition under vulcanize different as shown in table 2 with each routine cure time of mold pressing.Relation between table 2 explanation sulfuration clamp time and rubber layer and the polyurethane thin layer peel strength.
Table 2
The thickness of resulting vulcanized rubber article is approximately 6 millimeters.The goods of reference example 1-4 still leave pore and hole in layer of polyurethane, also some part is not have the hole fully.In addition, in the goods of reference example, vulcanize and insufficiently cause the peel strength between rubber layer and the polyurethane thin layer not improve fully.
Example 9-13
In sizing material, adopt different gum contents, as shown in the table, C type microvoid polyurethane film (weight: 84 gram/rice
2; Thickness: 0.18 millimeter; Apparent density 0.47 gram per centimeter
3) 165 ℃ of temperature, pressure 50 kilograms per centimeter
2Thereby condition under the sulfuration mold pressing made vulcanized rubber article in 5 minutes.This products thickness is 6 millimeters, about 0.074 millimeter of thin polyurethane layer thickness, and peel strength is very high as shown in table 3.
| Prescription | Gum content | ||
| 25％ | 50％ | 75％ | |
| Rubber (polymer) | 100.0 part | 100 parts | 100 parts |
| Sulfur | 1.9″ | 1.9″ | 1.9″ |
| |
5″ | 5″ | 5″ |
| Stearic acid | 1″ | 1″ | 1″ |
| Vulcanization accelerator | 1.5″ | 1.5″ | 1.5″ |
| Calcium carbonate | 291″ | 91″ | 24.0″ |
Table 3
Example 14
As at the vulcanized rubber article described in the example 5, produce the part that sole contacts with ground with same method.Resulting part is carried out preheating, be injection molded into polyurethane thin layer sole up in the injection molding of packing into then.Then will be by the poly-dihydric alcohol ester of hexanedioic acid butylidene ester type, 1, the semi-rigid foam polyurethane that 4-butanediol and MDI are synthesized is packed into and is made sole in this mould.The injection molding condition comprises: emulsification times (Cream time) 8 seconds (raise time) 43 seconds, 145 ℃ of 5 minutes hardening times and molding temperatures.The vulcanized rubber layer of obtained sole and the peel strength between the foam polyurethane layer are 3.0 ± 0.5 kilograms per centimeter, and fabulous durability is arranged.
Compare with the goods in the example 14, by the example 5 described vulcanized rubber articles that make with quadrat method, except sulfuration with clamp time reached 20 minutes, all the other all are molded into sole by above-mentioned same condition.Peel strength between prepared its semi-hard polyurethane of sole goods and the rubber layer is 1.8 kilograms per centimeter, and as sole, its cohesive force is big not enough.
Example 15
By example 14 described same quadrat methods, the part that the sole that makes contacts with ground is coated on the surface of polyurethane thin layer with a kind of acrylic acid modified polyurethane binder, and in the mould of packing into.Then, pour polyvinyl chloride sizing material (polyvinyl chloride (degree of polymerization is 1000): 100 parts into; Plasticizer (DOP): 90 parts; Stabilizing agent; Capacity; Calcium carbonate: 10 parts) and with injection be molded into sole.The vulcanized rubber layer of resulting sole and the peel strength between the polyvinyl chloride layer are 4.0 kilograms per centimeter, have fabulous adherence.
Example 16
With the adhesive of polyurethane-type, various materials are bonded on the polyurethane thin layer of example 5 prepared vulcanized rubber articles, survey its peel strength.The results are shown in table 4, for the ease of relatively, the peel strength of the product object of making by former technology is listed in the table too.
Table 4
Though the present invention has simplified technology, made sole goods more still have equal peel strength with the goods of producing by former technology.
Example 17
The rub resistance (intensity) on the vulcanized rubber article surface of example 5, oil resistivity, and resistance to ozone cracking are measured by following condition.
(a). rub resistance
The mensuration of rub resistance is that abrasion machine by an Akron type (AKron type) is with carrying out under 1000 conditions of 6 ft lbfs polishing.
(b). oil resistivity
By the regulation of Japanese industrial standard (JIS), sample is following to 2 at 40 ℃
#Oil processing is measured after 22 hours again.
(c). resistance to ozone cracking
Measure by ozonograph under the condition that stretch 10% at sample, ozone concentration is 50PPm.Its fabulous result is as shown in table 5.
Table 5
Example 18
The C type film of example 5 is bored a hole, and pitch-row is 2 millimeters.The gas permeability of resulting perforated films is 7 seconds/100 milliliters, and toughness is 3600 kilograms, %/2.5 centimetre.With example 5 described same procedure, perforated films is made vulcanized rubber article through 5 minutes sulfuration and mold pressing.Peel strength between its rubber layer of resulting goods and the polyurethane thin layer is 3.1 kilograms per centimeter.
To be dissolved in C type polyurethane solution casting among the DMF on polyethylene sheets, then in drier with the solvent evaporation, the thickness of the polyurethane film of the atresia that obtains thus is 0.08 millimeter.Polyurethane film is bored a hole, and pitch-row is 2 millimeters, and the hole will penetrate.The gas permeability of the film in resulting many holes is 12 seconds/100 milliliters, and toughness is 4480 kilograms, %/2.5 centimetre.
The polyurethane film of this porous and rubber composite with composition identical with example 5 when 140 ℃ of temperature, sulfuration and mold pressing 10 minutes, resulting vulcanized rubber article, the peel strength between its vulcanized rubber layer and the polyurethane thin layer is 1.5 kilograms per centimeter.On the other hand, by above-mentioned same method, adopted 165 ℃ of cure times of temperature 5 minutes when just vulcanizing, the peel strength between its vulcanized rubber layer of then resulting vulcanized rubber article and the polyurethane thin layer is 2.0 kilograms per centimeter.
Reference example 5
By example 18 described same quadrat methods, just the polyurethane film of atresia does not carry out the punching processing, and makes vulcanized rubber article.Peel strength between its vulcanized rubber layer of resulting goods and the polyurethane thin layer is: when 140 ℃ of curing temperatures, be 0.4 kilograms per centimeter, and when 165 ℃ of curing temperatures, be 0.6 kilograms per centimeter.These two kinds of goods all leave bubble and can not get rid of between vulcanized rubber layer and polyurethane thin layer, thereby adhesive property is relatively poor.
Claims (7)
1, a kind of vulcanized rubber article, its composition comprises: the uniform thermoplastic polyurethane of one deck vulcanized rubber and one deck or which floor atresia, average thickness at least one lip-deep that layer polyurethane of vulcanized rubber layer is 0.02 to 1.0 millimeter, this layer of polyurethane integrally fuses together with vulcanized rubber, and the peel strength between rubber layer and the layer of polyurethane is at least 1.2 kilograms per centimeter.
2, by the described vulcanized rubber article of claim 1, the soft chain segment that wherein constitutes thermoplastic polyurethane has at least 15% to be polyether components.
3, according to claim 1 or 2 described vulcanized rubber articles, wherein the surface of polyurethane thin layer is and synthetic resin article, cloth material products or leather fusion or be bonded together.
4, the production method of vulcanized rubber article comprises the following steps
A half finished rubber is put in the mould, in order to moulding,
At least on a surface of half finished rubber, put the thermoplastic polyurethane film of lastblock porous, the fusing point of this polyurethane should be high than the curing temperature of rubber 30 to 100 ℃ and have tangible gas permeability, and then, cure time (T is vulcanized in the fusion pressurization simultaneously
2Minute) be (T hardening time
1Minute) 1 to 4 times.Can get vulcanized rubber article thus, thermoplastic polyurethane film wherein disappears owing to fusing makes pore, its average thickness is 0.02 to 1.0 millimeter, it integrally is laminated at least one surface of vulcanized rubber layer gets on, and the peel strength between rubber layer and the polyurethane thin layer is at least 1.2 kilograms per centimeter.
5, method according to claim 4, wherein the toughness that has of the thermoplastic polyurethane film of porous is at least 250 kilograms of %/2.5 centimetre.
6, according to claim 4 or 5 described methods, wherein thermoplastic polyurethane is made up of the soft chain segment that comprises 15% polyethers at least.
7, method according to claim 6, the soft chain segment that wherein constitutes thermoplastic polyurethane are the butylidene compositions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106873.1A CN1005023B (en) | 1985-09-13 | 1985-09-13 | Vulcanized rubber article and the process for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85106873.1A CN1005023B (en) | 1985-09-13 | 1985-09-13 | Vulcanized rubber article and the process for production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106873A true CN85106873A (en) | 1987-03-11 |
| CN1005023B CN1005023B (en) | 1989-08-23 |
Family
ID=4795330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106873.1A Expired CN1005023B (en) | 1985-09-13 | 1985-09-13 | Vulcanized rubber article and the process for production thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005023B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947873A (en) * | 2010-07-30 | 2011-01-19 | 罗清林 | Preparation method of polyurethane elastomer veneer |
| CN103302945A (en) * | 2012-03-09 | 2013-09-18 | 陕西飞机工业（集团）有限公司 | Preparation method for standard sealant test piece |
| CN103815619A (en) * | 2009-02-06 | 2014-05-28 | 耐克国际有限公司 | Thermoplastic non-woven textile elements |
| US9682512B2 (en) | 2009-02-06 | 2017-06-20 | Nike, Inc. | Methods of joining textiles and other elements incorporating a thermoplastic polymer material |
| US9732454B2 (en) | 2009-02-06 | 2017-08-15 | Nike, Inc. | Textured elements incorporating non-woven textile materials and methods for manufacturing the textured elements |
| US11779071B2 (en) | 2012-04-03 | 2023-10-10 | Nike, Inc. | Apparel and other products incorporating a thermoplastic polymer material |
-
1985
- 1985-09-13 CN CN85106873.1A patent/CN1005023B/en not_active Expired
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103815619A (en) * | 2009-02-06 | 2014-05-28 | 耐克国际有限公司 | Thermoplastic non-woven textile elements |
| US9682512B2 (en) | 2009-02-06 | 2017-06-20 | Nike, Inc. | Methods of joining textiles and other elements incorporating a thermoplastic polymer material |
| US9732454B2 (en) | 2009-02-06 | 2017-08-15 | Nike, Inc. | Textured elements incorporating non-woven textile materials and methods for manufacturing the textured elements |
| US10131091B2 (en) | 2009-02-06 | 2018-11-20 | Nike, Inc. | Methods of joining textiles and other elements incorporating a thermoplastic polymer material |
| US10138582B2 (en) | 2009-02-06 | 2018-11-27 | Nike, Inc. | Thermoplastic non-woven textile elements |
| US10174447B2 (en) | 2009-02-06 | 2019-01-08 | Nike, Inc. | Thermoplastic non-woven textile elements |
| US10625472B2 (en) | 2009-02-06 | 2020-04-21 | Nike, Inc. | Methods of joining textiles and other elements incorporating a thermoplastic polymer material |
| US10982364B2 (en) | 2009-02-06 | 2021-04-20 | Nike, Inc. | Thermoplastic non-woven textile elements |
| US10982363B2 (en) | 2009-02-06 | 2021-04-20 | Nike, Inc. | Thermoplastic non-woven textile elements |
| CN101947873A (en) * | 2010-07-30 | 2011-01-19 | 罗清林 | Preparation method of polyurethane elastomer veneer |
| CN103302945A (en) * | 2012-03-09 | 2013-09-18 | 陕西飞机工业（集团）有限公司 | Preparation method for standard sealant test piece |
| US11779071B2 (en) | 2012-04-03 | 2023-10-10 | Nike, Inc. | Apparel and other products incorporating a thermoplastic polymer material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005023B (en) | 1989-08-23 |
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