CN1068294A - Vulcanised rubber article for shoes and manufacture method thereof - Google Patents
Vulcanised rubber article for shoes and manufacture method thereof Download PDFInfo
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- CN1068294A CN1068294A CN 91105369 CN91105369A CN1068294A CN 1068294 A CN1068294 A CN 1068294A CN 91105369 CN91105369 CN 91105369 CN 91105369 A CN91105369 A CN 91105369A CN 1068294 A CN1068294 A CN 1068294A
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- polyurethane
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Abstract
The present invention relates to vulcanised rubber article for shoes and method for making thereof.Lamination is had has the one side of layer of polyurethane superimposed with the surperficial ground connection mutually of vulcanized rubber composition not in the base fabric of polyurethane, after heating pressurization, vulcanized rubber composition is not added sulphur, layer of polyurethane is bonded on this rubber composition surface, then base cloth is peeled off.The invention still further relates to the vulcanised rubber article is sole and the forming method that has the footwear of this sole.Be in the die cavity of footwear, to inject the thick liquid of polyurethane to carry out direct Sole moulding, on the ad-hoc location of end mold, keep vulcanised rubber article, and make it and the direct bonding sole that becomes of polyurethane.
Description
The present invention relates to vulcanised rubber article for shoes and manufacture method thereof, particularly relevant is grounding parts sole and the preparation method that has the footwear at this end with this vulcanised rubber article.
When for example using, synthetic resin article such as vulcanized rubber material and semi-rigid polyurethane or leather and fur products etc. are carried out powerful bonding processing so that it has the durability of adaptation to big external force is necessary as the ground plane material of footwear with vulcanized rubber.
In the past, above-mentioned bonding processing is that the vulcanized rubber material is once pressurizeed behind the vulcanizing/forming, need be this bonding plane roughening of polishing, and this face is carried out chlorination handle, carrying out primary coat again handles, carry out very complicated treatment process such as bonding processing then, even and carry out above-mentioned processing, its cementability still can not be satisfactory.
In order to address this problem, a kind of not vulcanized rubber composition that loads in mould has been proposed in the public clear 63-28021 communique of spy, and on one face, load the apertured film of thermoplasticity polyurethane at least with specific components and rerum natura, it is integrated that hot pressing makes both laminations then, leans against rubber article and give first formed polyurethane layer and improve method motion with the bonding force of semi-rigid polyurethane synthetic resin article etc.Yet there is following problem in this manufacture method.
1) to spend when removing the heating pressurization the unnecessary man-hour of incidental flash on vulcanised rubber article.In addition in mould by the flash of the resulting this vulcanised rubber article of heating pressurization, decorative pattern (パ-テ イ Application ダ ラ イ Application) line position at mould is the thick thin foil shape of 0.01mm～0.1mm, in order to remove it, need to carry out handwork carefully with sharp keen sword thing.。
2) state owing to formed polyurethane aspect on the vulcanised rubber article surface that obtains is very smooth, the synthetic resin article of it and semi-rigid polyurethane etc. or leather and fur products etc. when bonding, do not have securing effect, in order to improve both bonding forces, select bonding agent and carry out loaded down with trivial details bonding process.
3) in heating pressurization the vulcanized rubber composition is being flowed and during by figuration in the mold for forming along die cavity, to produce the crack on the part that polyurethane and rubber composition connect airtight, for preventing this situation, need make suitable thickness to film that (thickness after the moulding is 0.02mm～1.00mm) so that it has obdurability.And thick like this thin layer is pressed on the vulcanised rubber article, has not only influenced the flexibility of rubber, and owing to make the shrinkage factor of polyurethane and rubber composition be subjected to different influences, makes goods be easy to produce the reflex action song.
4) in mold for forming and since the polyurethane film with the direct state of contact of mould under, be subjected to pressurized, heated, so the rust of die surface, dirt etc. are attached on the pellicular front, hinder its bonding reason thereby become.
For understanding the problems referred to above, the inventor finds after deliberation, carry out the polyurethane layer side of polyurethane lamination base fabric superimposed with the surperficial ground connection mutually of vulcanized rubber composition not, and only pass through pressurized, heated, just can make this rubber layer and polyurethane layer bonding securely, and with the vulcanised rubber article that obtains like this and when being provided with as the ground bottom surface of footwear, do not need with primary coat, bonding agent, and as long as polyurethane stoste is carried out injection molding, just can obtain good cementability, thereby finish the present invention.
Be that the present invention is the following invention of putting down in writing.
1. the manufacture method of vulcanised rubber article for shoes is characterized in that:
When vulcanized rubber and polyurethane are laminated into integrally manufactured vulcanised rubber article for shoes, make the polyurethane layer side of polyurethane lamination base fabric carry out superimposed with the surperficial ground connection mutually of vulcanized rubber composition not, after the heating pressurization, the vulcanized rubber composition does not add sulphur, make the polyurethane layer mutually bonding simultaneously, then base fabric is peeled off with this rubber composition surface.
2. according to above-mentioned the 1st the resulting vulcanised rubber article for shoes of record method.
3. the manufacturing process of footwear, it is characterized in that: the shoe tree and the sole shaping dies that will comprise vamp are combined, die cavity to such formation injects polyurethane stoste, in this direct sole method, on the ad-hoc location of end mold, the vulcanised rubber article of the 2nd record of note in the maintenance utilizes direct sole method to make this rubber and polyurethane portion direct bonding and as ground bottom surface.
4. the manufacturing process of sole body is characterized in that when carrying out sole body with polyurethane stoste when being shaped, and the vulcanised rubber article and the polyurethane portion of the 2nd record of last note is directly bonding, and with it as ground bottom surface.
Employed not vulcanized rubber in the manufacture method of vulcanised rubber article for shoes of the present invention can use at least a in the rubber-like of moulding material of the be common to rubber outside natural rubber, styrene butadiene EVA (SBR), acrylonitrile butadiene EVA (NBR), isoprene rubber (IR), the butadiene rubber footwear such as (BR).As required, these not vulcanized rubber can suitably cooperate known filler in the mill, crosslinking agent, antiaging agent, softening agent, promoter, activating agent and pigment etc. make not that the vulcanized rubber composition uses.As filler as calcium carbonate, micro mist silicic acid, clay etc.; As crosslinking agent as Sulfur, zinc oxide etc.; Phenol type substances as antiaging agent as styrene phenolic ester etc.; As the black factice of the higher fatty acids as polymeric fatty acid esters class, stearic acid etc. of softening agent, the processing oil of cycloalkanes hydrocarbon system wet goods (プ ロ セ ス オ イ Le), dark substitute (サ Block ノ), white factice etc. and DOP etc.; As the thiazole accelerator as 2-mercaptobenzothiazole, bisbenzothiazole disulphide etc. of promoter, the thuriam acceserator of tetra methylthiuram list sulphite; Activating agent is as diphenyl two ring hexamines, polyethylene glycol etc.; Pigment is titanium oxide, iron oxide red and various organic pigment.
In the above-mentioned not vulcanized rubber composition, the content of rubber under the situation that does not lose the rubber performance, is not done special restriction, generally 20%-90%(weight preferably).
Base fabric in the polyurethane laminated base fabric that can use simultaneously with above-mentioned not vulcanized rubber for example can be weaving cotton cloth of being formed such as natural fiber, synthetic fibers, also can be non-woven fabric or braid.In addition, giving earlier on base fabric stacked polyurethane is that mean molecule quantity is 1000～4000 polyethylene glycols and at least a polyurethane that obtains that reacts in organic isocyanate class and the various chain elongation agent class.
Above-mentioned polyethylene glycols for example is the glycol (ジ オ-Le) etc. of the polyethers of polyethylene glycol adipate, PPA, poly adipate succinic acid ester, poly-adipic acid hexylidene diol ester and their copolymerization ethylene glycol, poly-tetrafluoro methylene ethylene glycol (Port ソ テ ト メ チ レ Application Network ソ コ-Le) etc.
The organic isocyanate class, for example be toluene support vulcabond, diphenyl methane-4,4 '-vulcabond, XDI, naphthyl vulcabond, diphenyl methane-4,4 '-the hydrogen addition product of vulcabond, the hydrogen addition product of XDI, hexamethylene diisocyanate, IPDI.
In addition, chain elongation agent class is low molecular weight diols that 2 active hydrogen atoms are arranged, low-molecular-weight diamines etc.
During synthetic above-mentioned polyurethane, can preferably go to select the proportioning of polyethylene glycols, organic isocyanate class and chain elongation agent class according to the heatmeltable that makes the polyurethane that as a result of obtains and with the cementability of above-mentioned rubber composition.
The principal element of decision polyurethane characteristic is the ratio of NCO/reactive hydrogen base, and the urethane ester content compares, aromatic ring content compares etc.
The present invention mainly is by adjusting NCO/reactive hydrogen base than deciding above-mentioned cooperation, preferably NCO/reactive hydrogen base ratio being deployed into 0.90～1.02, then can obtaining good polyurethane.
When above-mentioned polyurethane is used for when base fabric is stacked, can make the film shape in advance, and the thickness of film is not had special restriction, as long as can be the time with polyurethane stoste reaction-injection moulding sole, can remain in the desired scope just as the bonding force of the ground bottom surface of vulcanised rubber article of the present invention, usually being taken at the preceding value of heating extrusion forming is greater than 0.01mm, preferably about 0.01～0.05mm.
To the laminating method of the polyurethane of base fabric, and not specially provided for, the solvent borne bonding agent that for example also can be coated with on the polyurethane of film shape with its homogeneity or similar composition is laminated on the base fabric then.And on the surface of base fabric, should impose fluffing at this moment, so that can be intertwined well with polyurethane.
The base fabric of stacked polyurethane in the manufacture method of vulcanised rubber article of the present invention except that resulting by last note, also comprises the synthetic leather of the common spendable urethanes class in this area.
Illustrate
What Fig. 1 represented is the schematic diagram intention of the vulcanised rubber article manufacture method of the present invention the 1st embodiment.
Longitudinal sectional drawing when Fig. 2 represents to carry out direct sole injection moulding state.
Fig. 3 represents to be undertaken by injection molded the longitudinal sectional drawing of sole shaped state.
The example of a manufacture method of vulcanised rubber article of the present invention is described hereinafter with reference to Fig. 1.
In advance calculate the material that can go out rubber burr according to known technology, weigh not vulcanized rubber composition (2) by this degree, and it is inner that it is loaded into the bed die (1) that moulding uses, the mode of joining by the polyurethane thin layer (4) of the stacked cloth (3) of polyurethane and rubber composition (2), (3) be put into vulcanized rubber composition not above. At polyurethane laminated base fabric (3) and vulcanized rubber composition (2) when overlaping not, be coated with earlier suitable priming paint and also had no relations even give at the polyurethane face of this base fabric (3).
Closed mold (not shown) is at 120 ℃～180 ℃ temperature and 100kg/cm2-200kg/cm
2Pressure condition under, carry out 3～10 minutes hot pressing, and the polyurethane thin layer (4) of this base fabric bonded on the rubber composition (2). This moment remaining rubber composition (2) and polyurethane thin layer, pattern line through upper and lower mould, generate in the rubber burr (6) in ditch (5), remain in pattern line section, forming the thickness that links to each other with rubber burr (6) is the thin foil shape section (7) of 0.01～0.1mm.
After opening mold, if peel off the base fabric (3) that twines with rubber burr (6) in high temperature, the above-mentioned paper tinsel shape section (7) shown in 1 figure right-hand member then is because being wrapped on the base fabric (3), so fully separated from goods.
On the surface of the upper stacked bonding polyurethane thin layer (4) of so resulting rubber composition (2), the face that forms by base fabric (3) is turned to tiny concavo-convex (8) of copying.
In addition, when usually at the upper set rag design of bed die (1) mild, catch the base fabric (3) that twines burr rubber (6), just easily rubber from Take out in the bed die (1).
In this case, when taking out, catch respectively immediately the base fabric (3) that twining rubber burr (6) and the end of rubber, carry out strip off, then can obtain final rubber.
Resulting vulcanised rubber article when for example using with its ground bottom surface as footwear, is exactly very practical material as mentioned above. Namely, this add the sulphur goods since on the surface of polyurethane with tiny concavo-convex, when being configured to the ground bottom surface of footwear when carrying out the sole injection molded with polyurethane, polyurethane layer to sole body just can play fixing effect, and need not use priming paint, bonding agent etc., just can carry out this set.
Describe an embodiment of the method for the ground bottom surface use take above-mentioned vulcanised rubber article as footwear in detail hereinafter with reference to Fig. 2.
Fig. 2 is the key diagram of direct sole method, at the upper jacket vamp (24) of shoe tree (21), again side form (22) and the bed die (23) of it and sole part shaping usefulness are grouped together, from inlet (a) to by injection polyurethane stoste in the formed die cavity after the combination.
Understand such as Fig. 2 indication, the polyurethane thin layer (29) of vulcanised rubber article of the present invention (27) is placed up and remained on the fixed position of bed die (23), in this state, inject polyurethane stoste (28) according to well-established law to die cavity. At this moment, just do not need as existing method vulcanised rubber article primer coating, bonding agent etc. And process by following well-established law, just can obtain with take the footwear of vulcanised rubber article of the present invention as ground connection sole face.
In addition, if direct sole method that need not be above-mentioned (ダ イ レ Network ト ソ-リ Application グ method), after sole body is shaped, with itself and vamp and in the end be bonded together and to make the method for footwear good.
And this sole body can be used the sole finishing die, forms by well-established law.
For example such shown in the figure (3), the polyurethane thin layer (36) of vulcanised rubber article of the present invention (33) is put into institute's allocation of mo(u)ld bottom half (32) and remains in this place towards the top, inject polyurethane stoste (35) in the die cavity that forms to being combined by mo(u)ld top half (31) and mo(u)ld bottom half (32) then, form the body that just can obtain with the sole take vulcanised rubber article of the present invention as ground plane with following well-established law. This situation is with above-mentioned the same, fully need to be on vulcanised rubber article primer coating, bonding agent etc.
Because the present invention has above structure and effect, so bring following effect.
1) in the manufacture method of vulcanised rubber article, when peeling off base fabric, produce the paper tinsel shape section that is consisted of by rubber and polyurethane in pattern line section, because itself and burr rubber all are intertwined with base fabric, so it also can separate from rubber fully, therefore implement at an easy rate the removal that thickness is the paper tinsel shape burr of 0.01mm～0.1mm, thereby solved this a great problem in the prior art.
2) vulcanised rubber article of the present invention, because the effect of copying of turning to by base fabric, on the surface that is bonded in the polyurethane thin layer on the rubber, formed tiny concavo-convex, when the synthetic resin articles such as itself and semi-rigid polyurethane or leather and fur products etc. are bonding, just can play good fixed effect, its result has improved the bonding force between the bi-material, and can save in the past the selection bonding agent and loaded down with trivial details bonding process.
When 3) in the manufacture method of this vulcanised rubber article, heating pressurization, because the polyurethane thin layer that connects airtight with rubber composition is supported by base fabric, even the vulcanized rubber composition can not produce the crack flowing along the die cavity in the mold for forming even formed thin layer is very thin yet. Therefore there is no need as in the past, to have kept its obdurability by the thickness that increases polyurethane. Its result, the flexibility that the vulcanised rubber article after the moulding namely can do harm to rubber can not be subjected to the thin layer shrinkage factor yet Impact and make goods produce warpage.
When 4) in the vulcanised rubber article manufacture method, heating pressurization; in mold for forming; polyurethane does not directly contact with mould because of the protection of base fabric, and the sort of rust and dirt owing to die surface is attached on the polyurethane thin layer surface and hinders bonding problem so can not occur in the past.
When 5) in the vulcanised rubber article manufacture method, carrying out pressurized, heated, because the ventilative effect of base fabric woven design,, can not produce accumulating of air fully at mould and polyurethane thin layer or not on the contact-making surface of vulcanized rubber composition.And, can very successfully carry out the demoulding because the centre has base fabric to get involved.
6) owing on the surface of resulting vulcanised rubber article, having formed the polyurethane resin composition, even,, also can not bring obstruction after shelving for a long time to bonding force so this rubber is re-used through placing things such as also can not oozing out plasticizer.
Below by further describing the present invention for embodiment.
When making the sport footwear of polyurethane shaping, answer the adhesive rubber sheet at the most severe foot-operated position of sole friction with direct sole injection method.This sheet rubber is the ester ratio of putting down in writing by among the table 1A, is the thin slice of the not vulcanized rubber composition of 5mm with the resulting thickness of general processing method.
From this not on the vulcanized rubber composition sheet, cut not the vulcanized rubber sheet by the capacity that can go out the rubber burr after, it is loaded into vulcanizing/forming with in the bed die.On the lamina plane of the polyurethane of commercially available urethanes class synthetic leather (Soft Roll (ソ Off ト パ イ Le) 510-P Xiao Song refining (strain) system), be coated with in advance the priming paint of composition as shown in table 2 thinly, and block by the size that covers bed die, by priming paint coated face and last note rubber composition sheet mutually ground connection overlap, after making this urethanes class synthetic leather become upper side ground to place, closed mold is that 150 ℃ of pressure are 150kg/cm in mold temperature
2Condition under carry out adding in 5 minutes sulphur.
This moment, remaining not vulcanized rubber constituent produced burr rubber after the pattern line portion by mould up and down.And at same pattern line position, rubber composition and polyurethane thin layer become the following paper tinsel shape portion as thin as a wafer of 0.01mm, itself and be continuous state with burr rubber that base fabric is intertwined.
After opening mold, temperature do not descend during, catch the burr rubber of aminomethyl acetoacetic ester class synthetic leather just can easily the base fabric continuous with it be stripped down.
At this moment, above-mentioned paper tinsel shape portion because of and base fabric be intertwined, so can from goods, fully separate, make on the rubber composition, residual by stacked bonding polyurethane thin layer equably.And on the surface of polyurethane thin layer, transfer printing concavo-convex corresponding tiny concavo-convex with base fabric.Obtained final vulcanized rubber sheet therefrom.
This sheet rubber, remain on the sole mould fixed place, when utilizing direct sole manufactured sport footwear,, carry out the notes type and make its sclerosis with well-established law with general urethanes foaminess stoste.As test portion, press the test method(s) of JISK6301 regulation with it, measure the peel strength of two materials, its result is for when show value is 3.5kgf/cm, and material is destroyed.
Embodiment 2:
Use the rubber of table 1B record to cooperate, vulcanized rubber composition not is loaded in the mould that vulcanizing/forming uses, again 1300 by the foregoing description 1
#The one side of jeanette on, the thermoplasticity polyurethane that stacked about 0.03mm is thick, this thermoplasticity polyurethane is with polycaprolactone ethylene glycol (Port リ カ プ ロ ラ Network ト Application グ リ ュ-Le), diphenyl methane-4, and 4-vulcabond and ethylene glycol are main component.In the above-mentioned thermoplastic polyurethane of being laminated with.
The polyurethane face side of the stacked cloth of polyurethane, coating is thinly in advance gone up and press the priming paint of forming shown in the table 2, below will with embodiment 1 similarly pressurize sulphur with peel off base fabric after, obtain the vulcanized rubber sheet.
On the position of the bonding vulcanized rubber of setting on the bottom surface of (エ ニ Star ト ソ-Le) at the bottom of the assembled shoe of giving the resulting polyurethane system in foaming sclerosis back, use has mixed the bonding agent of isocyanates RF5% by well-established law in commercially available urethanes class bonding agent (non-adhesive tape type (ノ-テ-Block) the non-adhesive tape industry of 3050# (strain) system) lining, this vulcanized rubber sheet is bonding.Peel strength between two materials is measured by the test method of JISK6301 regulation, and when institute's indicating value was the 3.2kgf/cm value, material was destroyed.
Embodiment 3:
Use the rubber of putting down in writing in the 1st Table A to cooperate, by the foregoing description 1 vulcanized rubber constituent not is loaded in the mould that vulcanizing/forming uses in the tool, makes and make that urethanes synthetic leather (ラ モ Star Network 5000 the 1st changes into (strain) system) intactly directly contacts with vulcanized rubber composition not, following and the above embodiments 1,2 are pressurizeed sulphur equally and obtained the vulcanized rubber sheet behind the urethane laying up.
Then, same with embodiment 1 again after placing 1 month under the condition of room temperature this vulcanized rubber sheet, casting foaminess urethanes stoste, and make its sclerosis.,, measure the result that two materials peel off and be as test portion with it by the experimental method of stipulating in the JISK6301, when showing the 4.3kgf/cm value, material damage.
Embodiment 4:
Use the rubber of the 1st table C to cooperate, make the urethanes face of the urethane laying up of being remembered among the embodiment 2, directly contact with the face of vulcanized rubber composition not, below the sulphur that similarly pressurizes, and obtain the vulcanized rubber sheet.
Then with embodiment 1,3 similarly, by well-established law urethanes stoste is carried out injection moulding, and makes its sclerosis.According to JISK6301, when the peel strength of two storerooms was 4.1kgf/cm, material was destroyed.
The 1st table
A B C
SBR 50.0 - -
Polymerisation in solution SBR-17.0-
NBR 20.0 - 67.0
Aqueous NBR--4.0
IR - 29.0 -
BR - 23.0 -
Sulfur 1.4 1.3 1.1
Zinc oxide 1.8 1.8 1.8
Stearic acid 1.3 1.2 1.3
Promoter 1) 1.7 1.5 1.7
Activating agent 2) 0.7 1.6 0.9
Micro mist silicic acid 3) 14.4 23.0 15.4
Titanium dioxide 5.0--
Cycloalkane oil 4) 3.0--
DOP - - 3.5
Polymeric fatty acid esters 5)--0.5
Dark substitute 6)--2.2
Styrenated phenol 0.7 0.6 0.6
(unit: weight portion)
Annotate:
1) mercaptobenzothiazoler 45% weight
Bisbenzothiazole disulphide 45% weight
Tetra methylthiuram list sulphite 10% weight
2) diphenyl two ring hexamines
(" ア Network チ Application グ SL " lucky rich pharmacy (strain) system)
3) ultra micron silica
" ニ Star Block シ-Le VN3 " Japanese シ リ カ (strain) system
4) " NA24 " bright dipping oil (strain) system
5) " ス ト ラ Network ト-Le WB " West Germany SCHILL and SEILACHER GmbH system
6) Sulfur ointment
The 2nd table
The not vulcanized rubber 100 of the 1st Table A
Toluene 100
NEK 150
(unit: weight portion)
Claims (4)
1, a kind of manufacture method of vulcanised rubber article for shoes is characterized in that:
When making by vulcanized rubber and polyurethane lamination all-in-one-piece vulcanised rubber article for shoes, make the polyurethane layer side of polyurethane lamination base fabric carry out superimposed with the surperficial ground connection mutually of vulcanized rubber composition not, the heating pressurization, vulcanized rubber composition is not added sulphur, make poly-aethylis carbamas layer and this rubber composition surface bonding simultaneously, then base fabric is peeled off.
2, a kind of vulcanised rubber article for shoes that makes by the described method of claim 1.
3, a kind of manufacturing process of footwear, described method be with jacket the shoe tree of vamp combine with the sole molding die, in the die cavity of such formation, inject the direct sole method of polyurethane stoste, it is characterized in that on the ad-hoc location of end mold, keep the described vulcanised rubber article of claim 2, utilize direct sole method to make this rubber and polyurethane portion direct bonding and be provided as ground bottom surface.
4, a kind of manufacturing process of sole body is characterized in that when carrying out the sole body shaping with polyurethane stoste, and described vulcanised rubber article of claim 2 and polyurethane portion is directly bonding, and it is provided as ground bottom surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91105369 CN1038921C (en) | 1991-07-10 | 1991-07-10 | Vulcanised rubber article for shoes, and producing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91105369 CN1038921C (en) | 1991-07-10 | 1991-07-10 | Vulcanised rubber article for shoes, and producing method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1068294A true CN1068294A (en) | 1993-01-27 |
| CN1038921C CN1038921C (en) | 1998-07-01 |
Family
ID=4907111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91105369 Expired - Fee Related CN1038921C (en) | 1991-07-10 | 1991-07-10 | Vulcanised rubber article for shoes, and producing method therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038921C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101534672B (en) * | 2006-06-30 | 2011-12-07 | Alc富兰科集团公司 | Machine and relative, method for applying an adhesive layer to a surface of an object, such as an inner sole of a shoe |
| CN103042750A (en) * | 2012-12-20 | 2013-04-17 | 龚亭民 | Process for preparing rubber-polyurethane composite product for sole |
-
1991
- 1991-07-10 CN CN 91105369 patent/CN1038921C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101534672B (en) * | 2006-06-30 | 2011-12-07 | Alc富兰科集团公司 | Machine and relative, method for applying an adhesive layer to a surface of an object, such as an inner sole of a shoe |
| CN103042750A (en) * | 2012-12-20 | 2013-04-17 | 龚亭民 | Process for preparing rubber-polyurethane composite product for sole |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1038921C (en) | 1998-07-01 |
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