CN1334054A - Sole with three-layer structure and its manufacture method - Google Patents
Sole with three-layer structure and its manufacture method Download PDFInfo
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- CN1334054A CN1334054A CN 00128099 CN00128099A CN1334054A CN 1334054 A CN1334054 A CN 1334054A CN 00128099 CN00128099 CN 00128099 CN 00128099 A CN00128099 A CN 00128099A CN 1334054 A CN1334054 A CN 1334054A
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Abstract
The present invention provides a shoe sole in which at least a portion of the grounding part is a rubber formed of a thermoplastic elastomer. Such rubber is installed with a rubber bonding interface modified by an unsaturated acid or acid derivative. A thermoplastic resin or a thermoplastic elastomer is used to form a bonding layer. The rubber bonding interface and the rubber are integrally bonding together by melting. A base formed of a thermoplastic resin or a thermoplastic elastomer is integrally bonded together with the bonding layer by melting. The rubber and the base are strongly bonded together, thereby increasing the appearance of the shoe sole and highly assuring the functionality of the shoe sole.
Description
The present invention relates to sole, more particularly, relate to by following step and thermoplastic elastomer (TPE) the sheet material sole and the manufacture method thereof of integrally formed three-decker simultaneously: rubber and thermoplastic elastomer (TPE) sheet material simultaneously behind the monolithic molding, with the thermoplastic elastomer (TPE) injection molded, are formed base portion.
The molding material of sole can be various material known.For example, in the open communique of Japan's special permission 1996 No. 294933, disclose with after the rubber surface halogenation by compression molding or injection molded, with the manufacture method of the athletic shoe sole of thermoplastic polychrome mould-formings such as polyurethane elastomer or polyamide elastomer on the rubber surface of this halogenation.
In the open communique of Japan special permission nineteen ninety-five No. 195622, disclose relate to by dynamically will with graininess be dispersed in thermoplastic elastomer (TPE) (TPV) that the vulcanization of rubber in the thermoplastic matrix obtains and with the invention of the composite article (that is the article of forming by thermoplastic and TPV) of the bonding thermoplastic material of TPV.And, the footwear that are moulded shape or two look injection moldeds as embedding are also disclosed, injection moulding TPV alloy (thermoplastic/rubber alloy) on the sole of, the distortion polyether ester amides that hysteresis quality is low, low-temperature characteristics is excellent strong in fatigue resistance and embedding is moulded the shaping of the sole of shape.
In the open communique of Japanese PCT special permission 1996 No. 505333,2 layers of article that disclose the composition of the thermoplastic elastomer (TPE) that will contain lighting are bonded in the sole that forms on the close material of thermoplastic of the not lighting that is selected from polyetheramides, polyether ester, polyurethane.
In the open communique of Japanese PCT special permission 1996 No. 511741, composite structure that the elastomer of the sulfuration that will contain carboxyl obtains with containing the combinations of thermoplastic polymers of block is disclosed and on thermoplastic polymer with the manufacture method of the athletic shoe sole of elastomer sulfuration.
In addition, with the open communique of Japan special permission 1996 No. 294933 in disclosed sole similarly, by after preliminary treatment such as primary coat or halogenation are carried out on the surface of the rubber of vulcanization forming, embedding in the injection mould and with the athletic shoe sole commercialization of base material injection molded.
But in open 1996 No. 294933 disclosed method of communique of above-mentioned Japan special permission, need carry out the secondary surface activation process, promptly need carry out preliminary treatment such as primary coat or halogenation on the surface of the rubber of vulcanization forming, operation is miscellaneous.And in this manufacture method, when thermoplastic plastic injectings such as polyurethane elastomer, polyamide elastomer were shaped, vulcanized rubber can be owing to injection pressure be out of shape, and thermoplastic is reeled on the surface of the rubber part with pattern, causes open defect.
Therefore,, rubber hardness need be set in the scope of Shore 75-85A, improve the hardness of rubber part and increase the thickness of rubber part, to withstand injection pressure for preventing this defective.Thus, as material for sole of shoe, can only provide rigidity inappropriate sole big and really up to the mark.
Disclosed as the open communique of Japanese PCT special permission 1996 No. 505333, be bonded in the sole that forms on the close material of thermoplastic of the not lighting that is selected from polyetheramides, polyether ester, polyurethane at 2 layers of article of the composition of the thermoplastic elastomer (TPE) that will contain lighting, because the poor durability of the thermoplastic elastomer (TPE) self of lighting, exist the possibility that the endurance quality of the sole self of goods descends.
In the open communique of Japanese PCT special permission 1996 No. 511741, the composite structure that the elastomer of the sulfuration that will contain carboxyl obtains with containing the combinations of thermoplastic polymers of block is disclosed.Though disclose the manufacture method of the athletic shoe sole of on thermoplastic polymer, elastomer being vulcanized, do not described the concrete manufacture method of sole in detail.Yet, for example when adopting die pressing, exist and have rubber burr (overlay film) formation on the thermoplastic polymer, can't carry out problems such as commercialization in appearance.
In addition, in aforesaid these manufacture method of sole, because the forming temperature of thermoplastic elastomer (TPE) sheet material surpasses heat distortion temperature, therefore, the distortion meeting when thermal deformation is with cooling after the demoulding is residual.For preventing distortion, sole needs a cooling device with the injection molded mould, so just must dispose very costliness and complex apparatus, increases manufacturing cost.Thus, wish to have a kind of durability sole good, that form by the material for sole of shoe of the hardness with appropriateness, pliability, slow neutrality and traction property and productivity ratio height, low cost of manufacture and the manufacture method of sole.
The objective of the invention is, a kind of cohesive that can overcome above-mentioned shortcoming of the prior art, improve rubber and base portion is provided, has stable quality, also can further improves outward appearance, reduce cost and improve the sole of performance.
In the present invention, above-mentioned purpose is to realize like this.
One aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, and it is that thermoplastic elastomer (TPE) injection molded by will being used to form base portion makes above-mentioned rubber bodies and the base portion sole of integrally formed three-decker simultaneously on the rubber bodies that constitutes with rubber adhesion all-in-one-piece thermoplastic elastomer (TPE) sheet material.Another aspect of the present invention provides a kind of sole with the rubber bodies that is formed by synthetic rubber and thermoplastic elastomer (TPE) sheet material, and wherein, described synthetic rubber and thermoplastic elastomer (TPE) sheet material form one, have the rubber profile.
Another aspect of the present invention provides a kind of sole that is engaged the all-in-one-piece rubber bodies by synthetic rubber and the thermoplastic elastomer (TPE) sheet material that is the sole profile that has.
Another aspect of the present invention provides a kind ofly to be had by a synthetic rubber and another piece synthetic rubber by the link into an integrated entity sole of the rubber bodies that is the sole profile that forms of thermoplastic elastomer (TPE) sheet material.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described rubber has the rubber bonding interface through unsaturated acids or acid derivative modification, described sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into the adhesive linkage that one engages by above-mentioned rubber bonding interface with aforementioned rubber, described base portion and above-mentioned adhesive linkage are melt into one.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described rubber contains unsaturated acids or acid derivative, described sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with aforementioned rubber and the adhesive linkage that engages, described base portion and above-mentioned adhesive linkage are melt into one.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described sole has the adhesive linkage that is formed by thermoplastic resin or thermoplastic elastomer (TPE), this adhesive linkage has the adhesive linkage bonding interface through unsaturated acids or acid derivative modification, and being melt into the adhesive linkage that one engages with above-mentioned rubber by bonding interface, described base portion and above-mentioned adhesive linkage are melt into one.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described sole have by contain unsaturated acids or acid derivative and therefore and the thermoplastic resin of modification or thermoplastic elastomer (TPE) form, be melt into one with above-mentioned rubber and the adhesive linkage that engages, described base portion and above-mentioned adhesive linkage are melt into one.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described sole has does the thermoplastic resin that mixes with unsaturated acids or acid derivative or thermoplastic elastomer powder is melted and form one with above-mentioned rubber and the adhesive linkage that engages, and described base portion and above-mentioned adhesive linkage are melt into one.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with above-mentioned rubber and the adhesive linkage that engages, described rubber contains thermoplastic resin or the thermoplastic elastomer (TPE) that mixes with above-mentioned adhesive linkage material height, and described base portion and above-mentioned adhesive linkage are melt into one.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with above-mentioned rubber and the adhesive linkage that engages, described base portion and above-mentioned adhesive linkage are melt into one and partly have male portion or concave shaped portion in the convex of above-mentioned rubber grounded part.
Another aspect of the present invention provides a kind of its base portion partly has male portion or concave shaped portion in the convex of above-mentioned rubber grounded part sole.
Another aspect of the present invention provides the sole of the rubber that a kind of at least a portion with the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part forms by thermo-setting elastomer, wherein, described sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with above-mentioned rubber and the adhesive linkage that engages, described base portion and above-mentioned adhesive linkage are melt into one, and the rubber surface bonding with above-mentioned adhesive linkage has the 3 D stereo curved surface.
Another aspect of the present invention provides the sole that the bonding rubber surface of a kind of and above-mentioned adhesive linkage has the 3 D stereo curved surface.
Another aspect of the present invention provides a kind of like this manufacture method of sole, wherein, uncrosslinked synthetic rubber is kneaded, the demoulding forms sheet material, then the gained rubber sheet is placed the rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with rubber and place metal pattern with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of recess profile, pressurized, heated once again, make rubber and thermoplastic elastomer (TPE) sheet material monolithic molding, form rubber bodies, with this rubber bodies be trimmed to background with the pattern of injection molded metal pattern with recess shapes after, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, will be used to form the thermoplastic elastomer (TPE) injection molded of base portion then, make above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion thus, form three-decker.
Another aspect of the present invention provides a kind of like this manufacture method of sole, wherein, uncrosslinked synthetic rubber is kneaded, the demoulding forms sheet material, then the gained rubber sheet is placed the rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of rubber soles profile and place metal pattern, pressurized, heated once again, make above-mentioned synthetic rubber and thermoplastic elastomer (TPE) sheet material monolithic molding, form rubber bodies, after this rubber bodies is trimmed to the sole shape, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, will be used to form the thermoplastic elastomer (TPE) injection molded of base portion then, make above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion thus, form three-decker.
Another aspect of the present invention provides a kind of like this manufacture method of sole, wherein, crosslinked synthetic rubber is kneaded in the future, the demoulding forms sheet material, then the gained rubber sheet is placed a plurality of rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of rubber soles profile and place metal pattern, pressurized, heated once again, above-mentioned a plurality of synthetic rubber is linked into an integrated entity by the thermoplastic elastomer (TPE) sheet material, form rubber bodies, after this rubber bodies is trimmed to the sole shape, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, will be used to form the thermoplastic elastomer (TPE) injection molded of base portion then, make above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion thus, form three-decker.
Above-mentioned and other purposes of the present invention, feature, aspect and advantage are by becoming clearer below in conjunction with accompanying drawing to the detailed description that the present invention did.
Fig. 1 is the plane of sole of the present invention.
Fig. 2 is along the profile of II-II section in the sole of the present invention of Fig. 1.
Fig. 3 A-3D shows the rubber of sole of the present invention respectively.
Fig. 4 A-4D is respectively the profile of the rubber of Fig. 3 A-3D, and wherein, Fig. 4 A is the profile along the IVA-IVA section, and Fig. 4 B is the profile along the IVB-IVB section, and Fig. 4 C is the profile along the IVC-IVC section, and Fig. 4 D is the profile along the IVD-IVD section.
Fig. 5 A-5B is respectively the profile of an operation that shows the manufacture method of sole of the present invention.
Fig. 6 is the profile of an operation that shows the manufacture method of sole of the present invention.
Fig. 7 illustrates curelasto cross-linking curve of the present invention.
Fig. 8 is the side view of sole of the present invention.
Fig. 9 is the plane of sole of the present invention.
Figure 10 A-10B is respectively along the profile of X-X section in the sole of the present invention of Fig. 9.
Figure 11 is the side view of sole of the present invention.
Figure 12 is the plane of sole of the present invention.
Figure 13 A-13B is respectively the profile of the sole of the present invention of Figure 12, and wherein, Figure 13 A is the profile along the XIIIA-XIIIA section, and Figure 13 B is the profile along the XIIIB-XIIIB section.
Figure 14 is the side view of sole of the present invention.
Figure 15 is the plane of sole of the present invention.
Figure 16 is along the profile of XVI-XVI section in the sole of the present invention of Figure 15.
Below embodiments of the present invention are elaborated. That is, sole of the present invention be take the thermoplastic elastomer (TPE) injection molded by will being used to form base portion by engage with synthetic rubber make on the rubber bodies that all-in-one-piece thermoplastic elastomer (TPE) sheet material consists of above-mentioned rubber bodies and base portion simultaneously integrally formed three-decker as the sole of feature. In the present invention, synthetic rubber also comprises the projections such as the pattern part that is made of common relief pattern etc., cleat, anti-skid stud, but below, and the outer bottom that only has a relief pattern with regard to rubber describes.
In addition, sole of the present invention be a kind of take with synthetic rubber and thermoplastic elastomer (TPE) sheet integral and form the rubber profile and will be used to form the thermoplastic elastomer (TPE) injection molded of base portion and make above-mentioned rubber bodies and base portion simultaneously monolithic molding, form three-decker as the sole of feature.
Sole of the present invention or a kind of take synthetic rubber and the thermoplastic elastomer (TPE) sheet material that forms the sole profile be bonded into one and will be used to form the thermoplastic elastomer (TPE) injection molded of base portion and make above-mentioned rubber bodies and base portion simultaneously monolithic molding, form three-decker as the sole of feature.
The present invention or a kind of take the thermoplastic elastomer (TPE) injection molded that a synthetic rubber and another synthetic rubber is linked into an integrated entity, forms the sole profile by the thermoplastic elastomer (TPE) sheet material and will be used to form base portion make above-mentioned rubber bodies and base portion simultaneously monolithic molding, form three-decker as the sole of feature.
The present invention or a kind of sole that obtains with following methods: the rubber that is formed by thermo-setting elastomer at least a portion of grounded part arranges bonding interface through unsaturated acids or acid derivative modification, will be melted into one with rubber by the rubber bonding interface by the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form and engage, the base portion and the adhesive linkage that are formed by thermoplastic resin or thermoplastic elastomer (TPE) are melted into one.
With unsaturated acids or acid derivative the modification that rubber surface carries out is undertaken by rubber surface distribution unsaturated acids or acid derivative in the uncrosslinked rubber surface of kneading or precrosslink.
The melting of adhesive linkage and rubber bonding interface integrated by after with the means such as stacked that above-mentioned rubber and adhesive linkage is overlapping in pressing mold the heating pressurization carry out.
The rubber bodies that is formed by the bonding of rubber and adhesive linkage is such as being inserted in injection mold assembly etc. and with thermoplastic resin or thermoplastic elastomer (TPE) injection molded and rubber bodies and base portion are melted into one.
Sole of the present invention or a kind of sole that obtains with following methods: in the rubber that at least a portion of grounded part is formed by thermo-setting elastomer, add unsaturated acids or acid derivative, to be melted into one and engage with above-mentioned rubber by the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form, will be melted into one by base portion and the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form.
Unsaturated acids or acid derivative add when kneading rubber, are distributed in the rubber.
The melting of adhesive linkage and rubber integrated by after with the means such as stacked that above-mentioned rubber and adhesive linkage is overlapping in pressing mold the heating pressurization carry out.
The rubber bodies that is formed by the bonding of rubber and adhesive linkage for example is inserted in the injection mold assembly and with thermoplastic resin or thermoplastic elastomer (TPE) injection molded and rubber bodies and base portion are melted into one.
Sole of the present invention or a kind of sole that obtains with following methods: will be formed by thermoplastic resin or thermoplastic elastomer (TPE), have to be melted into one by above-mentioned adhesive linkage bonding interface through the adhesive linkage of the bonding interface of unsaturated acids or acid derivative modification and rubber that at least a portion of grounded part is formed by thermo-setting elastomer and engage, and will be melted into one by base portion and the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form.
The formation of the bonding interface on the adhesive linkage is by being coated with unsaturated acids or acid derivative, the thermoplastic resin that makes the adhesive linkage surface or thermoplastic elastomer modified carrying out at adhesive linkage.
The melting of adhesive linkage and rubber integrated by after above-mentioned rubber and adhesive linkage bonding interface is overlapping in pressing mold the heating pressurization carry out.
The rubber bodies that is formed by the bonding of rubber and adhesive linkage for example is inserted in the injection mold assembly and with thermoplastic resin or thermoplastic elastomer (TPE) injection molded and rubber bodies and base portion are melted into one.
The present invention or a kind of sole that obtains with following methods: will by contain unsaturated acids or acid derivative and therefrom the thermoplastic resin of modification or the adhesive linkage that thermoplastic elastomer (TPE) forms be melted into one and engage with the rubber that at least a portion of grounded part is formed by thermo-setting elastomer, and will be melted into one by base portion and the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form.
The interpolation in the adhesive linkage that is formed by thermoplastic resin or thermoplastic elastomer (TPE) of unsaturated acids or acid derivative is to knead unsaturated acids or acid derivative in thermoplastic resin or the thermoplastic elastomer (TPE) by methods such as extrusion moldings when making adhesive linkage and be mixed into one.
The melting of adhesive linkage and rubber integrated by after with the means such as stacked that above-mentioned rubber and adhesive linkage is overlapping in pressing mold the heating pressurization carry out.
The rubber bodies that is formed by the bonding of rubber and adhesive linkage for example is inserted in the injection mold assembly and with thermoplastic resin or thermoplastic elastomer (TPE) injection molded and make rubber bodies and base portion be melt into one.
Sole of the present invention still is a kind of sole that obtains in order to following method: will do on the rubber that at least a portion that the thermoplastic resin that mixes or thermoplastic elastomer powder be sprayed on grounded part forms by thermo-setting elastomer with unsaturated acids or acid derivative, then with powder melts, form and the incorporate adhesive linkage of above-mentioned rubber, will be melt into one by base portion and the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form again.
The interpolation in thermoplastic resin or thermoplastic elastomer powder (spherolite) of unsaturated acids or acid derivative can be by carrying out thermoplastic resin or thermoplastic elastomer powder (spherolite) with doing of unsaturated acids or acid derivative is mixed.
The fusion of adhesive linkage and rubber is integrated by being sprayed on thermoplastic resin or thermoplastic elastomer powder (spherolite) on the above-mentioned rubber, the heating pressurization in pressing mold of above-mentioned rubber and the overlapping back of adhesive linkage being carried out.
The rubber bodies that is formed by the bonding of rubber and adhesive linkage for example is inserted in the injection mold assembly and with thermoplastic resin or thermoplastic elastomer (TPE) injection molded and make rubber bodies and base portion be melt into one.
Sole of the present invention still is a kind of sole that obtains in order to following method: the adhesive linkage that will be formed by thermoplastic resin or thermoplastic elastomer (TPE) is melt into one with the rubber that at least a portion of grounded part is formed by thermo-setting elastomer and engages, and will be melt into one by base portion and the adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form, described rubber contains thermoplastic resin or the thermoplastic elastomer (TPE) that mixes with the adhesive linkage material height.
Thermoplastic resin that above-mentioned rubber contains or thermoplastic elastomer (TPE) and above-mentioned adhesive linkage material height mix.That is, thermoplastic resin that above-mentioned rubber contains or thermoplastic elastomer (TPE) are identical with the material of above-mentioned adhesive linkage, or SP value (solubility parameter: the material that difference solubility parameter) is little, intermiscibility is big.
Join in the rubber when kneading rubber with the material that material is identical or intermiscibility is big of above-mentioned adhesive linkage.The material that joins in the rubber is preferably pulverous.
The fusion of adhesive linkage and rubber is integrated by with above-mentioned rubber and adhesive linkage is stacked or thermoplastic resin or thermoplastic elastomer powder (spherolite) are sprayed on the above-mentioned rubber, the heating pressurization in pressing mold of the bonding back of above-mentioned rubber and adhesive linkage is carried out.
The rubber bodies that is formed by the bonding of rubber and adhesive linkage for example is inserted in the injection mold assembly and with thermoplastic resin or thermoplastic elastomer (TPE) injection molded and make rubber bodies and base portion be melt into one.
The present invention still is that the rubber that formed by thermo-setting elastomer of at least a portion of a kind of grounded part is melt into one with the adhesive linkage that is formed by thermoplastic resin or thermoplastic elastomer (TPE) and engages and be melt into one, described base portion partly have male portion or concave shaped portion in the convex of rubber grounded part sole by base portion and adhesive linkage that thermoplastic resin or thermoplastic elastomer (TPE) form.
The rubber that grounded part has male portion makes its bonding plane have convex corresponding with pressing mold or spill by rubber is heated pressurization in pressing mold.
Rubber is for example inserted in the injection mold assembly, and, make rubber and base portion be melt into one, and make the thermoplastic resin or the thermoplastic elastomer (TPE) that form base portion form convex or spill thermoplastic resin or thermoplastic elastomer (TPE) injection molded.
Sole of the present invention still is that the rubber that formed by thermo-setting elastomer of at least a portion of a kind of grounded part is melt into one with the adhesive linkage that is formed by thermoplastic resin or thermoplastic elastomer (TPE) and the base portion that engages and formed by thermoplastic resin or thermoplastic elastomer (TPE) and adhesive linkage are melt into one, have the sole of 3 D stereo curved surface with the bonding rubber gluing of surfaces of above-mentioned adhesive linkage.
The rubber that has the 3 D stereo curved surface with the gluing of surfaces of adhesive linkage can make its bonding plane have the 3 D stereo curved surface corresponding with pressing mold by rubber is heated pressurization in pressing mold.
Above-mentioned rubber is for example inserted in the injection mold assembly, and, make rubber and sole base portion be melt into one, and make the thermoplastic resin or the thermoplastic elastomer (TPE) that form base portion form the 3 D stereo curved surface thermoplastic resin or thermoplastic elastomer (TPE) injection molded.
Manufacture method of sole of the present invention be a kind of like this be the manufacture method of the sole of feature with the three-decker: uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding gained rubber sheet is placed the rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with rubber and place metal pattern with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of recess profile, pressurized, heated once again, make rubber and thermoplastic elastomer (TPE) sheet material monolithic molding, form rubber bodies, with this rubber bodies be trimmed to background with the pattern of injection molded metal pattern with recess shapes after, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, the thermoplastic elastomer (TPE) injection molded of base portion be will be used to form then, above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion made thus.
Manufacture method of sole of the present invention is still a kind of like this to be the manufacture method of the sole of feature with the three-decker: uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding gained rubber sheet is placed the rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of rubber soles profile and place metal pattern, pressurized, heated once again, make above-mentioned synthetic rubber and thermoplastic elastomer (TPE) sheet material monolithic molding, form rubber bodies, after this rubber bodies is trimmed to the sole shape, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, the thermoplastic elastomer (TPE) injection molded of base portion be will be used to form then, above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion made thus.
Manufacture method of sole of the present invention is still a kind of like this to be the manufacture method of the sole of feature with the three-decker: uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding gained rubber sheet is placed a plurality of rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of rubber soles profile and place metal pattern, pressurized, heated once again, above-mentioned a plurality of synthetic rubber is linked into an integrated entity by the thermoplastic elastomer (TPE) sheet material, form rubber bodies, after this rubber bodies is trimmed to the sole shape, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, the thermoplastic elastomer (TPE) injection molded of base portion be will be used to form then, above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion made thus.
The unsaturated acids that is used for sole of the present invention can be maleic anhydride, phthalic anhydride, fumaric acid, maleic acid, phthalic acid, butanedioic acid, malic acid etc.The acid derivative that is used for sole of the present invention can be these sour derivatives.
The thermoplastic resin that constitutes adhesive linkage can be polyamide, polyurethane resin, vistanex, polystyrene resin, Corvic, mylar, chlorinated polyethylene resin etc.In addition, the thermoplastic elastomer (TPE) that constitutes adhesive linkage can be polyamide elastomer, polyurethane elastomer, polyolefin elastomer, EVA based elastomers, polystyrene based elastomers, polyvinyl chloride based elastomers, polyester elastomer, haloflex based elastomers, 1,2-polybutadiene based elastomers etc.
Basal thermoplastic resin can be polyamide, polyurethane resin, vistanex, polystyrene resin, Corvic, mylar, chlorinated polyethylene resin etc.In addition, basal thermoplastic elastomer (TPE) can be polyamide elastomer, polyurethane elastomer, polyolefin elastomer, EVA based elastomers, polystyrene based elastomers, polyvinyl chloride based elastomers, polyester elastomer, haloflex based elastomers, 1,2-polybutadiene based elastomers etc.
But also can use these resins or elastomeric foaming body.The foaming of these resins can be undertaken by the method for using blowing agents such as volatile foaming agent or decomposability blowing agent or the method for using microballoon (microballoon) etc.
As the thermoplastic elastomer (TPE) that can be used for adhesive linkage and base portion, the example of polyamide elastomer has the PEBAX of ATOFINA company, the VESTAMID of Daicel-Huels company etc.; Polyurethane elastomer has polyesters and polyethers, the ELASTOLLAN of BASF AG, the Takelac of BASF PolyurethanePolymers company are for example arranged, Elastollen, the DESMOPAN of DIC Bayer Polymer company etc., the example of polyolefin elastomer has the Modiper of the Milastomer of Mitsui Petrochemical Industries, Ltd., NOF Corp etc.
With thermoplastic elastomer (TPE) as matrix resin, use is strengthened by the short fiber that grinds fiber, chopped strand and so on that carbon fiber, glass fibre, aramid fibre, h etc. form, and the form of all right fibre-reinforced thermoplastic (FRTP) is used.
In addition, be preferably, also the thermoplastic elastomer (TPE) as matrix resin can be flooded the fabric or the nonwoven that be formed by fortifying fibres such as carbon fiber, glass fibre, aramid fibre, hs, become can in the sheet-form of pressing, and it is used as fibre-reinforced thermoplastic (FRTP).By above-mentioned FRTP, can in the form of the sheet material of pressing, can improve the rigidity and the conformality of sole, and owing to use these fortifying fibres, shrinkage factor difference between the sheet material that makes synthetic rubber and be made of separately thermoplastic elastomer (TPE) reduces, except that preventing the rubber deformation, the design freedom of sole is wideer, can be at various needs of endoadaptation on a large scale.
The thermo-setting elastomer that forms at least a portion of rubber grounded part for example can be NBR (acrylonitrile-butadiene rubber), X-NBR (carboxylated acrylonitrile-butadiene rubber), SBR (SBR styrene butadiene rubbers), X-SBR (carboxylated SBR styrene butadiene rubbers), BR (butadiene rubber), IR (isoprene rubber), NR (natural rubber), EVA, EPDM (ethylene-propylene-diene), EU, AU etc.
NBR for example can be NIPOL, the CHEMIGUM of Goodyear company etc. of the JSR N of JSR company, Japanese Zeon Co., Ltd..In addition, X-NBR can be LACSER of the NIPOL of the JSR N64OH of JSR company, Japanese Zeon Co., Ltd., big Japanese Ink and Chemicals company etc.SBR can be NIPOL, the JSR of JSR company etc. of Japanese Zeon Co., Ltd..
Can in above-mentioned thermo-setting elastomer, add softening agent, white filler, plasticizer, vulcanization accelerator, age resister, tackifier, pigment, antiscorching agent, promoter etc.
Softening agent is as required, uses in order further to improve mixing processability, and for example can be petroleum line softeners such as process oil, lubricating oil, paraffin, atoleine, asphalt, vaseline; Castor oil, linseed oil, rapeseed oil, coconut wet goods fatty oil softener; Tall oil; Black factice; Wax classes such as beeswax, Brazil wax, lanolin; Linoleic acid, palmitic acid, stearic acid, laurate etc.
The white filler for example can be silica, clay, aluminium oxide, talcum powder, calcium carbonate, magnesium carbonate, aluminium hydroxide, magnesium hydroxide, magnesia, iron oxide etc.They can share separately or more than two kinds.Especially preferred white filler is silica, clay, aluminium hydroxide and aluminium oxide.
Plasticizer for example can be DMP (repefral); DEP (diethyl phthalate); DBP (dibutyl phthalate); DHP (dibutyl phthalate (DHP)); DOP (dioctyl phthalate); DINP (diisononyl phthalate); DIDP (diisooctyl phthalate); BBP (butyl phthalate benzyl ester); DLP (dilauryl phthalate); DCHP (dicyclohexyl phthalate); the hydrogenated phthalates dehydrate; TCP (tricresyl phosphate); TEP (triethyl phosphate); TBP (tributyl phosphate); TOP (trioctyl phosphate); TCEP (tricresyl phosphate (chloroethene ester)); TDCPP (tricresyl phosphate (dichloro propyl ester)); TBXP (tricresyl phosphate (butoxy ethyl ester)); TCPP (tricresyl phosphate (β-chlorine propyl ester)); TPP (triphenyl phosphate); the octyl phosphate diphenyl ester; phosphoric acid (three (isopropyl phenyl ester)); DOA (dioctyl adipate); DINA (diisononyl adipate); DIDA (diisodecyl adipate (DIDA)); D610A (adipic acid dialkyl 610); BXA (adipic acid two (butyldiglycol ester)); DOZ (azelaic acid two (2-Octyl Nitrite)); DBS (dibutyl sebacate); DOS (di-n-octyl sebacate); CitroflexA-2; citroflex A-4; DBM (dibutyl maleate); DOM (maleic acid (2-Octyl Nitrite)); DBF (dibutyl fumarate) etc.
Age resister can be amine system, phenol system, imidazoles system, carbamic acid slaine, wax etc.
Tackifier can be that rosin series, terpenic series, terpenes phenol system, phenol system, coumarone indene is resin, Petropols etc.Specifically, can be Tackiroll 101, Hitanol1501, Tackiroll130-G, Hitanol 5501 etc.
Pigment can be any in inorganic pigment and the organic pigment.Inorganic pigment for example can be that mica shape iron oxide, white lead, red lead, chrome yellow, vermilion, ultramarine, dark purple, cobalt oxide, titanium dioxide, the mica of titanium dioxide coating, strontium chromate, titan yellow, titanium are black, zinc chromate, iron oxide black, chrome vermillion, strontium molybdate, lead monoxide, lithopone, emerald green, guignet green, cadmium yellow, cadmium red, cobalt blue etc.Organic pigment for example can be insoluble azo colour, solubility AZOpigments, phthalocyanine blue, color lake, isoindolinone, quinacridone, dioxazine violet, perinone perylene dye etc.
Antiscorching agent for example can be nitroso compounds such as organic acids such as salicylic acid, benzoic acid, N nitrosodiphenyl amine, N-cyclohexylthiophthalimide etc.
Promoter for example can be to contain that to be selected from sulfenamide system, thiazole system, thiuram system, thiocarbamide system, guanidine system, dithiocar-bamate system, aldehyde-amine system or aldehyde-ammonia system, imidazoline system and xanthates be at least a promoter in the vulcanization accelerator.
Sulfenamide is that vulcanization accelerator for example can be CBS (N-cyclohexyl-2-[4-morpholinodithio base sulfenamide), TBBS (the N-tert-butyl group-2-[4-morpholinodithio base sulfenamide), N, N-dicyclohexyl-2-[4-morpholinodithio base sulfenamide, N-oxydiethylene-2-[4-morpholinodithio base sulfenamide, N, N-diisopropyl-sulfenamide based compounds such as 2-[4-morpholinodithio base sulfenamide etc.
Thiazole is that vulcanization accelerator for example can be MBT (2-mercaptobenzothiazole), MBTS (dibenzothiazyl-disulfide), the sodium salt of 2-mercaptobenzothiazole, zinc salt, mantoquita, cyclohexylamine salt, 2-(2, the 4-dinitrophenyl) thiazole compound such as mercaptobenzothiazoler, 2-(2,6-diethyl-4-morpholino sulfo-) benzothiazole etc.
Thiuram is that vulcanization accelerator for example can be TMTD (tetramethylthiuram disulfide), tetraethylthiuram disulfide, sulfuration tetra methylthiuram, curing two-1,5-pentylidene thiuram, sulfuration two-1,5-pentylidene thiuram, tetra-sulfurized pair-1,5-pentylidene thiuram, six sulfurations two-1,5-pentylidene thiuram, tetrabutylthiuram disulfide, four sulfurations-1, thiuram based compounds such as 5-pentylidene thiuram.
Thiocarbamide is that vulcanization accelerator for example can be thiourea compounds such as thiocarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, di-o-tolyl thiocarbamide etc.
Guanidine is that vulcanization accelerator for example can be guanidine based compounds such as diphenylguanidine, di-o-tolylguanidine, triphenyl guanidine, adjacent toluene biguanides (orthotolylbiganide), diphenylguanidine phthalate.
Aminodithioformic acid is that vulcanization accelerator for example can be a zinc-ethylphenyl dithiocarbamate, the butyl phenyl zinc dithiocarbamate, SDD, PZ, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc diamyldithiocarbamate, the dipropyl zinc dithiocarbamate, 1, the complex salt of 5-pentylidene zinc dithiocarbamate and piperidines, palmityl (or octadecyl) isopropyl zinc dithiocarbamate, zinc dibenzyl dithiocarbamate, sodium diethyldithiocarbamate, 1, the 5-piperidine pentamethylene dithiocarbamate, Selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, aminodithioformic acid based compounds such as diamyl dithiocarbamate cadmium etc.
Aldehyde-amine system or aldehyde-ammonia are that vulcanization accelerator for example can be aldehyde such as acetaldehyde-aniline reaction thing, butyl aldehyde aniline condensation product, hexa, acetaldehyde-ammonia react thing-amine system or aldehyde-ammonia based compound etc.
Imidazoline is that vulcanization accelerator for example can be imidazoline based compounds such as 2-mercaptoimidazoline etc.
Xanthates is that vulcanization accelerator for example can be xanthates based compounds such as dibutyl xanthic acid zinc etc.
The present invention will be described below by embodiment.
Embodiment 1
As depicted in figs. 1 and 2, it is on the rubber bodies 4 one, that constitute as the thermoplastic elastomer (TPE) sheet material 3 of adhesive linkage that the thermoplastic elastomer (TPE) 5 that will be used to form base portion with the injection molded method is injection-moulded in by engaging with synthetic rubber 2, make rubber bodies 4 and 6 while of base portion monolithic molding, form the three-decker of the feature that constitutes sole 1.
In another embodiment of the present invention, as depicted in figs. 1 and 2, in rubber bodies 4, synthetic rubber 2 becomes the profile of rubber 2 with thermoplastic elastomer (TPE) sheet material 3 monolithic moldings, and by thermoplastic elastomer (TPE) 5 injection moldeds that will be used to form base portion, make above-mentioned rubber bodies 4 and 6 while of base portion monolithic molding, form the three-decker of the feature that constitutes sole 1.
In another embodiment of the present invention, shown in Fig. 3 A, 3B, 3C, 3D and Fig. 4 A, 4B, 4C, 4D, in rubber bodies 4, synthetic rubber 2 is bonded into one with the thermoplastic elastomer (TPE) sheet material 3 that forms the sole profile, and (not marking among the figure) will be by being used to form the thermoplastic elastomer (TPE) injection molded of base portion, make above-mentioned rubber bodies 4 and 6 while of base portion monolithic molding, form the three-decker that constitutes the sole feature.
In another embodiment of the present invention, shown in Fig. 3 A, 3B, 3C, 3D and Fig. 4 A, 4B, 4C, 4D, in rubber bodies 4, by thermoplastic elastomer (TPE) sheet material 3 synthetic rubber 2 is linked into an integrated entity with another synthetic rubber 2, form the sole profile, and (not marking among the figure) makes above-mentioned rubber bodies 4 and 6 while of base portion monolithic molding by being used to form the thermoplastic elastomer (TPE) injection molded of base portion, forms the three-decker that constitutes the sole feature.
In the manufacture method of sole 1 of the present invention, at first, as Fig. 5 A, shown in the 5B, uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding rubber bodies 2A is placed the rubber recess 8 of preform sole metal pattern 7, after the pressurized, heated (150-160 ℃), begin (to look elastomeric prescription and different before crosslinked at this rubber bodies 2A, usually in after beginning in pressurized, heated 1-3 minute, be advisable), open metal pattern, then, to have with rubber and place metal pattern with conform to the substantially thermoplastic elastomer (TPE) sheet material 3 of shape of recess 8 profiles, with hot press pressurized, heated once again, when making above-mentioned uncrosslinked synthetic rubber 2 crosslinked, thermoplastic elastomer (TPE) sheet material 3 is melt into one, form rubber bodies 4, then, metal pattern is cooled to below 120 ℃, make rubber bodies 4 demouldings, then, as shown in Figure 6, with this rubber bodies 4 be trimmed to background with the pattern of injection molded metal pattern 9 with recess shapes after, sandwich background with in the injection molded metal pattern 9, make itself and pattern identical with recess 10, then, to be used to form thermoplastic elastomer (TPE) 5 injection moldeds of base portion, make the thermoplastic elastomer (TPE) sheet material 3 and 6 while of base portion monolithic molding of above-mentioned rubber bodies 4, form the three-decker of the feature that constitutes sole 1.
Describe below in conjunction with the manufacture method of curelasto cross-linking curve shown in Figure 7 the sole 1 of three-decker of the present invention.At first, uncrosslinked synthetic rubber is kneaded, formed sheet material, after the demoulding rubber bodies 2A is placed the rubber recess 8 of preform sole metal pattern 7, pressurized, heated (150-160 ℃).Then, open metal pattern in the crosslinked initial stage of this rubber bodies 2A.That is, open metal pattern in the A time period of the curelasto of Fig. 7 cross-linking curve.This A time period is looked elastomeric prescription and different, is advisable in 1-3 minute to begin the back in pressurized, heated usually, when vulcanizing with sulphur, about about 2-3 minute, carries out when crosslinked roughly about about 1-2 minute with peroxide.
Then, to have with rubber and place metal pattern, with hot press pressurized, heated once again, when above-mentioned uncrosslinked synthetic rubber 2 is crosslinked with conform to the substantially thermoplastic elastomer (TPE) sheet material 3 of shape of recess 8 profiles, 3 fusions of thermoplastic elastomer (TPE) sheet material are bonded into one, form rubber bodies 4.That is, the B at the smooth crosslinking temperature of the curelasto cross-linking curve that arrives Fig. 7 stops heating process during the time period.Then, preform sole metal pattern is cooled to about below 120 ℃, with rubber bodies 4 demouldings.That is because 150-160 ℃ heating-up temperature, polyamide elastomer is a molten condition, and, polyamide elastomer different with elastomeric shaping shrinkage rate (polyamide elastomer: 8/1000, synthetic rubber: 23/1000), therefore, must cool off.
Then, rubber bodies 4 is shaped as and background with the pattern of injection molded metal pattern 9 with the identical shape of recess shapes, perhaps edge trimming is become than pattern with the big 0.1-5mm of recess shapes (about preferably big 0.1-0.3mm).Then, it is sandwiched background with in the injection molded metal pattern 9, itself and pattern are coincide with recess 10.Promptly, it is believed that, with the rubber bodies 4 that disposes like this, when thermoplastic elastomer (TPE) 5 injection moldeds that are used to form base portion, by rubber bodies 4 being pressed into the effect of the pin of drafting department, can make rubber bodies 4 edge shapes play a part to prevent that the resin of injection moulding from spreading or the gum filler of seepage, generation flash.And, do so also and can shorten operation.
Above-mentionedly carry out pressurized, heated by hot press, the condition that when making above-mentioned uncrosslinked synthetic rubber 2 crosslinked thermoplastic elastomer (TPE) sheet material 3 is melt into one, forms rubber bodies 4 is looked each material and different, but usually, consider the melt temperature of elastomeric crosslinking temperature and thermoplastic elastomer (TPE) sheet material, under about 150-180 ℃ temperature conditions, need 1-3 minute curring time.Thus, synthetic rubber 2 is crosslinked, and thermoplastic elastomer (TPE) sheet material 3 extends by heating.And synthetic rubber 2 and consequent flash become the state that is adhered to thermoplastic elastomer (TPE) sheet material 3 that is crosslinked.
In the manufacture method of the sole of another embodiment of the present invention, uncrosslinked synthetic rubber is kneaded, form sheet material, again rubber bodies 2A is placed the rubber recess 8 of preform sole metal pattern 7 after the demoulding, after the pressurized, heated, open metal pattern in the crosslinked initial stage of this rubber bodies 2A, then, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material 3 of shape of sole profile and place metal pattern, pressurized, heated once again, make above-mentioned synthetic rubber 2 and thermoplastic elastomer (TPE) sheet material 3 form one, become rubber bodies 4, after this rubber bodies 4 is trimmed to the sole shape, sandwich background with in the injection molded metal pattern 9, itself and pattern are coincide, with recess 10 by base portion being formed thermoplastic elastomer (TPE) sheet material 5 injection moldeds of usefulness, make above-mentioned thermoplastic elastomer (TPE) sheet material 3 and base portion 6 monolithic molding simultaneously, form the three-decker of the feature that constitutes sole 1.
In the manufacture method of the sole of further embodiment of this invention, uncrosslinked synthetic rubber is kneaded, form sheet material, again rubber bodies 2A is placed a plurality of rubber recess 8 of preform sole metal pattern 7 after the demoulding, after the pressurized, heated, open metal pattern in the crosslinked initial stage of this rubber bodies 2A, then, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material 3 of shape of sole profile and place metal pattern, pressurized, heated once again, make above-mentioned a plurality of synthetic rubber 2 and thermoplastic elastomer (TPE) sheet material 3 form one, become rubber bodies 4, after this rubber bodies 4 is trimmed to the sole shape, sandwich background with in the injection molded metal pattern 9, itself and pattern are coincide, with recess 10 by base portion being formed thermoplastic elastomer (TPE) sheet material 5 injection moldeds of usefulness, make the thermoplastic elastomer (TPE) while monolithic molding of above-mentioned thermoplastic elastomer (TPE) sheet material 3 and base portion 6, form the three-decker of the feature that constitutes sole 1.
The thickness of synthetic rubber 2 of the present invention preferably is set at about about 1-5mm.On the other hand, thermoplastic elastomer (TPE) sheet material 3 preferably has thickness about about 0.1-1.0mm and the Shore D hardness of 35-65.But in the present invention, consider adhesive strength, thickness is preferably in about 0.5-0.75mm.In addition, the resin of injection molded can be above-mentioned polyamide-based elastomer sheet, if can merge, also can be polyurethane series elastomer or polystyrene based elastomers.For example, if use PEBAX 5533 (trade names, ATOFINAJAPAN company product) as above-mentioned polyamide-based elastomer, then use PEBAX 6333 (trade names, ATOFINA JAPAN company product) resin as injection molded can merge, and forms hot strength and the spring rate base portion higher than PEBAX 5533.In addition, by selected these materials, can make the athletic shoe sole that is fit to all kinds motion.
The example of the rubber compounding of sole of the present invention is shown in table 1, table 2 and table 3.
Table 1 (formula table 1)
The following batching of dotted line adds sulfur-crosslinked condition (5mm sheet material) by grinding machine
| Batching name batching | Sulfur-crosslinked prescription | ||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | |
| X-NBR SBR NBR stearic acid silica *-1 plasticizer *-2 PEG#4000 vulcanization accelerator *-3 age resister *-4 tackifier *-5 titanium oxide ultramarine antiscorching agent *-6 | ????100 ????- ????- ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 | ????75 ????- ????25 ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 | ????50 ????- ????50 ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 | ????25 ????- ????75 ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 | ????75 ????25 ????- ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 | ????50 ????50 ????- ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 | ????25 ????75 ????- ????1 ????40 ????10 ????2 ????0.3 ????1 ????5 ????5 ????0.05 ????0.3 |
| Zinc oxide sulphur powder accelerator CBS (CZ) diphenylguanidine OTG (DT) TM monex TM (TS) crosslink agent DCP-40 | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- | ????3 ????1.7 ????2.0 ????0.3 ????0.3 ????- |
| Amount to | ????171.9 ????5 | ????171.9 ????5 | ????171.9 ????5 | ????171.9 ????5 | ????171.9 ????5 | ????171.9 ????5 | ????171.9 ????5 |
Crosslinking temperature: 160 ℃
Crosslinking time: about 17 minutes
Table 2 (formula table 2)
The following batching of dotted line adds peroxide crosslinking condition (5mm sheet material) by grinding machine
| Batching name batching | The peroxide crosslinking prescription | ||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | |
| X-NBR SBR NBR stearic acid silica *-1 plasticizer *-2 PEG#4000 vulcanization accelerator *-3 age resister *-4 tackifier *-5 titanium oxide ultramarine antiscorching agent *-6 | ????100 ????- ????- ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ????0.05 ????- | ????75 ????- ????25 ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ?0.05 ????- | ????50 ????- ????50 ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ????0.05 ????- | ????25 ????- ????75 ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ????0.05 ????- | ????75 ????25 ????- ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ????0.05 ????- | ????50 ????50 ????- ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ????0.05 ????- | ????25 ????75 ????- ????1 ????40 ????10 ????2 ????- ????1 ????5 ????5 ????0.05 ????- |
| Zinc oxide sulphur powder accelerator CBS (CZ) diphenylguanidine OTG (DT) TM monex TM (TS) crosslink agent DCP-40 | ????- ????- ????- ????- ????- ????5.0 | ????- ????- ????- ????- ????- ????5.0 | ????- ????- ????- ????- ????- ????5.0 | ????- ????- ????- ????- ????- ????5.0 | ????- ????- ????- ????- ????- ????5.0 | ????- ????- ????- ????- ????- ????5.0 | ????- ????- ????- ????- ????- ????5.0 |
| Amount to | ????169.55 | ????169.55 | ????169.50 | ????169.50 | ????169.50 | ????169.50 | ????169.50 |
Crosslinking temperature: 160 ℃
Crosslinking time: 15 minutes
Table 3 (formula table 3)
Crosslinking agent adds peroxide crosslinking condition (5mm sheet material) by grinding machine
| Batching name batching | The peroxide crosslinking prescription | ||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | |
| X-NBR SBR NBR stearic acid silica *-1 plasticizer *-2 PEG#4000 age resister *-4 tackifier *-5 titanium oxide ultramarine TAIC *-7 crosslink agent DCP-40 | ????100 ????- ????- ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 | ????75 ????- ????25 ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 | ????50 ????- ????50 ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 | ????25 ????- ????75 ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 | ????75 ????25 ????- ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 | ????50 ????50 ????- ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 | ????25 ????75 ????- ????1 ????45 ????15 ????2 ????1 ????5 ????10 ????0.05 ????2.0 ????4.0 |
| Amount to | ????185.05 | ????185.05 | ????185.05 | ????185.05 | ????185.05 | ????185.05 | ????185.05 |
Crosslinking temperature: 160 ℃
Crosslinking time: about 17 minutes
The rubber that uses be NBR and through the pug mill of carboxy-modified X-NBR as rubber.The weight proportion of kneading of NBR and X-NBR is 50: 50.As shown in table 4, the carboxyl concentration of X-NBR is 0.01-0.1EPHR.If the carboxyl concentration of X-NBR is less than 0.01EPHR, then by becoming not obvious with unsaturated acids or acid derivative modification to improve fusible effect, and if carboxyl concentration surpasses 0.1EPHR, then Pei Liao the operability of kneading may variation.The carboxyl concentration of X-NBR is preferably 0.06-0.08EPHR.In addition, as shown in table 6, except that NBR 50 weight portions, X-NBR50 weight portion, also contain stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG2 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, crosslink agent DCP-405 weight portion.
The rubber that to knead is put into die mould with the recess of metal pattern, 30 seconds to 1 of heating minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Then, open the die mould metal pattern, maleic anhydride is sprayed on rubber and the surface that adhesive linkage engages of precrosslink, form the rubber bonding interface.The quantity for spray of maleic anhydride is as shown in table 1, is 0.1-10mg/cm
2If quantity for spray is less than 0.1mg/cm
2, then the functional group concentration's who is produced by modification increase may be insufficient, and cementability can not substantially improve, and if surpass 10mg/cm
2, then can cause bad order, operability is variation also.The quantity for spray of maleic anhydride is preferably 0.2-2mg/cm
2
Then, on the rubber bonding plane, form polyamide elastomer sheet material (for example the PEBAX5533 that produces of ATOFINA company, thick 0.3mm) as after the adhesive linkage, again the die mould metal pattern that closes, heating is 11-13 minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Since with the bonding plane of polyamide elastomer sheet material by maleic anhydride modified, the concentration that is imbued with reactive functional group increases, therefore, rubber bonding interface and polyamide elastomer sheet material are by strong bond, consequently, form the polyamide elastomer adhesive linkage at rubber surface, and form rubber thus and the polyamide elastomer sheet material is engaged the all-in-one-piece rubber bodies.
Then, rubber bodies is inserted in the injection mold assembly, (for example PEBAX6333 of ATOFINA company production) forms base portion with polyamide elastomer.
Thus, can make the polyamide elastomer sheet material of rubber surface engage, form securely one with the base portion fusion.
The gained sole has been carried out adhesive test, and the result is as shown in table 4, and elastomeric material surpasses 10N/mm in the strength that applies
2The time destroyed, show the bonding very good of rubber and base portion.
The rubber that uses is SBR and through the pug mill of carboxy-modified X-NBR.The weight proportion of kneading of SBR and X-NBR is 75: 25.As shown in table 4, the carboxyl concentration of X-NBR is 0.01-0.1EPHR.
In addition, as shown in table 6, except that SBR75 weight portion, X-NBR25 weight portion, also contain stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG 2 weight portions, vulcanization accelerator 0.3 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, antiscorching agent 0.3 weight portion, zinc oxide 3 weight portions, sulphur powder 1.7 weight portions, CBS2 weight portion, DOTG0.3 weight portion, TMTM0.3 weight portion as promoter.
When kneading rubber, in batching, add the fumaric acid of 0.5-1.5PHR.If addition is less than 0.5PHR, then the functional group concentration's who is produced by modification increase is insufficient, and cementability can not substantially improve, and if surpass 1.5PHR, then curingprocess rate becomes too fast, may produce harmful effect to cementability.Therefore, the addition of fumaric acid is preferably 0.8-1.2PHR.
Then, the rubber that will knead is put into die mould with the recess of metal pattern, 30 seconds to 1 of heating minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Then, open the die mould metal pattern, on the pre-warmed rubber gluing of surfaces of process, (for example form the polyurethane elastomer sheet material, the ET1190 that BASF AG produces, thick 0.3mm) as after the adhesive linkage, again the die mould metal pattern that closes, heating is 11-13 minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Because rubber is by the fumaric acid modification, the concentration that is imbued with reactive functional group increases, therefore, rubber with the bonding surface of polyurethane elastomer sheet material and polyurethane elastomer sheet material by strong bond, form the polyurethane elastomer adhesive linkage at rubber surface, and form rubber thus and engage the all-in-one-piece rubber bodies with the polyurethane elastomer sheet material.
Then, rubber bodies is inserted in the injection mold assembly, formed base portion with elastic polyurethane foaming body (for example the ET1190 that produces of BASF AG, proportion 0.9-1.2).Used blowing agent is the heat absorption blowing agent of the shear heat when utilizing injection molded etc.
Thus, can make the polyurethane elastomer sheet material of rubber surface engage, form securely one with the base portion fusion.
The gained sole has been carried out adhesive test, and the result is as shown in table 4, and elastomeric material surpasses 10N/mm in the strength that applies
2The time destroyed, show the bonding very good of rubber and base portion.
The rubber that uses is NBR.As shown in table 6, except that the NBR100 weight portion, also contain stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG2 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, crosslink agent DCP-405 weight portion.
As the polyamide elastomer sheet material of adhesive linkage (for example the PEBAX5533 that produces of ATOFINA company, thick 0.3mm) surface coating maleic anhydride 0.1-10mg/cm
2(0.2-2mg/cm preferably
2).If the coating weight of maleic anhydride is less than 0.1mg/cm
2, then the functional group concentration's who is produced by modification increase may be insufficient, and cementability can not substantially improve, and if surpass 10mg/cm
2, then may cause bad order, operability is variation also.
Then, the rubber that will knead is put into die mould with the recess of metal pattern, 30 seconds to 1 of heating minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Then, open the die mould metal pattern, on rubber, form the polyamide elastomer sheet material, make the surface that has been coated with maleic anhydride become with the bonding surface of rubber after, again the die mould metal pattern that closes, heating is 11-13 minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Because the maleic anhydride of coating makes the lip-deep concentration increase that be imbued with reactive functional group bonding with rubber, therefore, the bonding interface of rubber and polyamide elastomer sheet material adhesive linkage is by strong bond, consequently, form the polyamide elastomer adhesive linkage at rubber surface, and form rubber thus and engage the all-in-one-piece rubber bodies with the polyamide elastomer sheet material.
Then, rubber bodies is inserted in the injection mold assembly, formed base portion with polyamide elastic foam (for example the PEBAX5533 that produces of ATOFINA company, proportion 0.8-1.0).Used blowing agent is a volatile foaming agent.
Thus, can make the polyamide elastomer sheet material of rubber surface engage, form securely one with the base portion fusion.
The gained sole has been carried out adhesive test, and the result is as shown in table 4, interface peel occurs though observe a part of sole, and elastomeric material is 11-15N/mm in the strength that applies
2The time destroyed, show the bonding very good of rubber and base portion.
The rubber that uses be NBR and through the pug mill of carboxy-modified X-NBR as rubber.The weight proportion of kneading of NBR and X-NBR is 25: 75.As shown in table 4, the carboxyl concentration of X-NBR is 0.01-0.1EPHR.As shown in table 6, except that NBR25 weight portion, X-NBR75 weight portion, also contain stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG2 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, crosslink agent DCP-405 weight portion.
The polyamide elastomer sheet material (for example, the PEBAX5533 that ATOFINA company produces, thick 0.3mm) that can use the maleic acid 0.5-5 weight % that kneaded is as adhesive linkage.If the amount of kneading of maleic acid is less than 0.5 weight %, the increase that then is imbued with reactive functional group concentration is insufficient, and cementability can not substantially improve, and if surpass 5 weight %, then may cause bad order, and operability is variation also.Therefore, the amount of kneading of maleic acid is preferably 1-1.5 weight %.As shown in table 4, the maleic acid of 0.5-1.5 weight % is kneaded to the polyamide elastomer sheet material.
At first, the rubber that will knead is put into die mould with the recess of metal pattern, 30 seconds to 1 of heating minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Then, open the die mould metal pattern, through after placing the polyurethane elastomer sheet material on pre-warmed rubber and the surface that adhesive linkage engages, the die mould metal pattern that closes again heated 11-13 minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Because the maleic acid of kneading to the polyamide elastomer sheet material makes the concentration that is imbued with reactive functional group increase, therefore, rubber and adhesive linkage are formed rubber and engage the all-in-one-piece rubber bodies with the polyamide elastomer sheet material by strong bond.
Then, rubber is inserted in the injection mold assembly, (for example ET890 of BASFPolyurethane Polymers company production) forms base portion with polyurethane elastomer.
Thus, can make the polyamide elastomer sheet material of rubber surface engage, form securely one with the polyurethane elastomer fusion of base portion.
The gained sole has been carried out adhesive test, and the result is as shown in table 4, and elastomeric material surpasses 15N/mm in the strength that applies
2The time destroyed, show the bonding very good of rubber and base portion.
The rubber that uses is SBR and through the pug mill of carboxy-modified X-NBR.The weight proportion of kneading of SBR and X-NBR is 50: 50.As shown in table 4, the carboxyl concentration of X-NBR is 0.01-0.1EPHR.
The powder that uses is to do the polyamide elastomer powder that mixes with 0.5-1.5 weight % phthalic acid.The polyamide elastomer powder for example can be the VESTAMID55 that Daicel-Huels company produces.As shown in table 4, use the polyamide elastomer powder of average grain diameter as 200-800 μ m.If the particle diameter of polyamide elastomer powder is less than 200 μ m, the polyamide elastomer powder may disperse when then scattering, and operability is poor.And if surpass 800 μ m, then in the thermoplastic resin adhesive linkage that the polyamide elastomer powder melts is formed, occur gas easily and gather (foaming).Therefore, the average grain diameter of polyamide elastomer powder is preferably 400-600 μ m.
At first, the rubber that will knead is put into die mould with the recess of metal pattern, 30 seconds to 1 of heating minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Then, open the die mould metal pattern, scattering through the surface of pre-warmed rubber and the dried polyamide elastomer powder 10-100mg/cm that mixes of phthalic acid
2(20-40mg/cm preferably
2) afterwards, the die mould metal pattern that closes again, heating is 11-13 minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.If the dispersion volume of polyamide elastomer powder is less than 10mg/cm
2, then can not form fully thick adhesive linkage, may cause bad with engaging of the thermoplastic resin of base portion or thermoplastic elastomer (TPE).And if surpass 100mg/cm
2, then in the adhesive linkage that the polyamide elastomer powder melts is formed, occur gas easily and gather (foaming).
Because phthalic acid makes the concentration be imbued with reactive functional group increase, and therefore, forms the adhesive linkage of fusion all-in-one-piece polyamide elastomer securely on the bonding interface of rubber, and form rubber thus and engage the all-in-one-piece rubber bodies with adhesive linkage.
Then, rubber bodies is inserted in the injection mold assembly, (for example VESTAMID55 of Daicel-Huels company production) forms base portion with polyamide elastomer.
Thus, can make the adhesive linkage of the polyamide elastomer of rubber surface engage, form securely one with the base portion fusion of polyamide elastomer.
The gained sole has been carried out adhesive test, and the result is as shown in table 4, and elastomeric material surpasses 15N/mm in the strength that applies
2The time destroyed, show the bonding very good of rubber and base portion.
The rubber that uses is SBR and through the pug mill of carboxy-modified X-NBR.The weight proportion of kneading of SBR and X-NBR is 50: 50.As shown in table 4, the carboxyl concentration of X-NBR is 0.01-0.1EPHR.
As shown in table 6, except that SBR50 weight portion, X-NBR50 weight portion, also contain stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG2 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, crosslink agent DCP-405 weight portion.
At first, when kneading rubber, in batching, add the polyolefin elastomer powder of 0.5-1.5PHR.If addition is less than 0.5PHR, if then high by the intermiscibility of the elastomer that adds and thermoplastic resin or thermoplastic elastomer (TPE) adhesive linkage and the DeGrain of the raising cementability that produces, and above 1.5PHR then can cause the rubber surface bad order after crosslinked.Therefore, the addition of polyolefin elastomer powder is preferably 0.8-1.2PHR.
The polyolefin elastomer powder for example can be the Modiper A8200 of NOF Corp's production etc.In addition, the average grain diameter of polyolefin elastomer powder can be 200-800 μ m, is good with 300-500 μ m.If less than 200 μ m, powder can disperse when then kneading, and operability is poor.And if surpass 800 μ m, then the bad dispersibility of powder in the rubber batching causes rerum natura to descend and adhesive strength decline.
Then, the rubber that will knead is put into die mould with the recess of metal pattern, 30 seconds to 1 of heating minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.
Then, open the die mould metal pattern, at the bonding interface distribution vistanex powder 10-100mg/cm of the rubber that passes through precrosslink
2(20-40mg/cm preferably
2) afterwards, the die mould metal pattern that closes again, heating is 11-13 minute under temperature 160-170 ℃, the condition of pressure 8-10MPa.The vistanex powder for example can be the Milastomer 8032 of Mitsui Petrochemical Industries, Ltd.'s production etc.In addition, can use the vistanex powder of average grain diameter as 200-800 μ m (preferably 400-800 μ m).
Because the polyolefin elastomer powder that adds in the rubber batching is big with the intermiscibility of the adhesive linkage that is formed by vistanex, thereby on the bonding interface of rubber, form the adhesive linkage of fusion all-in-one-piece vistanex securely, and form rubber thus and engage the all-in-one-piece rubber bodies with adhesive linkage.
Then, rubber bodies is inserted in the injection mold assembly, (for example Milastomer 8032 of Mitsui Petrochemical Industries, Ltd.'s production) forms base portion with polyolefin elastomer.
Thus, can make the adhesive linkage of the vistanex of rubber surface engage, form securely one with the base portion fusion of polyolefin elastomer resin.
The gained sole has been carried out adhesive test, and the result is as shown in table 4, and elastomeric material surpasses 8.5N/mm in the strength that applies
2The time destroyed, show the bonding very good of rubber and base portion.
According to the result of table 4, in the sole of embodiment 2-7, observe the ruined phenomenon of elastomeric material, show that rubber and base portion are bonding securely.
On the other hand, comparative example 1 is the sole that is formed by following rubber, adhesive linkage and base portion: at least a portion of grounded part is to be the rubber that main material forms with NBR, adhesive linkage is formed by polyamide elastomer, be melt into one with above-mentioned rubber and engage, base portion is formed by polyamide elastomer, is melt into one with above-mentioned adhesive linkage.As shown in table 6, rubber also contains stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG2 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, crosslink agent DCP-405 weight portion except the NBR100 weight portion.The adhesive test result of comparative example 1 is as shown in table 5, when the strength that applies is 1-2N/mm
2The time interface peel appears.
Comparative example 2 is the soles that formed by following rubber, adhesive linkage and base portion: at least a portion of grounded part is to be the rubber that main material forms with SBR and X-NBR, adhesive linkage is formed by polyurethane elastomer, be melt into one with above-mentioned rubber and engage, base portion is formed by polyurethane elastomer, is melt into one with above-mentioned adhesive linkage.As shown in table 6, rubber also contains stearic acid 1 weight portion, silica 40 weight portions, plasticizer 10 weight portions, PEG2 weight portion, vulcanization accelerator 0.3 weight portion, age resister 1 weight portion, tackifier 5 weight portions, titanium oxide 5 weight portions, ultramarine 0.05 weight portion, antiscorching agent 0.3 weight portion, zinc oxide 3 weight portions, sulphur powder 1.7 weight portions, the CBS2 weight portion as promoter, DOTG0.3 weight portion, TMTM0.3 weight portion except SBR75 weight portion and X-NBR25 weight portion.The adhesive test result of comparative example 2 is as shown in table 5, when the strength that applies is 5-7N/mm
2The time interface peel appears.
Table 4
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Base portion | Polyamide elastomer (PEBAX6333) | Elastic polyurethane foaming body (ET1190 foaming body) | Polyamide elastic foam (PEBAX5533 foaming body) | Polyurethane elastomer (ET890) | Polyamide elastomer (VESTAMIDE55) | Polyolefin elastomer (Milastomer8032) |
| Rubber | NBR＋X-NBR | ?SBR＋X-NBR | ????NBR | ?NBR+X-NBR | ?SBR+X-NBR | ?SBR+X-NBR |
| Carboxyl concentration (EPHR) | ????0.01-0.1 | ????0.01-0.1 | ??????- | ????0.01-0.1 | ????0.01-0.1 | ????0.01-0.1 |
| Acid coating weight (mg/cm 2) | ????0.1-10 | ????????- | ??????- | ????????- | ????????- | ???????- |
| Addition (PHR) | ??????- | ????0.5-1.5 | ??????- | ????????- | ????????- | ????0.5-1.5 |
| Adhesive linkage | Polyamide elastomer (PEBAX5533) | Polyurethane elastomer (ET1190) | Polyamide elastomer (PEBAX5533) | Polyamide elastomer (PEBAX5533) | Polyamide elastomer powder (VESTAMIDE55) | Polyolefin powder (Milastomer8032) |
| Acid coating weight (mg/cm 2) | ??????- | ??????- | ????0.1-10 | ????????- | ????????- | ???????- |
| Adding rate (weight %) | ??????- | ??????- | ???????- | The 0.5-1.5 of adhesive linkage | The 0.5-1.5 of adhesive linkage | ???????- |
| Used powder average grain diameter (μ m) | ??????- | ??????- | ???????- | ????????- | ????200-800 | ????200-800 |
| Adhesive test result (N/mm 2) | Elastomeric material destroyed in 〉=16 o'clock | Elastomeric material destroyed in 〉=10 o'clock | Elastomeric material destroys during 11-15, the part interface peel | Elastomeric material destroyed in 〉=15 o'clock | Elastomeric material destroyed in 〉=15 o'clock | Elastomeric material destroyed in 〉=8.5 o'clock |
Table 5
| Comparative example 1 | Comparative example 2 | |
| Base portion | Polyamide elastomer (PEBAX5533) | Elastic polyurethane foaming body (ET1190) |
| Rubber | ??????NBR | ????SBR+X-NBR |
| Carboxyl concentration (EPHR) | ???????- | ?????0.01-0.1 |
| Acid coating weight (mg/cm 2) | ???????- | ?????????- |
| Addition (PHR) | ???????- | ?????????- |
| Adhesive linkage | Polyamide elastomer (PEBAX5533) | Polyurethane elastomer (ET1190) |
| Acid coating weight (mg/cm 2) | ???????- | ?????????- |
| Adding rate (weight %) | ???????- | ?????????- |
| Used powder average grain diameter (μ m) | ???????- | ?????????- |
| Adhesive test result (N/mm 2) | 1-2, interface peel | 5-7, interface peel |
Table 6
Embodiment 8
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | |
| X-NBR | ????50 | ????25 | ????75 | ????50 | ????50 | ????25 | ||
| NBR | ????50 | ????100 | ????25 | ????100 | ||||
| SBR | ????75 | ????50 | ????50 | ????75 | ||||
| Stearic acid | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 |
| Silica | ????40 | ????40 | ????40 | ????40 | ????40 | ????40 | ????40 | ????40 |
| Plasticizer | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 |
| PFG | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 |
| Vulcanization accelerator | ????- | ????0.3 | ????- | ????- | ????- | ????- | ????- | ????0.3 |
| Age resister | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 | ????1 |
| Tackifier | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 |
| Titanium oxide | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 |
| Ultramarine | ????0.05 | ????0.05 | ????0.05 | ????0.05 | ????0.05 | ????0.05 | ????0.05 | ????0.05 |
| Antiscorching agent | ????- | ????0.3 | ????- | ????- | ????- | ????- | ????- | ????0.3 |
| Zinc oxide | ????3 | ????3 | ||||||
| The sulphur powder | ????1.7 | ????1.7 | ||||||
| Accelerator CBS | ????2 | ????2 | ||||||
| Diphenylguanidine OTG | ????0.3 | ????0.3 | ||||||
| TM monex TM | ????0.3 | ????0.3 | ||||||
| Crosslink agent DCP-40 | ????5 | ????- | ????5 | ????5 | ????5 | ????5 | ????5 | ????- |
Fig. 8 illustrates from the observed sole of the present invention in side of the drafting department that is formed at rubber.Sole of the present invention is the rubber 2 that formed by thermo-setting elastomer of at least a portion by grounded part, form by thermoplastic resin or thermoplastic elastomer (TPE) be melt into one with rubber 2 and the sole 1 of the three-decker that the adhesive linkage 3 that engages and the base portion 6 that formed by thermoplastic resin or thermoplastic elastomer (TPE) constitute.Rubber 2 is melt into integratedly with adhesive linkage 3 and engages, and constitutes rubber bodies 4.
Fig. 9 illustrates from the observed sole 1 of the present invention of frontal of the drafting department that is formed at rubber 2.Figure 10 A is the profile of cutting open at the X-X of Fig. 9 section.The adhesive linkage 3 and rubber 2 melting adhered being integral that form by thermoplastic resin or thermoplastic elastomer (TPE), and fuse with adhesive linkage 3 by the base portion 6 that thermoplastic resin or thermoplastic elastomer (TPE) form.
Grounded part at rubber 2 is provided with convex rubber section 14.In convex rubber section 14, base portion 6 has male portion 15 or concave shaped portion 16.
Shown in Figure 10 B, in convex rubber section 14a, male portion 15 exists as core.Thus, when using than the hardness of the thermo-setting elastomer that is used in rubber 2 and rigidity is big and proportion is little thermoplastic elastomer (TPE) as the material of base portion 6, the rigidity of convex rubber section 14a is owing to male portion 15 increases, thereby can improve the performance on Part able to be adhered to sole ground.That is, convex rubber section 14a pricks soft ground such as soil, meadow easily owing to the increase of rigidity becomes, and not yielding, therefore, compares with the convex rubber section 14b that does not have male portion 15, attaches performance and improves.In addition, because the hardness of thermo-setting elastomer is little, therefore, for hardstands such as road surfaces, thermo-setting elastomer is yielding, can bring into play good grounding performance.And the thermo-setting elastomer of convex rubber section in the past then cracked and problems of crack can occur owing to undercapacity if hardness is too small, and because the existence of the core of male portion 15, convex rubber section 14a is not yielding, therefore, the problems referred to above can not take place.As a result,, therefore,, good grounding performance can be brought into play, shock-absorbing capacity can also be improved for hardstand owing to can use the thermo-setting elastomer of the soft that can't use in the past.The experience hardstand chance hardness of thermo-setting elastomer for a long time is preferably about Xiao A hardness 50-75, meets with hag face chance for a long time, and its Xiao A hardness is preferably about 65-90.When using than the hardness of the thermo-setting elastomer that is used in rubber 2 and rigidity is big and proportion is little thermoplastic elastomer (TPE), the rigidity of convex rubber section 14 is owing to male portion 15 increases, thereby sole is improved a lot to the grounding performance on ground.The thermoplastic elastomer (TPE) that hardness is big and proportion is little that is used in the thermoplastic elastomer (TPE) of rubber 2 for example can be the polyamide elastomer that does not have foaming.
In addition, because male portion 15 is present in the convex rubber section 14 as core, therefore, compare with base portion 6, the volume of heavy rubber 2 reduces, thereby can reduce the gross weight of sole.
When base portion 6 has concave shaped portion 16 in convex rubber section 14, can reduce the rigidity of its convex rubber section 14, the resiliency of raising sole and flexible, thus it is more comfortable that footwear are worn.
Illustrative sole can be used as the sole of football boot, olive sneakers, spike etc. among the embodiment 8.
Figure 11 illustrates from the observed sole 1 of the present invention in side of the drafting department that is formed at rubber 2.On the rubber bonding interface, be formed with complicated 3 D stereo curved surface.Sole 1 is to be melt into one by rubber 2, with rubber 2 and three-decker that the adhesive linkage 3 that engages and base portion 6 constitute.Rubber 2 is melt into integratedly with adhesive linkage 3 and engages, and constitutes rubber bodies 4.
Figure 12 illustrates from the observed sole shown in Figure 11 1 of frontal of the drafting department that is formed at rubber 2.Figure 13 A is the profile of cutting open at the XIIIA-XIIIA of Figure 12 section.Figure 13 B is the profile of cutting open at the XIIIB-XIIIB of Figure 12 section.The adhesive linkage 3 and rubber 2 melting adhered being integral that form by thermoplastic resin or thermoplastic elastomer (TPE), and fuse with adhesive linkage 3 by the base portion 6 that thermoplastic resin or thermoplastic elastomer (TPE) form.
Because the bonding plane with adhesive linkage 3 of rubber 2 has the 3 D stereo curved surface, therefore, after forming rubber to engage the all-in-one-piece rubber bodies, rubber bodies inserted in the injection mold assembly when thermoplastic elastomer (TPE) being fused, can improve the cementability of base portion and rubber bodies by means such as injection moldeds with adhesive linkage.
In addition, since can make the miscellaneous simplified control of the polishing processing, primary coat processing, adhesive coating, pressing working procedure etc. of the necessary rubber of laminating in the past or not need these operations, therefore, in the process of manufacturing sole, operating process is significantly simplified, thereby and reduced cost.
And, because silane coupling agent and adhesive can not ooze out, therefore, also can improve outward appearance, significantly improve the added value of commodity.
In addition, in the laminating of in the past carrying out, after the rubber that formation has a 3 D stereo curved surface engages the all-in-one-piece rubber bodies with adhesive linkage, rubber bodies inserted in the injection mold assembly when thermoplastic elastomer (TPE) being fused by means such as injection moldeds, the difference that breach and bonding force can occur, and in the present invention, bonding evenly and intensity big.
Illustrative sole can be used as the sole of football boot, olive sneakers, spike etc. among the embodiment 9.
Figure 14 illustrates from the observed sole 1 of the present invention in side of the drafting department that is formed at rubber 2.Sole 1 of the present invention is to be melt into one by rubber 2, with rubber 2 and the sole 1 of the three-decker that the adhesive linkage 3 that engages and base portion 6 constitute.
Figure 15 illustrates from the observed sole 1 of the present invention of frontal of the drafting department that is formed at rubber 2.Figure 16 is the profile of cutting open at the XVI-XVI of Figure 15 section.The adhesive linkage 3 and rubber 2 melting adhered being integral that form by thermoplastic resin or thermoplastic elastomer (TPE), and fuse with adhesive linkage 3 by the base portion 6 that thermoplastic resin or thermoplastic elastomer (TPE) form.
As shown in figure 16, at the edge of rubber 2, be provided with the rubber projections portion 17 of vertically stretching out.Owing to be provided with this rubber projections portion 17, therefore, can increase the bond area of rubber 2 and base portion 6, improve the bonding force of rubber 2 and base portion 6.
In addition, as shown in figure 15, be provided with ditch shape drafting department 18 on the face being provided with of rubber 2.At ditch shape drafting department 18 where, can increase the bond area of rubber 2 and base portion 6, improve the bonding force of rubber 2 and base portion 6.
Illustrative sole can be used as the sole of running shoes, tennis shoes etc. among the embodiment 10.
In sole of the present invention and manufacture method thereof, because synthetic rubber and the thermoplastic elastomer (TPE) sheet material is crosslinked is bonded together, therefore, the hardness of sole is about D hardness 35-65, has rigidity.And in order to be arranged to meet the pattern recess of background with the injection molded metal pattern, the Xiao A hardness of rubber is 60-75, is suitable as material for sole of shoe.
In addition, owing to will make the thermoplastic elastomer (TPE) sheet material be arranged to match with recess shapes with the pattern of background with the injection molded metal pattern than the rubber bodies of the big 0.1-5mm of elastomeric periphery, therefore, when the thermoplastic elastomer (TPE) injection molded is formed base portion, can effectively prevent from around synthetic rubber, to spread.
In addition, in the manufacture method of in the past sole, usually, the manufacturing firm of rubber is different often with injection molded producer, and therefore, such combination of materials can cause production efficiency to descend.And in the present invention, consider production efficiency, produce in batches synthetic rubber and the crosslinked bonding rubber bodies of thermoplastic elastomer (TPE) sheet material, this rubber bodies is inserted background with in the injection molded metal pattern by injection molded producer by rubber manufacturing firm, make base portion, improve production efficiency thus.Like this, the base portion injection molded can be formed different shape, thereby improve the free degree in the design.
In the present invention, owing to can make the bonding interface modification, increase the density of reactive functional groups, therefore, rubber is engaged securely with adhesive linkage by modification.In addition, by improving intermiscibility, rubber is engaged securely with adhesive linkage.Since rubber is engaged securely with adhesive linkage, therefore, the also corresponding raising of safety coefficient aspect joint difference.
In addition, in the present invention, because thermoplastic resin or thermoplastic elastomer (TPE) adhesive linkage are formed on the 3 D stereo curved surface of complexity of rubber bonding interface, therefore, by means such as injection moldeds thermoplastic resin or thermoplastic elastomer (TPE) are being merged when forming base portion on this adhesive linkage, can easily form base portion and base portion has good zygosity.And, owing to miscellaneous operations such as the polishing processing that can save the necessary rubber of laminating in the past, primary coat processing, adhesive coating, pressing working procedure, therefore, in sole manufacturing process, operating process is significantly simplified, thereby and be reduced cost.
And, because silane coupling agent and adhesive can not ooze out, therefore, also can improve outward appearance, significantly improve the added value of commodity.
In addition, in laminating in the past, in the time will having the rubber adhesion of complicated 3 D stereo curved surface, the difference of breach and bonding force can appearance can appear, and in the present invention, by merging, can make bonding evenly and intensity big.
Also have, in the convex rubber section of rubber grounded part, with thermoplastic resin or the thermoplastic elastomer (TPE) formation convex or the spill of base portion, to improve the sole quality and to make the function design become very easy.For example, in sport footwear, can be fit to the outstanding design of project characteristic etc.That is, for example, when the thermoplastic resin of base portion or thermoplastic elastomer (TPE) were formed convex, because bond area increases, bonding force improved, the outstanding pattern of rubber since the core of thermoplastic resin or thermoplastic elastomer (TPE) and rigidity increases paste the ground ability and improve.In addition,, can use the thermo-setting elastomer of the soft that in the past can't use, thereby design freedom improves, the grounding performance design that can suit owing to the existence of core.Also have, under the little situation of thermoplastic resin or thermoplastic elastomer (TPE) proportion, also can reduce sole weight.And when the thermoplastic resin of base portion or thermoplastic elastomer (TPE) formed spill, bonding force is increased, but owing to the rigidity of rubber projections reduces on the contrary, therefore, the resiliency of sole and flexible raising, thus it is more comfortable that footwear are worn.
Above the present invention has been done detailed explanation, but obviously should understand, they only are of the present invention illustrating, but not are limitation of the invention, and the spirit and scope of the present invention are limited by appended claims.
Claims (17)
1. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein, the thermoplastic elastomer (TPE) that is used to form base portion is injection molding to be shaped and makes above-mentioned rubber bodies and base portion monolithic molding simultaneously on the rubber bodies that the all-in-one-piece thermoplastic elastomer (TPE) constitutes in engaging by rubber with rubber, forms three-decker.
2. sole as claimed in claim 1, wherein, described rubber bodies constitutes by forming whole synthetic rubber and thermoplastic elastomer (TPE) sheet material, has the rubber profile.
3. sole as claimed in claim 1, wherein, described rubber bodies is bonded into one by synthetic rubber with the thermoplastic elastomer (TPE) sheet material with sole profile and forms.
4. sole as claimed in claim 1, wherein, described rubber bodies is linked into an integrated entity by the thermoplastic elastomer (TPE) sheet material by a synthetic rubber and another piece synthetic rubber and forms, and has the sole profile.
5. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Described rubber has the bonding interface through unsaturated acids or acid derivative modification,
Sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into the adhesive linkage that one engages by above-mentioned bonding interface and rubber,
Described base portion and above-mentioned adhesive linkage are melt into one.
6. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Described rubber contains unsaturated acids or acid derivative,
Sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into the adhesive linkage that one engages by above-mentioned bonding interface and rubber,
Described base portion and above-mentioned adhesive linkage are melt into one.
7. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Sole has the adhesive linkage that is formed by thermoplastic resin or thermoplastic elastomer (TPE), and this adhesive linkage has through the bonding interface of unsaturated acids or acid derivative modification and is melt into one by bonding interface with above-mentioned rubber and engages,
Described base portion and above-mentioned adhesive linkage are melt into one.
8. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Sole have by contain unsaturated acids or acid derivative and therefore and the thermoplastic resin of modification or thermoplastic elastomer (TPE) form, be melt into one with above-mentioned rubber and the adhesive linkage that engages,
Described base portion and above-mentioned adhesive linkage are melt into one.
9. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Sole has does the thermoplastic resin that mixes with unsaturated acids or acid derivative or thermoplastic elastomer powder is melted and form one with above-mentioned rubber and the adhesive linkage that engages,
Described base portion and above-mentioned adhesive linkage are melt into one.
10. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with above-mentioned rubber and the adhesive linkage that engages,
Described rubber contains thermoplastic resin or the thermoplastic elastomer (TPE) that mixes with above-mentioned adhesive linkage material height,
Described base portion and above-mentioned adhesive linkage are melt into one.
11. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with above-mentioned rubber and the adhesive linkage that engages,
Described base portion and above-mentioned adhesive linkage are melt into one and partly have male portion or concave shaped portion in the convex of above-mentioned rubber grounded part.
12. as each described sole among the claim 5-10, wherein, described base portion partly has male portion or concave shaped portion in the convex of rubber grounded part.
13. sole, it has the rubber that at least a portion of the base portion that formed by thermoplastic resin or thermoplastic elastomer (TPE) and grounded part is formed by thermo-setting elastomer, wherein,
Sole have form by thermoplastic resin or thermoplastic elastomer (TPE), be melt into one with above-mentioned rubber and the adhesive linkage that engages,
Described base portion and above-mentioned adhesive linkage are melt into one,
The rubber surface bonding with above-mentioned adhesive linkage has the 3 D stereo curved surface.
14. as each described sole among the claim 5-11, wherein, the rubber surface bonding with above-mentioned adhesive linkage has the 3 D stereo curved surface.
15. the manufacture method of sole, wherein, uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding gained rubber sheet is placed the rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with rubber and place metal pattern with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of recess profile, pressurized, heated once again, make rubber and thermoplastic elastomer (TPE) sheet material monolithic molding, form rubber bodies, with this rubber bodies be trimmed to background with the pattern of injection molded metal pattern with recess shapes after, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, will be used to form the thermoplastic elastomer (TPE) injection molded of base portion then, make above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion thus, form three-decker.
16. the manufacture method of sole, wherein, uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding gained rubber sheet is placed the rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of rubber soles profile and place metal pattern, pressurized, heated makes above-mentioned synthetic rubber and thermoplastic elastomer (TPE) sheet material monolithic molding once again, forms rubber bodies, after this rubber bodies is trimmed to the sole shape, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, will be used to form the thermoplastic elastomer (TPE) injection molded of base portion then, make above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion thus, form three-decker.
17. the manufacture method of sole, wherein, uncrosslinked synthetic rubber is kneaded, form sheet material, after the demoulding gained rubber sheet is placed a plurality of rubber recess of preform sole metal pattern, after the pressurized, heated, open metal pattern in the initial stage that above-mentioned rubber sheet is crosslinked, to have with conform to the substantially thermoplastic elastomer (TPE) sheet material of shape of rubber soles profile and place metal pattern, pressurized, heated makes above-mentioned a plurality of synthetic rubber link into an integrated entity by the thermoplastic elastomer (TPE) sheet material once again, forms rubber bodies, after this rubber bodies is trimmed to the sole shape, sandwich background with in the injection molded metal pattern, itself and pattern are coincide with recess, will be used to form the thermoplastic elastomer (TPE) injection molded of base portion then, make above-mentioned thermoplastic elastomer (TPE) sheet material and the thermoplastic elastomer (TPE) while monolithic molding that is used to form base portion thus, form three-decker.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000217762A JP3392395B2 (en) | 2000-07-18 | 2000-07-18 | Shoe sole |
| JP217762/2000 | 2000-07-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1334054A true CN1334054A (en) | 2002-02-06 |
| CN1180929C CN1180929C (en) | 2004-12-22 |
Family
ID=18712823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001280996A Expired - Fee Related CN1180929C (en) | 2000-07-18 | 2000-11-29 | Sole with three-layer structure and its manufacture method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3392395B2 (en) |
| CN (1) | CN1180929C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102783754A (en) * | 2012-08-17 | 2012-11-21 | 茂泰(福建)鞋材有限公司 | Shock-absorbing sole |
| CN103313620A (en) * | 2010-12-23 | 2013-09-18 | 彪马欧洲公司 | Shoe, in particular sports shoe, and method for producing same |
| CN104231346A (en) * | 2014-08-29 | 2014-12-24 | 广东志达行新材料有限公司 | Preparation method of inflatable ventilative shoe sole composite material |
| CN104411197A (en) * | 2012-06-20 | 2015-03-11 | 耐克创新有限合伙公司 | Sole structure for article of footwear |
| CN106572717A (en) * | 2014-07-11 | 2017-04-19 | 健乐士股份公司 | Method for providing parts of waterproof and breathable shoes, parts of waterproof and breathable shoes provided with the method, and waterproof and breathable soles provided with the shoe parts |
| CN109367091A (en) * | 2018-09-30 | 2019-02-22 | 沈丹 | A kind of manufacture craft and healthy shoe of sole |
| CN111513422A (en) * | 2020-04-28 | 2020-08-11 | 广东鹏骏新材料科技有限公司 | Glue-free foamed sole and manufacturing method thereof |
| CN112135727A (en) * | 2018-05-08 | 2020-12-25 | 彪马欧洲股份公司 | Method for producing soles for shoes, in particular sports shoes |
| US11744322B2 (en) | 2018-05-08 | 2023-09-05 | Puma SE | Sole of a shoe, particularly an athletic shoe |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007116968A1 (en) * | 2006-04-06 | 2007-10-18 | Midori Anzen Co., Ltd. | Sheet for shoe bottom, shoe bottom, shoes, and footwear |
| JP5705427B2 (en) * | 2008-12-11 | 2015-04-22 | 美津濃株式会社 | Shoe sole and method of manufacturing shoe sole |
| WO2017115417A1 (en) * | 2015-12-28 | 2017-07-06 | 株式会社アシックス | Shoe member, shoe, and method for manufacturing same |
| JP7039651B2 (en) * | 2020-06-05 | 2022-03-22 | 美津濃株式会社 | Rubber foam for soles |
| CN115519815A (en) * | 2022-09-02 | 2022-12-27 | 浙江奥康鞋业股份有限公司 | Polyurethane and rubber synthetic pouring bottom process |
-
2000
- 2000-07-18 JP JP2000217762A patent/JP3392395B2/en not_active Expired - Fee Related
- 2000-11-29 CN CNB001280996A patent/CN1180929C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103313620A (en) * | 2010-12-23 | 2013-09-18 | 彪马欧洲公司 | Shoe, in particular sports shoe, and method for producing same |
| US9839255B2 (en) | 2012-06-20 | 2017-12-12 | Nike, Inc. | Sole structure for article of footwear |
| CN104411197A (en) * | 2012-06-20 | 2015-03-11 | 耐克创新有限合伙公司 | Sole structure for article of footwear |
| CN102783754A (en) * | 2012-08-17 | 2012-11-21 | 茂泰(福建)鞋材有限公司 | Shock-absorbing sole |
| CN106572717B (en) * | 2014-07-11 | 2021-06-29 | 健乐士股份公司 | Method for providing a part of a waterproof and vapor-permeable shoe, part of a waterproof and vapor-permeable shoe provided with said method, and waterproof and vapor-permeable sole provided with said part of a shoe |
| CN106572717A (en) * | 2014-07-11 | 2017-04-19 | 健乐士股份公司 | Method for providing parts of waterproof and breathable shoes, parts of waterproof and breathable shoes provided with the method, and waterproof and breathable soles provided with the shoe parts |
| CN104231346A (en) * | 2014-08-29 | 2014-12-24 | 广东志达行新材料有限公司 | Preparation method of inflatable ventilative shoe sole composite material |
| CN112135727A (en) * | 2018-05-08 | 2020-12-25 | 彪马欧洲股份公司 | Method for producing soles for shoes, in particular sports shoes |
| CN112135727B (en) * | 2018-05-08 | 2023-02-03 | 彪马欧洲股份公司 | Method for producing soles for shoes, in particular sports shoes |
| US11744322B2 (en) | 2018-05-08 | 2023-09-05 | Puma SE | Sole of a shoe, particularly an athletic shoe |
| US11926115B2 (en) | 2018-05-08 | 2024-03-12 | Puma SE | Method for producing a sole of a shoe, in particular of a sports shoe |
| CN109367091A (en) * | 2018-09-30 | 2019-02-22 | 沈丹 | A kind of manufacture craft and healthy shoe of sole |
| CN111513422A (en) * | 2020-04-28 | 2020-08-11 | 广东鹏骏新材料科技有限公司 | Glue-free foamed sole and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002028002A (en) | 2002-01-29 |
| CN1180929C (en) | 2004-12-22 |
| JP3392395B2 (en) | 2003-03-31 |
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