CN113619254A - Method for adhering vulcanized shoes and multifunctional treating agent used for method - Google Patents
Method for adhering vulcanized shoes and multifunctional treating agent used for method Download PDFInfo
- Publication number
- CN113619254A CN113619254A CN202010383173.1A CN202010383173A CN113619254A CN 113619254 A CN113619254 A CN 113619254A CN 202010383173 A CN202010383173 A CN 202010383173A CN 113619254 A CN113619254 A CN 113619254A
- Authority
- CN
- China
- Prior art keywords
- rubber
- shoe
- treating agent
- multifunctional
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 93
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 143
- 239000000463 material Substances 0.000 claims abstract description 141
- 239000000853 adhesive Substances 0.000 claims abstract description 64
- 230000001070 adhesive effect Effects 0.000 claims abstract description 64
- 238000011282 treatment Methods 0.000 claims abstract description 53
- 229920001971 elastomer Polymers 0.000 claims description 41
- 239000005060 rubber Substances 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 239000004636 vulcanized rubber Substances 0.000 claims description 26
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- 229930195733 hydrocarbon Natural products 0.000 claims description 18
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 244000043261 Hevea brasiliensis Species 0.000 claims description 10
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
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- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
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- 239000005639 Lauric acid Substances 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
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- 229920003051 synthetic elastomer Polymers 0.000 claims description 3
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical group C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000004026 adhesive bonding Methods 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 27
- 238000001035 drying Methods 0.000 description 22
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- 239000010410 layer Substances 0.000 description 11
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- 238000004140 cleaning Methods 0.000 description 9
- 230000006870 function Effects 0.000 description 7
- -1 treatments Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 230000007613 environmental effect Effects 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
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- 239000002356 single layer Substances 0.000 description 4
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- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CKDDRHZIAZRDBW-UHFFFAOYSA-N henicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCC(O)=O CKDDRHZIAZRDBW-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
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- 238000005498 polishing Methods 0.000 description 2
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- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
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- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000008177 pharmaceutical agent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
- A43D25/00—Devices for gluing shoe parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J107/00—Adhesives based on natural rubber
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2437/00—Clothing
- B32B2437/02—Gloves, shoes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention relates to a method for the subsequent application of vulcanized shoes and a multifunctional treatment agent for use in said method, said method comprising applying one of a treatment agent and an adhesive to the surface to be applied of one or more of the shoe materials to be applied, prior to the application step, and wherein both said treatment agent and said adhesive are applied without overlapping each other to said surface to be applied. The invention further relates to a multifunctional treatment agent suitable for the adhesive bonding method and to the use thereof as an adhesive.
Description
Technical Field
The invention relates to a method for attaching in a shoe making procedure, which can effectively simplify the steps of the attaching method in the traditional shoe making procedure and is particularly suitable for the shoe making procedure of vulcanized shoes. The present invention also relates to a multifunctional treating agent for use in a method for bonding vulcanized shoes, which can treat and/or modify shoe materials such as soles and foxing, and can effectively bond the shoe materials.
Background
The traditional vulcanized shoe process relates to shoe materials of different materials such as vamps, soles, rubber enclosing strips and the like, and processes such as treating and combining the shoe materials, wherein in the process of attaching each shoe material, multiple chemical treatments are usually needed to the shoe materials to achieve the ideal attaching effect, the chemical treatments comprise cleaning the surface of the shoe materials by using a cleaning agent, coating a treating agent to modify the surface of the shoe materials, coating an adhesive or glue on the surface of the shoe materials and other treatments related to chemical agents, and the multi-step attaching method not only increases the cost, but also seriously reduces the shoe manufacturing efficiency. However, the material and shape of the shoe material vary greatly, and the desired effect of each step or the necessary sequence or mutual exclusion of the applied agents exist, so it is considered in the art that the multi-step attaching method is difficult to further simplify. For example, because the materials of the shoe materials are usually very different, the surface polarities of the shoe materials are different from each other, and the polarity of the shoe materials is also very different from that of the conventional glue, so that the shoe materials cannot be directly attached to each other; in addition, during manufacturing or warehousing of each shoe material, the surface of each shoe material may be contaminated with impurities or coated with chemicals such as an anti-adhesive agent which are helpful for preservation, and therefore, the shoe material must be further cleaned before being attached. In the field of shoe making, the treating agent not only has the function of modifying, but also has the cleaning function of removing impurities and chemical agents on the surface of a shoe material to be attached, so that the effect of attaching the subsequent shoe material is prevented from being influenced. Therefore, in the conventional vulcanized shoe manufacturing process, the surface of the shoe material must be treated by the treating agent, and the treating agent is dried and then coated with glue, so that the combination and the subsequent bonding can be carried out. For example, if the raw rubber foxing is to be covered and then attached to the shoe upper and the shoe body, the surface polarity of the rubber material is modified by treating with a treating agent, then the treated foxing is dried or baked, and then the surface to be attached, such as the shoe upper, the shoe body and the raw rubber foxing, is coated with the vulcanized rubber and then the subsequent processes are continued. In the flow production process, more than 2 persons are required to complete the operation of a flow line from the traditional modification to the following lamination step, which is very labor-consuming.
Because the treating agent has the function of modifying, when the treating agent is mixed with the glue, the glue can be layered, the stability of the glue is influenced, and meanwhile, if the glue is vulcanized glue, the vulcanizing agent contained in the vulcanized glue can also damage the property of the treating agent, so that the treatment effect of the treating agent is poor. Therefore, in the conventional practice in the art, the treating agent must be handled separately from the glue. In addition, various types of treating agents and glue are available in the market at present, but neither of the treating agents and the glue has good compatibility, and if the compatibility of the treating agents and the glue is not good, the adhesion effect is affected and even deteriorated, so that the treating agents are selected according to the material and the treatment purpose of each shoe material of the vulcanized shoes, and the type of the glue coated subsequently is also required to be considered. In addition, different treating agents and glues also generate different additional treating requirements, which not only increases the cost of shoe making, but also reduces the production efficiency, for example, some treating agents and vulcanizing glues require an activation step, and if the treating agents or vulcanizing glues are water-based, an additional drying step by adding an oven or other equipment is required in the shoe making step.
However, the multiple step-by-step bonding method of coating the treating agent and glue on the shoe material and the insufficient compatibility between the treating agent and glue often cause the shoe material to be bonded inefficiently or unstably, which also causes the extra cost for material waste in the manufacturing process and reduction of the production yield. Meanwhile, there is still a need in the art for various improvements to the conventional vulcanized rubber for vulcanized shoes, for example, it is desired to reduce or avoid additional activation and drying steps, or to improve the problems of Volatile Organic Compounds (VOC) generation and emission of the solvent-based vulcanized rubber, which may affect the environment and the health of people.
In view of the above, there is still a need to develop a vulcanized shoe bonding method that can solve the above problems, simplify the shoe manufacturing process, protect the environment, and effectively reduce the production cost. On the other hand, a treatment agent which has a wide application range, is suitable for various materials, is compatible with various types of glue, is environment-friendly and can effectively reduce the production cost is required to be developed so as to meet the current market demand.
Disclosure of Invention
On the basis, one of the objectives of the present invention is to improve the bonding method in the vulcanized shoe manufacturing process, so as to simplify the operations or steps required for bonding, further reduce labor power, production cost, increase production efficiency, reduce pollution caused by discharge of harmful substances such as VOC, and maintain good adhesion while simplifying the bonding method.
Another object of the present invention is to develop a novel treating agent which can be used in the simplified method for attaching vulcanized shoes in the present case, has good properties, is suitable for modifying and treating the surface of various materials of vulcanized shoes, such as rubber, foamed materials, etc., and can partially or completely replace adhesives (e.g., vulcanized rubber) to attach various shoe materials of vulcanized shoes, thereby reducing or even avoiding the use of adhesives.
In accordance with the above object, the present invention provides a method for attaching vulcanized shoes, which comprises applying a chemical treatment to a surface to be attached of one or more shoe materials to be attached, before the attaching step, wherein the chemical treatment comprises one of a treating agent and an adhesive, and wherein the surface to be attached treated with the chemical treatment does not contain both the treating agent and the adhesive. The invention provides a method for attaching vulcanized shoes, which comprises the step of coating one of a treating agent and an adhesive on the surface to be attached of one or more shoe materials to be attached before the attaching step, wherein the treating agent and the adhesive are not coated on the surface to be attached in an overlapping manner.
When the method for adhering the shoe material is used for manufacturing vulcanized shoes, the steps of coating the shoe material with a treating agent, an adhesive (such as vulcanized rubber) and/or other agents can be reduced, namely, the coating of the treating agent, the adhesive and/or other agents is reduced, particularly the coating of the treating agent and/or the adhesive is reduced, and then the treatment steps aiming at the coating, such as activation, drying and the like, can also be reduced, so that the method has the advantages of simplifying the operation mode, reducing the manpower requirement, shortening the processing time, reducing the cost and the like, and simultaneously, because the use of chemicals is reduced, the emission of VOC, residues or byproducts in the manufacturing process can be greatly reduced, and the requirement on environmental friendliness is met.
In accordance with the above object, the present invention further provides a multifunctional primer comprising a rubber, a tackifying resin and a hydrocarbon solvent, wherein the solid content of the multifunctional primer is 5 to 15 wt%.
In the multifunctional primer of the present invention, 10 to 20 parts by weight of rubber and 1 to 10 parts by weight of tackifying resin are included in addition to hydrocarbon solvent.
The present invention further provides the use of the multifunctional primer of the present invention as an adhesive for use in a process of attaching vulcanized shoes. Because the multifunctional finishing agent has special viscosity, the polarity of the surface of the shoe material of the vulcanized shoe is modified, and the modified shoe material can be directly adhered to other shoe materials made of different materials. When the multifunctional treating agent is used for manufacturing vulcanized shoes, the modified shoe materials do not need to be further coated with adhesives (such as vulcanized rubber), so that the multifunctional treating agent has the advantages of simplified operation mode, reduced manpower requirement, shortened processing time, reduced cost and the like, and simultaneously, the VOC emission in the manufacturing process can be greatly reduced due to the reduction of the use of the adhesives, thereby meeting the requirement of environmental friendliness.
Drawings
The invention will be further elucidated hereinafter on the basis of an example of embodiment schematically shown in the drawing, in which
FIG. 1 illustrates a subsequent application process in a vulcanized shoe manufacturing process in the prior art;
FIG. 2 illustrates a subsequent application process in a simplified vulcanized shoe process using the multifunctional primer of the present invention;
FIG. 3 is a schematic view of a shoe body manufactured according to the embodiment of the present disclosure;
FIG. 4 is a schematic flow chart of comparative example 3 of the present case; and
fig. 5 is a schematic flow chart of embodiment 2 of the present application.
Detailed Description
As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention, as such, and the language in the specification should not be construed as implying that any non-claimed method or condition may constitute essential features of the invention.
The recitation of numerical ranges by endpoints herein includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).
Unless otherwise stated, all numbers are to be considered as modified by the term "about," as used herein.
The term "preferred" in embodiments of the present invention indicates that certain benefits may be provided in certain circumstances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
As used herein, "shoe material" refers to the conventional components of a shoe product, such as the midsole, outsole, upper, foxing, etc.
In this context, "chemical treatment" refers to a treatment step of applying chemicals to the surfaces to be bonded of shoe materials to be bonded, prior to bonding of different or the same shoe materials, in a method of subsequent bonding in the field of shoemaking; the "agent" includes chemicals such as cleaning agents, surface modifiers, treatments, adhesives (including glues), etc., which treatments may directly or indirectly affect, enhance or provide the effects of the subsequent bonding.
Herein, "not including both the treating agent and the adhesive" is not intended to limit the time point of applying the treating agent and the adhesive, but indicates that both the treating agent and the adhesive are not present together. Thus, "not including both a treating agent and an adhesive on a surface to be bonded" means that there is no way to apply both a treating agent and an adhesive on the same surface to be bonded before it is bonded to another surface to be bonded, and vice versa.
According to one aspect of the application, the method for attaching vulcanized shoes of the invention reduces the step of applying at least one chemical agent in the conventional procedure for attaching shoe materials. Furthermore, the method for adhering vulcanized shoes of the invention reduces the steps of coating at least one treating agent or adhesive and the corresponding drying, activating and other procedures in the conventional procedure for adhering shoe materials; still further, the method for the subsequent application of vulcanized shoes according to the invention allows to reduce the step of applying at least one treatment agent or adhesive on one or more surfaces to be applied and the corresponding drying, activation, etc. steps. In the next fitting method for vulcanized shoes of the present invention, before the fitting step is performed, a chemical treatment is provided to the surface to be fitted of one or more of the shoe materials to be fitted, wherein the chemical treatment includes a treatment agent or an adhesive, and wherein when the chemical treatment is a treatment agent, the adhesive is not coated on the surface to be fitted which is treated with the chemical, and wherein when the chemical treatment is an adhesive, the treatment agent is not coated on the surface to be fitted which is treated with the chemical.
According to one aspect of the application, the method for the subsequent fitting of vulcanized shoes according to the invention removes the step of applying at least one pharmaceutical agent in the conventional procedure for the subsequent fitting of shoe materials. Furthermore, the method for adhering vulcanized shoes removes at least one coating step of a treating agent or an adhesive and corresponding drying, activating and other procedures in the conventional procedure for adhering shoe materials; still further, the method for the subsequent application of vulcanized shoes according to the present invention removes one or more surfaces to be applied, at least one step of applying a treatment agent or adhesive and the corresponding steps of drying, activating, etc. The subsequent fitting method for vulcanized shoes according to the present invention comprises applying one of a treatment agent and an adhesive to a surface to be fitted of one or more shoe materials to be fitted, before the fitting step is performed, and wherein the treatment agent and the adhesive are not applied to the same surface to be fitted in an overlapping manner with each other. The term "non-overlapping coating" as used herein means that the treating agent and the adhesive are not present on a single surface in any form, proportion, or order.
In accordance with one aspect of the present application, it has been found that it is not necessary to apply both a treatment and an adhesive to all surfaces of the shoe material to be attached to achieve satisfactory attachment. The method for attaching vulcanized shoes disclosed by the invention has the advantages that good adhesion can be still shown after the shoe material is attached to other shoe materials to be attached even if only one of the treating agent and the adhesive is coated on the surface to be attached of one shoe material to be attached; the present invention further finds that even if only one layer of treating agent is coated on the surface to be attached of one shoe material to be attached, the shoe material can still exhibit good adhesion after being attached to other shoe materials to be attached. The invention further discovers that even if only the surface to be attached of the foxing is coated with the treating agent and no adhesive is coated, the foxing can still show good adhesion after being attached with other shoe materials to be attached; the present invention further finds that the foxing exhibits good adhesion after being fitted to other shoe materials to be fitted, even if only one layer of treating agent and no adhesive is applied to the surface to be fitted of the foxing.
According to the method for attaching vulcanized shoes of the present invention, one skilled in the art can determine the number of coating layers of any one chemical, such as one layer, two layers, three layers, preferably one layer, on the surface to be attached of any shoe material to be attached according to the desired attaching effect or the corresponding processing steps. According to the method for the subsequent application of vulcanized shoes of the present invention, after the application of the shoe materials to be applied, the number of coating layers of the treating agent and the adhesive contained between two shoe materials is not more than five layers in total, preferably not more than three layers.
The invention relates to a method for attaching vulcanized shoes, which comprises the steps of providing the medicament treatment on the first surface of a first shoe material, wherein the medicament treatment comprises a treatment agent; coating a treating agent or an adhesive on the first surface of the second shoe material; and directly attaching the first surface of the first shoe material to the first surface of the second shoe material.
The invention relates to a method for adhering vulcanized shoes, which comprises the steps of coating the multifunctional treating agent on the first surface of a first shoe material, and coating the multifunctional treating agent or the adhesive on the first surface of a second shoe material; and directly attaching the first surface of the first shoe material to the first surface of the second shoe material.
According to the method for attaching vulcanized shoes of the present invention, the number of layers of the treating agent and the adhesive applied to the first surface of the first shoe material and the first surface of the second shoe material is not more than five layers in total, preferably not more than three layers.
In the method for attaching vulcanized shoes of the present invention, the adhesive is vulcanized rubber.
In the method for attaching vulcanized shoes of the present invention, depending on the type of shoe material and the process requirements, the second shoe material may be coated with only a single layer of the multifunctional treatment agent of the present invention, only a single layer of vulcanized rubber, or may be coated with vulcanized rubber after being coated with the multifunctional treatment agent of the present invention.
In the method for attaching vulcanized shoes according to the present invention, the first shoe material and the second shoe material may be the same or different shoe materials, such as, but not limited to, the following shoe materials: the shoe comprises a middle sole, an upper sole, a vamp and a foxing; and the first shoe material and the second shoe material can be made of different or same materials, wherein the materials comprise unvulcanized rubber materials, vulcanized rubber materials, semi-finished vulcanized rubber materials, non-rubber materials, synthetic fiber materials and natural fiber materials. Materials from which the sole may be formed generally include, but are not limited to, vulcanized rubber-like materials and non-rubber-like materials; materials that may form the upper generally include, but are not limited to, synthetic fiber materials, natural fiber materials, synthetic leather, and leather, such as: PU synthetic leather, genuine leather, cotton fiber material and polyester fiber cloth; while the materials forming the foxing strip generally include, but are not limited to, unvulcanized rubbers and vulcanized rubbers such as: green rubber and semi-green rubber with incomplete vulcanization.
In the method for attaching vulcanized shoes of the present invention, in order to further enhance the effect of attaching, the method may include the steps of coating a treating agent or an adhesive on the surface to be attached of the shoe material to be attached, and then performing other treatments on the surface, such as drying, wherein the drying step may be any known drying method, such as natural drying, oven heating drying, etc.; or, for example, activation, wherein the activation step can be performed by various conventional activation methods, such as oven heating activation, light irradiation activation, etc. For example, if a surface to be attached of a shoe material to be attached is coated with a vulcanized rubber, the shoe material to be attached can be placed into an oven to activate the rubber. In addition, the method for attaching vulcanized shoes according to the present invention may further comprise, after the step of directly attaching, a step of further processing the attached shoe material, such as, but not limited to, drying the attached shoe material, compacting the attached shoe material, and repeating the pressing, and the like, wherein the further processing steps may be selected according to the type of the shoe material and the process requirements, and the operation sequence thereof may be determined according to the requirements. After the shoe material is attached by the method for attaching a vulcanized shoe of the present invention, the vulcanizing process can be directly performed.
In the method for applying the adhesive to vulcanized shoes according to the present invention, the shoe materials (especially, the upper and the sole) may be treated before applying a treating agent or an adhesive (e.g., vulcanized rubber), and the treatment includes, but is not limited to: cleaning, drying, grinding, polishing, reinforcing and the like. The cleaning process may be any conventional cleaning method, such as: cleaning, dedusting, etc. The drying treatment may be any conventional drying method, such as: drying, air drying and the like. The grinding or polishing process can be any conventional grinding or polishing method, such as using sandpaper, a grinder, etc., to achieve a desired roughness or smoothness of the surface of the footwear. The reinforcement treatment may be any conventional reinforcement method, such as applying a reinforcing agent, fixing a reinforcing member, and the like. For example, the green foxing can be attached to the reinforced upper or sole by the attachment method of the present invention.
The multifunctional treating agent comprises the components, so that the treating agent has viscosity without influencing the original modifying function, and can partially or even completely replace vulcanized rubber in the manufacturing process of vulcanized shoes. In addition, the polarity of the multifunctional treating agent is between that of the conventional shoe material (such as cotton cloth or polyester fiber cloth) and rubber, so that the multifunctional treating agent can be compatible with the interface matching between different materials in the following adhering and vulcanizing process, and can also be compatible with more kinds of adhesives (such as vulcanized rubber).
The multifunctional primer of the present invention contains, in addition to the hydrocarbon solvent, about 10 to about 20 parts by weight of rubber, preferably about 12 to about 18 parts by weight, and more preferably about 14 to 16 parts by weight. The above values may include any range of values, both subranges, and any value within the range.
The multifunctional primer of the present invention contains the tackifying resin in an amount of about 1 to about 10 parts by weight, preferably about 1 to about 7 parts by weight, and more preferably about 2 to 6 parts by weight, in addition to the hydrocarbon solvent. The above values may include any range of values, both subranges, and any value within the range.
The components of the multifunctional treating agent except the hydrocarbon solvent are respectively subjected to rubber mastication and mixing in a proper proportion, and a semi-finished product of the multifunctional treating agent is obtained after uniform mixing; the semi-finished product is dissolved in a proper amount of hydrocarbon solvent to obtain a composition having a solid content ratio of about 3 wt% to about 20 wt%, preferably about 5 wt% to about 15 wt%, and more preferably about 7 wt% to about 12 wt%, which is the multifunctional treating agent of the present invention. If the solid content is more than 20 wt%, the problem of difficulty in coating due to a high viscosity is caused; if the solid content is less than 3% by weight, the tackiness of the multifunctional primer is impaired, the initial bonding strength is lowered, the function of replacing glue is greatly lowered, and the subsequent bonding process is adversely affected.
The rubber suitable for the multifunctional primer of the present invention may be any rubber known to one having ordinary skill in the art to which the present invention pertains to have subsequent bonding properties, such as, but not limited to, natural rubber, synthetic rubber, modified natural rubber, and combinations thereof. Synthetic rubbers which may be used include chloroprene rubber, styrene-butadiene rubber, nitrile rubber, butyl rubber, natural rubber, urethane rubber and the like, preferably chloroprene rubber, styrene-butadiene rubber, natural rubber and modified natural rubber, more preferably natural rubber or modified natural rubber.
The tackifying resin can affect the physical properties of the resulting treatment and can provide or enhance the adhesive properties of the treatment. The tackifying resin suitable for use in the multifunctional primer of the present invention can be any tackifying resin known to those of ordinary skill in the art having properties that increase the working time of a glue, such as, but not limited to, petroleum resins, modified petroleum resins, terpene phenolic or phenolic modified resins, rosins, modified rosin resins, and combinations thereof. The tackifying resins which can be used include petroleum resins, hydrogenated petroleum resins, alkyl phenol resins, rosins, modified rosin resins and the like, and preferably phenol-modified resins, C5 to C9 petroleum resins and hydrogenated petroleum resins.
The hydrocarbon solvent suitable for the multifunctional treating agent of the present invention includes benzene, ketone, alkane solvents or their combination, preferably alkane, ketone or their combination, preferably alkane with carbon number of 5 to 10, ketone with carbon number of 3 to 8 or their combination, more preferably butanone, methylcyclohexane or their combination. The multifunctional primer of the present invention may optionally further comprise other solvents to aid in cleaning, swelling the material or dissolving solids, such as carbonates, acetates, for example: ethyl acetate, butyl acetate, and the like.
The multifunctional treating agent of the invention preferably further comprises a zinc compound, and the zinc compound has the functions of promoting rubber vulcanization, activation, reinforcing treating agent and the like, and can also improve the heat resistance of the rubber material. The zinc compound suitable for the multifunctional primer of the present invention includes zinc oxide, zinc carbonate, zinc sulfate, zinc stearate or a combination thereof, preferably zinc oxide, zinc carbonate or a combination thereof. The zinc compound is added in an amount of about 0.1 to about 1 part by weight, preferably about 0.2 to about 0.8 part by weight, more preferably about 0.5 to 0.8 part by weight, based on the total weight of the multifunctional primer of the present invention, excluding the hydrocarbon solvent. The above values may include any range of values, both subranges, and any value within the range.
The multifunctional primer of the present invention preferably further comprises a saturated fatty acid, and more preferably comprises a saturated fatty acid having 12 to 24 carbon atoms. The saturated fatty acid having 12 to 24 carbon atoms has a vulcanization activity buffering property and contributes to vulcanization activation of the treating agent. The saturated fatty acid having a carbon number of 12 to 24, which is suitable for the multifunctional primer of the present invention, includes lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, pearlescent acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanoic acid, behenic acid, eicosanoic acid, lignoceric acid, or a combination thereof, preferably lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, or a combination thereof, more preferably myristic acid, palmitic acid, stearic acid, or a combination thereof. The content of the saturated fatty acid added is about 0.1 to about 1 part by weight, preferably about 0.2 to about 0.8 part by weight, more preferably about 0.4 to 0.6 part by weight based on the total weight of the multifunctional primer of the present invention, excluding the hydrocarbon solvent. The above values may include any range of values, both subranges, and any value within the range.
The multifunctional primer of the present invention optionally preferably further comprises a vulcanizing agent and/or a vulcanization accelerator. In response to the difference in the properties of the materials to be bonded, one of ordinary skill in the art can choose to add a vulcanizing agent and/or a vulcanizing accelerator to the multifunctional treating agent of the present invention to further enhance the bonding effect. The vulcanizing agent suitable for the multifunctional primer of the present invention can be any vulcanizing agent known to those of ordinary skill in the art to have crosslinked rubber properties, such as, but not limited to, sulfur, organic peroxides, polysulfide polymers, sulfur monoxide, and the like, and combinations thereof, preferably sulfur and tetramethylthiuram disulfide (TMTD). The vulcanizing agent is added in an amount of about 0.5 to about 2 parts by weight, preferably about 0.7 to about 1.5 parts by weight, more preferably about 0.9 to 1.2 parts by weight, based on the total weight of the multifunctional primer of the present invention, excluding the hydrocarbon solvent. The above values may include any range of values, both subranges, and any value within the range.
The vulcanization accelerator suitable for use in the multifunctional primer of the present invention may be any vulcanization accelerator known to one of ordinary skill in the art having the property of regulating the vulcanization rate, such as, but not limited to, thiuram compounds, amine salt compounds, diphenylguanidine, sulfenamides, thiazoles, zinc phosphate compounds, and combinations thereof. Vulcanization accelerators which can be used include benzothiazyl-2-Cyclohexylsulfenamide (CBS), zinc dibutyldithiocarbamate (BZ), Diphenylguanidine (DPG), 2-Mercaptobenzothiazole (MBT), zinc dibenzyldithiocarbamate (ZBEC) and the like, preferably CBS, BZ, MBT, more preferably BZ, MBT. The vulcanization accelerator is added in an amount of about 0.1 to about 2 parts by weight, preferably about 0.1 to about 1.0 part by weight, more preferably about 0.2 to 0.5 part by weight, based on the total weight of the multifunctional primer of the present invention, excluding the hydrocarbon solvent. The above values may include any range of values, both subranges, and any value within the range.
When the multifunctional treating agent is used, a curing agent can be additionally added according to needs so as to achieve better adhesion physical properties. Suitable hardeners include polyisocyanates or salts thereof and polyamide resins. The amount of the hardening agent added is 1 to 8 wt%, preferably 2.5 to 7 wt%, more preferably 3.5 to 5.5 wt% based on the total weight of the multifunctional primer.
The multifunctional primer of the present invention may further optionally include additives such as, but not limited to, stabilizers, tackifiers, detergents, and solubilizers. In the multifunctional primer of the present invention, the additive is present in an amount of about 1 to about 10 wt%, preferably about 1.2 to about 1.5 wt%, based on the total weight of the multifunctional primer.
The multifunctional treating agent of the invention not only has the effect and the application of surface modification, but also has the effect of cleaning the surface; the multifunctional treating agent of the invention has strong viscosity to the conventional shoe materials, especially to the foxing materials, so the multifunctional treating agent also has the application as an adhesive. When the multifunctional treating agent is used as an adhesive, the multifunctional treating agent can have the desired viscosity after being directly coated on a substrate without an additional activation process. The multifunctional treating agent has polarity between common shoe materials and rubber, so that the multifunctional treating agent can be widely applied to various shoe materials, particularly foxing materials, and can be used for surface modification and/or cleaning, is compatible with more types of vulcanized rubber, and ensures that the shoe materials keep good and durable bonding effect. In addition, since the multifunctional primer of the present invention is in a liquid state, it has good ductility and storage stability, and the amount of the multifunctional primer used and the thickness and range of the coating layer can be easily controlled during use, thereby maintaining a good adhesion to the bonding surface. The coating thickness of the multifunctional treating agent can be between 0.3mm and 0.1mm, even can reach below 0.1mm, so that the appearance or the function of the shoe can not be influenced by the extra thickness of the binding surface.
In conclusion, the multifunctional primer of the present invention, which comprises specific components and is applied to the process of attaching vulcanized shoes, can provide excellent, stable and reliable adhesive strength. Compared with the traditional process, the multifunctional treating agent can greatly reduce the use of adhesives such as vulcanized rubber, reduce OVC emission, meet the requirement of environmental protection, reduce the requirement of operation manpower, reduce the use of materials, machines and energy, have wider application range and simpler operation, and can better meet the requirement of international brands on environmental protection and waste reduction.
By using the method for adhering the vulcanized shoe and the multifunctional treating agent, the adhering strength of the shoe material can be effectively maintained or even improved while the steps of the adhering method are simplified, and the use of adhesives (such as vulcanized rubber) is reduced or avoided. In the field of shoe making, after the vamp and the foxing are attached, a pulling force of more than 3 kilograms per centimeter is required between the vamp and the foxing, namely the adhesive force between the vamp and the foxing is more than 3.0 kilograms per centimeter; the adhesive force between the outsole and the surrounding strip is required to be more than 2.5 kg/cm. The multifunctional treating agent can provide the adhesion force between the vamp and the foxing of more than 3.0 kg/cm, preferably more than 4.0 kg/cm, and more preferably more than 5.0 kg/cm; and provides an adhesion force between the outsole and the foxing of more than 3.0 kg/cm, preferably more than 4.0 kg/cm, and more preferably more than 5.0 kg/cm.
Meanwhile, the method for adhering and jointing vulcanized shoes and the multifunctional treating agent can effectively reduce the number of coating layers of the treating agent and the adhesive on the jointing surface of the shoe material, so that the thickness of the adhesive layer after the combination of glue, the treating agent and the like between the jointing surfaces of the shoe material can be effectively reduced, the glue overflow condition can be avoided when the shoe material is adhered, the appearance and the light weight of the shoes are facilitated, the production rate is increased, the production cost is reduced, and the fitting degree between the shoe materials is facilitated.
The following examples are illustrative of embodiments of the present invention and illustrate technical features of the present invention, and are not intended to limit the scope of the present invention. Any arrangement which can be easily changed or equalized by a person skilled in the art is included in the scope of the present invention, which is defined by the appended claims.
Example (c):
example 1 and comparative examples 1 and 2
A. Tension test
The shoe bodies or test pieces prepared in comparative examples 1 and 2 and example 1 were subjected to a tensile test using a tensile machine (GT-7010-D2E, high-speed rail technologies Co., Ltd.) to illustrate the following effects of the present invention. Two clamps are used for fixing two sides of a part to be tested, the part to be tested is pulled open towards two sides at a fixed testing speed, and when the attachment interfaces of the surrounding strip and the vamp, the surrounding strip and the sole and any one of the vamp and the sole are stripped, the pulling force value is recorded.
B. Test piece preparation and tensile test results
While conventional vulcanized shoes are subsequently laminated, the treated shoe material is coated with a vulcanized rubber (as shown in FIG. 1), the multifunctional primer of the present invention provides sufficient adhesion and no vulcanized rubber (as shown in FIG. 2). The test piece tensile test shows that the multifunctional treating agent of the invention has the effects of reducing the usage of vulcanized rubber and having good adhesion compared with the traditional treating agent sold in the market. In the test piece test, the foxing made of raw rubber is used as the first shoe material and the vamp made of cotton fiber is used as the second shoe material, i.e. the foxing is only coated with a single layer of the treating agent sold in the market or the invention, and the vamp is sequentially coated with the treating agent and the vulcanizing rubber according to the traditional process. Table 1 shows the commercial products used in the present invention for preparing the test pieces of comparative examples 1 and 2 and example 1, the multifunctional treatment agent of the present invention, and the reference numbers thereof. The multifunctional treating agent V277 of the present invention used in the present example comprises: the multifunctional treating agent V277 is prepared by mixing and refining 15 parts of natural rubber, 5 parts of modified phenolic resin, 4 parts of hydrogenated petroleum resin, 0.3 part of vulcanizing agent, 0.5 part of zinc oxide, 0.8 part of stearic acid and 0.5 part of antioxidant, adding 200 parts of hydrocarbon solvent as solvent, wherein the hydrocarbon solvent comprises 110 parts of methylcyclohexane, 70 parts of butanone and 20 parts of ethyl acetate, and dissolving and balancing.
| Water on the upper | Dadong resin, 6001L |
| Oily rubber processor | Nanbao resin, P515 |
| Oily rubber processor | Dadong resin, 299A |
| The multifunctional treating agent of the present invention | Dadong resin, V277 |
| Waterborne vulcanizing glue for vamp | Dadong resin, 6127T |
| Hardening | Dado resin, 366S |
TABLE 1
Preparation of a test piece: firstly, treating the surface to be attached of the vamp by a 6001L treating agent added with 5 weight percent of 366S hardening agent, then coating a single layer 6127T, and then putting the vamp into an oven to activate for 3 minutes at the temperature of 70 ℃ for later use; coating the surfaces of the enclosing strips to be attached with the treatment agents which are sold in the market or provided by the invention and are shown in the table 2 respectively; fitting the vamp and the foxing; compacting the attached vamp and the surrounding strip by a press under the pressurizing condition of 5 kilograms for 5 seconds; and vulcanizing the attached surrounding strips and the vamp at the temperature of 120 ℃ for 70 minutes, and finally cutting into test pieces with the length of 7 centimeters and the width of 2 centimeters for carrying out tension test.
| Surrounding strip | Treating agent for foxing |
| Comparative example 1 | P515 |
| Comparative example 2 | 299A |
| Example 1 | V277 |
TABLE 2
And (3) testing the tensile force of the test piece: the obtained test pieces were tested at a test speed of 20cm/min, and the tensile tests were repeated four times in each of comparative examples 1 and 2 and example 1, and the test results of the vamp-raw rubber foxing are shown in Table 3. As can be seen from table 3, the example test pieces using the multifunctional treatment agent of the present invention have adhesion force far better than the comparative test pieces using the conventional treatment agent on the market, and the example test pieces can even bear 16 times higher tensile force than the comparative test pieces. This experiment demonstrates that satisfactory or even excellent adhesion can be achieved with reduced application of the vulcanized rubber if the multifunctional primer of the present invention is used.
TABLE 3
Example 2 and comparative example 3
C. Shoe body preparation and tensile test results
This test shows that the multifunctional primer of the present invention can be applied to various kinds of shoe materials, and can maintain good adhesion. In the shoe body test, a complete shoe body (as shown in fig. 3) is manufactured by using a vamp made of cotton fiber, an outsole made of rubber and a foxing made of raw rubber, and the shoe body is subjected to a tension test. The shoe bodies of the comparative examples and the examples were prepared in the following manner, respectively.
Comparative example 3 was prepared: table 4 below shows the commercial products used in the preparation of comparative example 3 and their code references, and the shoe body of comparative example 3 was prepared according to the following procedure (as shown in fig. 4):
1. raw rubber surrounding strip: coating 299A treating agent added with 5 percent 299B vulcanizing assistant on the surface to be jointed of the foxing, naturally drying for 30 seconds to 1 minute, coating V99NTA vulcanizing adhesive comprising 5 percent V99NTB vulcanizing assistant and 5 percent 366S hardening agent on the treated surface, and naturally drying for 30 seconds to 1 minute for later use;
2. shoe upper: coating 6001L treating agent added with 5% 366S hardening agent on the surface of the vamp to be attached, placing the vamp in an oven, drying the vamp at the temperature of 60-65 ℃ for 2 minutes to 2 minutes and 30 seconds, coating 6127TC vulcanizing adhesive on the treated surface, and then placing the vamp in the oven, activating the vamp at the temperature of 55-60 ℃ for 2 minutes to 2 minutes and 30 seconds for later use;
3. the shoe outsole: coating 299A treating agent added with 5 percent 299B vulcanizing assistant on the surface of the outsole to be attached, drying the outsole in an oven at the temperature of 55-60 ℃ for 2 minutes to 2 minutes and 30 seconds, coating 6127TC vulcanizing adhesive on the treated surface, and then activating the outsole in the oven at the temperature of 55-60 ℃ for 2 minutes to 2 minutes and 30 seconds for later use;
4. attaching: the upper, outsole and foxing were fitted, and the body of the fitted shoe was compacted by a cross press at 22 kg for 4 seconds and then vulcanized at 120 ℃ for 70 minutes.
| Water on the upper | Dadong resin, 6001L |
| Oily rubber processor | Dadong resin, 299A |
| Oily rubber processor | Dadong resin, 299B |
| Waterborne vulcanizing glue for vamp | Dadong resin, 6127TC |
| Oily vulcanized rubber | Dadong resin, V99NTA |
| Vulcanization aid for oily rubber | Dadong resin, V99NTB |
| Hardening | Dado resin, 366S |
TABLE 4
Preparation example 2: table 5 below shows a comparison of the commercial products used in preparation example 2 and their code numbers, and the shoe body of example 2 was made according to the following procedure (as shown in fig. 5):
1. raw rubber surrounding strip: coating the V277 treating agent added with the 5% 632R hardening agent on the surface to be attached of the foxing, and naturally drying for 30 seconds to 1 minute for later use;
2. shoe upper: coating 6001L of treating agent added with 5% 366S hardening agent on the surface of the upper to be attached, placing the coated upper in an oven, activating at the temperature of 60-65 ℃ for 2 minutes to 2 minutes and 30 seconds, coating 6127T3 vulcanized rubber on the treated surface, and then placing the upper in the oven, activating at the temperature of 55-60 ℃ for 2 minutes to 2 minutes and 30 seconds for later use;
3. the shoe outsole: coating 6299W of treating agent on the surface to be attached of the outsole, placing the coated outsole in an oven, activating at the temperature of 55-60 ℃ for 2 minutes to 2 minutes and 30 seconds, coating 6127T3 vulcanized rubber on the treated surface, and then placing the outsole in the oven, activating at the temperature of 55-60 ℃ for 2 minutes to 2 minutes and 30 seconds for later use;
4. attaching: the upper, outsole and foxing were fitted, and the body of the fitted shoe was compacted by a press at 22 kg for 4 seconds, and then vulcanized at a temperature of 120 c for 70 minutes.
TABLE 5
Testing the tension of the shoe body: the outer side of the shoe body was cut out by one turn, and a sample test piece having a total length of 30 cm and a width of 1 cm was obtained, and the obtained shoe body was tested at a test speed of 100cm/min by taking out points (about 10 points in total) by pulling every 3 cm of the length of the sample of comparative example and example, and the test results are shown in tables 6 and 7. As is apparent from tables 6 and 7, the shoe body of example 2 using the multifunctional primer of the present invention exhibited better adhesion than that of comparative example 3 regardless of the adhesion between the upper and foxing or between the outsole and foxing. The multifunctional treating agent and the bonding method can be widely applied to bonding between different shoe materials, and the bonding of the shoe materials made of different materials shows good adhesion even exceeding that of the traditional treating agent, vulcanizing adhesive and bonding method.
TABLE 6
TABLE 7
Claims (16)
1. A method of subsequent fitting for vulcanized shoes, comprising providing a pharmaceutical treatment to a surface to be fitted of one or more of the shoe materials to be fitted prior to the fitting step, wherein the pharmaceutical treatment comprises one of a treating agent and an adhesive, and wherein the pharmaceutical-treated surface to be fitted does not simultaneously contain a treating agent and an adhesive thereon.
2. The method of claim 1 followed by applying, comprising the steps of:
(a) providing the pharmaceutical treatment on a first surface of a first shoe material, wherein the pharmaceutical treatment comprises a treatment agent;
(b) coating a treating agent or an adhesive on the first surface of the second shoe material; and
(c) directly attaching the first surface of the first shoe material to the first surface of the second shoe material.
3. The method of claim 2, wherein the number of layers of the treatment agent and the adhesive applied on the first surface of the first shoe material and the first surface of the second shoe material together does not exceed three.
4. The method of claim 2, wherein the adhesive is vulcanized rubber.
5. The method of claim 2, wherein the first shoe material is a rubber-like material that is uncured or cured semi-finished, and the second shoe material is a non-rubber material.
6. The method of next fitting according to claim 2, wherein the first shoe material is a green rubber foxing and the second shoe material is an upper or a sole.
7. The method of next pasting according to any one of claims 1 to 6, wherein the treatment agent comprises: rubber, tackifying resin and hydrocarbon solvent, wherein the solid content in the treating agent is 5-15 wt%.
8. The method of claim 7, wherein the components of the treatment agent other than the hydrocarbon solvent have the following ratios:
synthesizing rubber: 10 to 20 parts by weight; and
tackifying resin: 1 to 10 parts by weight.
9. A multifunctional primer, comprising: rubber, tackifying resin and hydrocarbon solvent, wherein the solid content in the multifunctional treating agent is 5-15 wt%.
10. The multifunctional primer according to claim 9, wherein the components other than the hydrocarbon solvent in the multifunctional primer have the following ratios: rubber: 10 to 20 parts by weight; and tackifying resin: 1 to 10 parts by weight.
11. The multifunctional primer according to claim 9 or 10, wherein said rubber is selected from the group consisting of natural rubber, synthetic rubber, modified natural rubber and combinations thereof, and said tackifying resin is selected from the group consisting of petroleum resin, terpene phenolic or phenolic modified resin, rosin modified resin and combinations thereof.
12. The multifunctional primer of claim 9 or 10, wherein the multifunctional primer further comprises one or more of a zinc compound, a saturated fatty acid having a carbon number of 12 to 24, a vulcanizing agent, and a vulcanization accelerator, wherein the zinc compound is selected from the group consisting of zinc oxide, zinc carbonate, zinc sulfate, zinc stearate, and combinations thereof, wherein the saturated fatty acid having a carbon number of 12 to 24 is selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and combinations thereof, wherein the vulcanizing agent is selected from the group consisting of sulfur, organic peroxides, polysulfide polymers, sulfur monoxide, and combinations thereof, and wherein the vulcanization accelerator is selected from the group consisting of benzothiazyl-2-Cyclohexylsulfenamide (CBS), zinc dibutyldithiocarbamate (BZ), Diphenylguanidine (DPG), 2-Mercaptobenzothiazole (MBT), and combinations thereof, Zinc dibenzyl dithiocarbamate (ZBEC) and combinations thereof.
13. The multifunctional primer according to claim 9 or 10, wherein said hydrocarbon solvent is selected from the group consisting of benzene solvents, ketone solvents, alkane solvents, and combinations thereof.
14. The multifunctional primer according to claim 9 or 10, further comprising 1 to 8 wt% of a hardener based on the total weight of the multifunctional primer.
15. The multifunctional primer according to claim 9 or 10, wherein the multifunctional primer is usable in the subsequent pasting method according to any one of claims 1 to 8.
16. Use of the multifunctional primer according to any one of claims 9 to 15 as an adhesive.
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| CN109401675A (en) * | 2018-10-31 | 2019-03-01 | 际华三五三七制鞋有限责任公司 | Suede type cow split skin hot vulcanized rubber boots water based adhesive system and its shoemaking technique for applying |
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| CN104789170A (en) * | 2015-04-09 | 2015-07-22 | 茂泰(福建)鞋材有限公司 | Shoe material bonding film, preparation method of film as well as method for using film for bonding soles |
| CN106318270A (en) * | 2016-08-24 | 2017-01-11 | 际华三五三七制鞋有限责任公司 | Black adhesive paste for waterproof boots, preparing method and application thereof |
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