TWI791989B - Bonding method in adhesive technology for vulcanization shoes, multi-function treatment agent used therein, and use of the multi-function treatment agent - Google Patents

Abstract

The subject application is related to a bonding method in adhesive technology for vulcanization shoes, comprising applying either a treatment agent or a binding agent on a binding surface of one or more shoe's components that are to be binded before the components are attached together, wherein the treatment agent does not overlap with the binding agent on the same surface, and the other way around. The subject application further relates to a multi-function treatment agent that is suitable for the bonding method and relates to a use of the multi-function treatment agent as an adhesive.

Description

A bonding method for vulcanized shoes, a multifunctional treatment agent for it, and uses of the multifunctional treatment agent

The invention relates to a bonding method in the shoe-making process, which can effectively simplify the steps of the bonding method in the traditional shoe-making process, and is especially suitable for the shoe-making process of vulcanized shoes. The present invention also relates to a multifunctional treatment agent that can be used in the vulcanized shoe bonding method, which can treat and/or modify shoe materials such as shoe soles or skirts, and can effectively bond these shoe materials.

The traditional vulcanized shoe manufacturing process involves shoe materials made of different materials such as uppers, soles, and raw rubber surrounds, as well as the processing and combination of these shoe materials. Multiple chemical treatments are required to achieve the desired bonding effect. The chemical treatment includes cleaning the surface of the shoe material with a cleaning agent, coating the surface of the shoe material with a treatment agent, coating the surface of the shoe material with an adhesive or glue, and other chemicals involved. However, this multi-step bonding method not only increases the cost, but also seriously reduces the efficiency of shoemaking. However, since the material and shape of the shoe material vary greatly, and there is a necessary sequence or occasional mutual exclusion between the effects to be achieved in each step or the medicaments used, it is generally considered in the art that the multi-step bonding method difficult to simplify further. For example, because the materials of the shoe materials are usually very different, the surface polarities of the shoe materials are not only different from each other, but also often very different from the conventional glue polarity, so the shoe materials cannot be directly bonded to each other; in addition, During manufacturing or storage, each shoe material of a shoe may be covered with impurities or coated with anti-adhesive chemicals to help preserve it, so it usually must be further cleaned before fitting. In the field of shoemaking, in addition to the function of modification, the treatment agent can also have the cleaning function of removing impurities and chemicals on the surface of the shoe material to be bonded, so as to avoid affecting the effect of subsequent shoe material bonding. Therefore, in the traditional vulcanized shoe manufacturing process, it is necessary to treat the surface of the shoe material with a treatment agent first, and then apply glue after the treatment agent dries before assembling and then laminating. For example, if you want to cover raw rubber surrounds and then attach them to the upper and the shoe body, you need to use a treatment agent to treat and modify the surface polarity of the rubber material, then dry or dry the treated surrounds, and then place them on the The surfaces to be bonded, such as shoe uppers, shoe bodies, and raw rubber surrounds, are coated with vulcanized rubber and then continue with the subsequent manufacturing process. In the assembly line production process, more than two people are required to complete the traditional modification to lamination steps to complete the operation of an assembly line, which is extremely labor-intensive.

Since the treatment agent has the effect of modifying the quality, when the treatment agent is mixed with the glue, it will cause the glue to delaminate and affect the stability of the glue. The nature of the agent, resulting in poor treatment effect of the treatment agent. Therefore, in the traditional operation in this field, the treatment agent must be operated separately from the glue. In addition, there are various types of treatment agents and glues on the market, but not all of them have good compatibility. If the compatibility of treatment agents and glues is not good, the bonding effect will be affected or even deteriorated. In addition to matching the material and processing purpose of each vulcanized shoe material, the selection must also consider the type of glue to be applied later. In addition, different treatment agents and glues will also have different additional processing requirements, which not only increases the cost of shoemaking but also reduces production efficiency. For example, some treatment agents and vulcanized glue require an activation step, and if If the glue is water-based, it is necessary to add an oven and other equipment for additional drying steps in the shoemaking step.

However, the multi-step bonding method of superimposed coating of treatment agent and glue on the shoe material and the lack of compatibility between the treatment agent and glue often lead to failure or instability of shoe material bonding, and this problem also leads to waste of materials in the manufacturing process And the additional cost required to reduce the production yield. At the same time, there are still many improvements in the field of conventional vulcanized rubber used for vulcanized shoes. For example, it is desired to reduce or avoid additional activation and drying steps, or to improve the production and emission of volatilized solvent-based vulcanized glue. Volatile Organic Compounds (Volatile Organic Compounds, hereinafter referred to as VOCs) cause problems affecting the environment and human health.

In view of this, there is still a need to develop a bonding method for vulcanized shoes that can solve the above problems, simplify the shoemaking process, be environmentally friendly and effectively reduce production costs. On the other hand, it is also necessary to develop a treatment agent that has a wide range of applications, is suitable for a variety of materials, is compatible with various types of glue, is environmentally friendly, and can effectively reduce production costs, so as to meet the needs of today's market.

On this basis, one of the goals of the present invention is to improve the bonding method in the vulcanized shoe manufacturing process, to simplify the operations or steps required for bonding, further reduce manpower, production cost consumption, improve production efficiency, and reduce VOC and other harmful substances are discharged and correspondingly generated pollution, and while simplifying the bonding method, good adhesion can still be maintained.

Another object of the present invention is to develop a novel treatment agent, which can be used in the simplified bonding method of vulcanized shoes in this case, and has good properties, and is suitable for modifying and treating the surface of different materials of vulcanized shoes, such as rubber, Foam materials, etc., and can partially or even completely replace adhesives (such as: vulcanized rubber) and can be attached to vulcanized shoe materials to reduce or even avoid the use of adhesives.

According to the above objectives, the present invention provides a method for bonding vulcanized shoes, which includes providing chemical treatment to the surface to be bonded of one or more shoe materials to be bonded before the bonding step, wherein the chemical treatment Contains one of a treatment agent and an adhesive, and the surface to be bonded that is treated with the agent does not contain the treatment agent and the adhesive at the same time. The bonding method for vulcanized shoes provided by the present invention, before the bonding step, one or more of the shoe materials to be bonded is coated with one of the treatment agent and the adhesive on the surface to be bonded, Wherein the treatment agent and the adhesive are coated on the surface to be pasted without overlapping each other.

When manufacturing vulcanized shoes, using the bonding method of the present invention can reduce the steps of coating treatment agents, adhesives (such as: vulcanized glue) and/or other agents on shoe materials, that is, reduce treatment agents, adhesives and Coatings of/or other agents, specifically coatings that reduce treatment agents and/or adhesives, can also reduce the processing steps for these coatings, such as activation, drying, etc., thus simplifying the operation mode , Reduced manpower requirements, shortened processing time, and reduced costs. At the same time, due to the reduction in the use of chemicals, it can greatly reduce the discharge of VOC, residues or by-products in the process, which meets the requirements of environmental friendliness.

According to the above objectives, the present invention further provides a multifunctional treatment agent, which includes rubber, tackifying resin and hydrocarbon solvent, wherein the solid content of the multifunctional treatment agent is 5% to 15% by weight.

In the multifunctional treatment agent of the present invention, in addition to the hydrocarbon solvent, it contains 10 to 20 parts by weight of rubber and 1 to 10 parts by weight of tackifying resin.

The present invention further provides an application of the multi-functional treatment agent of the present invention, which can be used as an adhesive in the bonding procedure of vulcanized shoes of the present invention. Due to the unique viscosity of the multi-functional treatment agent of the present invention, while modifying the surface polarity of the vulcanized shoe material, it can directly adhere the modified shoe material to other shoe materials of different materials. When manufacturing vulcanized shoes, using the multi-functional treatment agent of the present invention can make the modified shoe material no need to further apply adhesives (such as: vulcanized glue), so it has the advantages of simplified operation, reduced manpower requirements, and reduced processing time. Advantages such as shortening and cost reduction, at the same time, due to the reduction of the use of adhesives, VOC emissions in the process can be greatly reduced, which meets the requirements of environmental friendliness.

Herein, unless otherwise specified, the singular forms "a" and "the" also include their plural forms. The purpose of any and all examples and illustrative language ("such as" and "such as") herein is only to further highlight the present invention, not to limit the scope of the present invention, and the language in this case specification should not be regarded as implying any The claimed methods and conditions may constitute essential features in the practice of the invention.

As used herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (eg 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

Unless otherwise stated, as stated herein, all numbers are deemed to be modified by the term "about".

The term "preferably" in the embodiments of the present invention means that certain benefits may be provided under certain circumstances. However, other embodiments may also 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 present invention.

In this article, "shoe material" refers to the various components of the shoe, such as midsole, outsole, upper, skirt and other parts.

In this article, "pharmaceutical treatment" refers to the treatment step of coating the surface of the shoe material to be bonded with a chemical agent before different or the same shoe materials are bonded in the bonding method in the field of shoemaking; "Pharmaceuticals" include chemicals such as cleaning agents, surface modifiers, treatment agents, adhesives (including glues), etc. These chemical treatments may directly or indirectly affect, strengthen or provide the adhesion effect.

Herein, "not including the treatment agent and the adhesive at the same time" is not intended to limit the point of time when the treatment agent and the adhesive are applied, but indicates that both the treatment agent and the adhesive do not exist together. Therefore, "the surface to be bonded does not contain a treatment agent and an adhesive at the same time" means that on the same surface to be bonded, before it is bonded to another surface to be bonded, there is no coating of both the treatment agent and the adhesive. The state of covering the adhesive, and vice versa.

In detail, the bonding method for vulcanized shoes of the present invention reduces the step of applying at least one agent in the conventional bonding process of shoe materials. Furthermore, the bonding method for vulcanized shoes of the present invention reduces the need for at least one treatment agent or adhesive coating step and its corresponding drying, activation and other processes in the conventional shoe material bonding procedure; Furthermore, the bonding method for vulcanized shoes of the present invention reduces the steps of applying at least one treatment agent or adhesive and the corresponding drying and activation steps on one or more surfaces to be bonded. In the bonding method for vulcanized shoes of the present invention, prior to the bonding step, one or more surfaces of the shoe materials to be bonded are provided with a chemical treatment, wherein the chemical treatment includes a treatment agent or Adhesive, and wherein when the medicament is treated as a treatment agent, no adhesive is applied on the surface to be pasted treated by the medicament, and wherein when the medicament is treated as an adhesive, no adhesive is applied on the surface to be pasted treated by the medicament No treatment agent is applied to the joint surface.

In detail, the bonding method for vulcanized shoes of the present invention removes at least one agent coating step in the conventional shoe material bonding process. Furthermore, the adhesive bonding method for vulcanized shoes of the present invention removes at least one coating step of treatment agent or adhesive and its corresponding drying, activation and other processes in the conventional bonding process of shoe materials; Still further, the bonding method for vulcanized shoes of the present invention removes at least one treatment agent or adhesive coating step and its corresponding drying, activation and other processes on one or more surfaces to be bonded. In the adhesive bonding method for vulcanized shoes of the present invention, it includes, before the bonding step, one or more of the surfaces to be bonded of one or more shoe materials to be bonded is coated with one of the treatment agent and the adhesive or, and wherein the treatment agent and the adhesive are not overlapped and coated on the same surface to be bonded. The aforementioned "non-overlapping coating" means that the treatment agent and the adhesive do not exist on a single surface in any form, proportion or sequence.

In detail, the present invention finds that it is not necessary to coat both the treatment agent and the adhesive on all surfaces of the shoe materials to be bonded to achieve a satisfactory bonding effect. The bonding method of vulcanized shoes according to the present invention finds that even if only one of the treatment agent and the adhesive is coated on the surface of a shoe material to be bonded, the shoe material can be combined with other shoes to be bonded. After the materials are bonded, they can still show good adhesion; the present invention further finds that even if only one layer of treatment agent is applied on the surface of a shoe material to be bonded, the shoe material can be combined with other shoe materials to be bonded. Good adhesion can still be performed after bonding. The present invention further finds that even if only a treatment agent is applied on the surface of the bar to be bonded and no adhesive is applied, the bar can still exhibit good adhesion after being bonded to other shoe materials to be bonded; the present invention The invention further found that even if only one layer of treatment agent and no adhesive agent is applied on the surface of the apron to be bonded, the apron can still exhibit good adhesiveness after being bonded with other shoe materials to be bonded.

According to the bonding method for vulcanized shoes of the present invention, those with ordinary knowledge in the technical field of the present invention can determine the bonding effect of any shoe material to be bonded according to the desired bonding effect or corresponding processing steps. On the combined surface, the number of coating layers of any kind of agent, such as one layer, two layers, three layers, preferably one layer. According to the bonding method for vulcanized shoes of the present invention, after the shoe materials to be bonded are bonded, the total number of coating layers of the treatment agent and the adhesive contained between the two should not exceed five layers at most, which is higher than Preferably no more than three layers.

A method for bonding vulcanized shoes according to the present invention, which includes providing the chemical treatment on the first surface of the first shoe material, wherein the chemical treatment includes a treatment agent; coating the treatment agent on the first surface of the second shoe material or an adhesive; and make the first surface of the first shoe material and the first surface of the second shoe material directly bonded.

A bonding method for vulcanized shoes of the present invention, which comprises coating the multifunctional treatment agent of the present invention on the first surface of the first shoe material, and coating the multifunctional treatment agent of the present invention on the first surface of the second shoe material an agent or an adhesive; and directly bonding the first surface of the first shoe material to the first surface of the second shoe material.

According to the bonding method for vulcanized shoes of the present invention, the total 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 does not exceed five at most. layers, preferably no more than three layers.

In the bonding method for vulcanized shoes of the present invention, the adhesive is vulcanized glue.

In the bonding method for vulcanized shoes of the present invention, depending on the type of shoe material and the requirements of the manufacturing process, the second shoe material can be coated with only a single layer of the multifunctional treatment agent of the present invention or a single layer of vulcanized rubber. , or the vulcanizate can be coated after coating the multifunctional treatment agent of the present invention.

In the bonding method for vulcanized shoes of the present invention, the first shoe material and the second shoe material may be the same or different shoe materials, for example, but not limited to the following shoe materials: shoe midsole, shoe outsole , shoe uppers and skirts; and the first shoe material and the second shoe material may have different or the same materials, and the materials include unvulcanized rubber-like materials, vulcanized rubber-like materials, and vulcanized semi-finished products Rubber materials, non-rubber materials, synthetic fiber materials and natural fiber materials. Materials that can form soles usually include but are not limited to vulcanized rubber materials and non-rubber materials; materials that can form uppers usually 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 materials and polyester fiber fabrics; and the materials forming the apron usually include but are not limited to unvulcanized rubber and vulcanized rubber, such as: raw rubber and semi-raw rubber with incomplete vulcanization Glue.

In the adhesive bonding method for vulcanized shoes of the present invention, in order to further enhance the adhesive bonding effect, it may include coating the surface of the shoe material to be bonded with a treatment agent or an adhesive, and then treating the surface. Other processing steps, such as drying, wherein the drying step can adopt various known drying methods, such as natural drying, oven heating drying, etc.; or such as activation, wherein the activation step can adopt various known activation methods, such as oven heating activation, light activation wait. For example, if the surface of a certain shoe material to be bonded is coated with vulcanized glue, it can be placed in an oven to activate the glue. In addition, the bonding method for vulcanized shoes of the present invention may also include a step of further processing the bonded shoe material after the direct bonding step, such as, but not limited to, drying the bonded shoe material, Compacting the laminated shoe material, and repeated lamination, etc., the above further processing steps can be selected according to the type of shoe material and the requirements of the manufacturing process, and the order of operation can be determined according to the needs. After the shoe material is pasted by the bonding method for vulcanized shoes of the present invention, it can be directly vulcanized.

In the adhesive bonding method for vulcanized shoes of the present invention, in order to further enhance the adhesive bonding effect, the shoe material (especially the upper and the sole) can be coated with a treatment agent or adhesive (for example: vulcanized glue). ) for treatment, which includes, but is not limited to: cleaning, drying, grinding, polishing and reinforcement. The cleaning treatment can be any known cleaning method, such as washing, dust removal and the like. The drying process can be any known drying method, such as drying, air drying and the like. The grinding or polishing treatment can be any known grinding or polishing method, such as using sandpaper, grinder, etc., to make the surface of the shoe material reach the desired roughness or smoothness. The reinforcing treatment can be any known reinforcing method, such as coating a reinforcing agent, fixing a reinforcing component, and the like. For example, the raw rubber surround can be bonded to the reinforced upper or sole according to the bonding method of the present invention.

The components contained in the multifunctional treatment agent of the present invention can make the treatment agent viscous without affecting the original modifying function, so it can partially or even completely replace the use of vulcanized rubber in the vulcanized shoe manufacturing process. In addition, the polarity of the multifunctional treatment agent of the present invention is between that of conventional shoe materials (such as cotton or polyester fabric) and rubber, so it can take into account the interface compatibility between different materials in the bonding and vulcanization procedures , and therefore can be compatible with more types of adhesives (eg: vulcanized glue).

In the multifunctional treatment agent of the present invention, except the hydrocarbon solvent, the content of rubber is about 10 to about 20 parts by weight, preferably about 12 to about 18 parts by weight, more preferably about 14 to 16 parts by weight. Each of the above numerical values may include smaller ranges of any numerical value within that range or have any numerical value.

In the multifunctional treatment agent of the present invention, except the hydrocarbon solvent, the content of the tackifying resin is about 1 to about 10 parts by weight, preferably about 1 to about 7 parts by weight, more preferably about 2 to 6 parts by weight. Each of the above numerical values may include smaller ranges of any numerical value within that range or have any numerical value.

With the components of the multifunctional treatment agent of the present invention except the hydrocarbon solvent, carry out rubber kneading and kneading respectively with the above-mentioned appropriate proportioning ratio, and after being mixed uniformly, it becomes the semi-finished product of the multifunctional treatment agent of the present invention; the semi-finished product Soluble in an appropriate amount of hydrocarbon solvent, so that the proportion of solid content in the resulting composition is about 3% by weight to about 20% by weight, preferably about 5% by weight to about 15% by weight, more preferably about 7% by weight % to 12% by weight is the multifunctional treatment agent of the present invention. If the solid content is higher than 20% by weight, it will cause high viscosity and difficult to apply; if the solid content is lower than 3% by weight, it will affect the stickiness of the multi-functional treatment agent, reduce the initial bonding strength, and replace glue The function will be greatly reduced, which will have a bad impact on the subsequent bonding process.

The rubber suitable for the multifunctional treatment agent of the present invention can be any rubber known by those skilled in the art to which the present invention has adhesive properties, such as, but not limited to, natural rubber, synthetic rubber, modified natural rubber and its combination. Usable synthetic rubbers include neoprene, styrene-butadiene rubber, nitrile rubber, butyl rubber, natural rubber, polyurethane rubber and the like, preferably neoprene, styrene-butadiene rubber, natural rubber and modified natural rubber, More preferably, it is natural rubber or modified natural rubber.

Tackifying resins 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 the multifunctional treatment agent of the present invention can be any tackifying resin that has the property of prolonging the working time of glue known to those with ordinary knowledge in the technical field of the present invention, such as, but not limited to, petroleum resin, modified petroleum resin, etc. Resins, terpene phenolic or phenolic modified resins, rosins, modified rosin resins, and combinations thereof. Usable tackifying resins include petroleum resins, hydrogenated petroleum resins, alkylphenolic resins, rosins, modified rosin resins, and the like, preferably phenolic modified resins, C5 to C9 petroleum resins, and hydrogenated petroleum resins.

Hydrocarbon solvents suitable for the multifunctional treatment agent of the present invention include benzenes, ketones, alkanes or combinations thereof, preferably alkanes, ketones or combinations thereof, preferably alkanes with 5 to 10 carbon atoms , ketones with 3 to 8 carbon atoms or a combination thereof, more preferably butanone, methylcyclohexane or a combination thereof. The multifunctional treatment agent of the present invention may additionally contain other solvents to help clean, swell materials or dissolve solids, such as carbonates and acetates, such as ethyl acetate and butyl acetate.

The multifunctional treatment agent of the present invention preferably further includes a zinc compound. The zinc compound has the functions of promoting rubber vulcanization, activation, reinforcing treatment agent, etc., and can also improve the heat resistance of the rubber compound. The zinc compound suitable for the multifunctional treatment agent 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 content of the added zinc compound is about 0.1 to about 1 part by weight, preferably about 0.2 to about 0.8 parts by weight, more preferably about 0.5 to about 0.8 parts by weight. Each of the above numerical values may include smaller ranges of any numerical value within that range or have any numerical value.

The multifunctional treatment agent of the present invention preferably further comprises saturated fatty acids, especially saturated fatty acids with 12 to 24 carbon atoms. Saturated fatty acids with 12 to 24 carbons have the property of vulcanization activity buffer, which is helpful for the vulcanization activation of the treatment agent. The saturated fatty acids with 12 to 24 carbons suitable for the multifunctional treatment agent of the present invention include lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, pearlescent fatty acid, stearic acid, nonadecanoic acid, peanut Acid, behenic acid, behenic acid, eicosic acid, lignoceric acid or combinations thereof, preferably lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid or combinations thereof, more Preferably it is myristic acid, palmitic acid, stearic acid or a combination thereof. The content of the added saturated fatty acid is, except the hydrocarbon solvent, the total weight of the multifunctional treatment agent of the present invention 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 about 1 part by weight 0.6 parts by weight. Each of the above numerical values may include smaller ranges of any numerical value within that range or have any numerical value.

The multifunctional treatment agent of the present invention preferably further includes a vulcanizing agent and/or a vulcanization accelerator as appropriate. Due to the difference in the material properties of the shoe materials to be bonded, those skilled in the art of the present invention can choose to add vulcanizing agents and/or vulcanization accelerators to the multifunctional treatment agent of the present invention to further enhance the bonding effect. The vulcanizing agent suitable for the multifunctional treatment agent of the present invention can be any vulcanizing agent known to have cross-linked rubber properties in the technical field to which the present invention belongs, such as, but not limited to, sulfur, organic peroxide, polysulfide Polymer, sulfur monoxide, etc. and combinations thereof, preferably sulfur and tetramethylthiuram disulfide (TMTD). The content of the vulcanizing agent added is, in addition to the hydrocarbon solvent, the total weight of the multifunctional treatment agent of the present invention is 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 about 2 parts by weight 1.2 parts by weight. Each of the above numerical values may include smaller ranges of any numerical value within that range or have any numerical value.

The vulcanization accelerator suitable for the multifunctional treatment agent of the present invention can be any vulcanization accelerator known by those skilled in the art to which the present invention has the property of regulating the vulcanization rate, such as, but not limited to, thiuram compounds, amine salts Compounds, diphenylguanidines, sulfenamides, thiazoles, zinc phosphate compounds, and combinations thereof. Vulcanization accelerators that can be used include benzothiazolyl-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 content of the added vulcanization accelerator is, except the hydrocarbon solvent, the total weight of the multifunctional treatment agent of the present invention is about 0.1 to about 2 parts by weight, preferably about 0.1 to about 1.0 parts by weight, more preferably about 0.2 to 0.5 parts by weight. Each of the above numerical values may include smaller ranges of any numerical value within that range or have any numerical value.

When the multi-functional treatment agent of the present invention is used, additional hardening agent may be added to achieve better adhesive properties. Suitable hardeners include polyisocyanates or salts thereof and polyamide resins. The added hardener is 1 to 8% by weight based on the total weight of the multifunctional treatment agent, preferably 2.5 to 7% by weight, more preferably 3.5 to 5.5% by weight.

The multifunctional treatment agent of the present invention may further contain additives as required, such as but not limited to stabilizers, tackifiers, cleaning agents, and co-solvents. In the multifunctional treatment agent of the present invention, the additive accounts for about 1% to about 10% by weight of the total weight of the multifunctional treatment agent, preferably about 1.2% to about 1.5% by weight.

In addition to the effect and application of surface modification, the multi-functional treatment agent of the present invention can also have the effect of cleaning the surface; and because the multi-functional treatment agent of the present invention has a very good effect on conventional shoe materials, especially skirt materials Strong viscosity, so it is also used as an adhesive. And when used as an adhesive, the multifunctional treatment agent of the present invention can have the desired viscosity when directly coated on the substrate without additional activation process. The multifunctional treatment agent of the present invention has a polarity between general shoe materials and rubber, so it can be widely used in modification and/or cleaning of various shoe materials, especially apron materials, and with more types of materials Compatible with vulcanized rubber, so that the shoe material maintains a good and long-lasting adhesive effect. In addition, since the multifunctional treatment agent of the present invention is liquid, it has good extensibility and preservation, and it is easy to control the dosage, coating thickness and range during use, and can maintain good adhesion on the bonding surface. The coating thickness of the multifunctional treatment agent of the present invention can range from 0.3 mm to 0.1 mm, or even less than 0.1 mm, so it will not cause extra thickness on the bonding surface and affect the appearance or function of the shoe.

To sum up, the multifunctional treatment agent of the present invention containing specific components, and the application of the multifunctional treatment agent in the bonding process of vulcanized shoes can obtain excellent and stable and reliable adhesive strength. Compared with the traditional process, the use of the multi-functional treatment agent of the present invention can greatly reduce the use of adhesives, such as vulcanized glue, and reduce OVC emissions, which meets the needs of environmental protection, and can reduce the demand for manpower and reduce the use of materials, equipment and energy. , and the scope of application is wider, the operation is easier, and it can better meet the requirements of international brands for environmental protection and waste reduction.

Using the bonding method for vulcanized shoes of the present invention and the multi-functional treatment agent of the present invention can simplify the steps of the bonding method, reduce or avoid the use of adhesives (such as: vulcanized rubber) while still effectively maintaining It can even improve the strength of shoe material bonding. In the field of shoemaking, it is generally required that after the shoe upper and the skirt are glued together, the tension between the two needs to be greater than 3 kg/cm, which means that the adhesion between the shoe upper and the skirt must be greater than 3.0 kg/cm; and The adhesion between the outsole and the surrounding bar is required to be greater than 2.5 kg/cm. The multifunctional treatment agent of the present invention can provide an adhesive force of more than 3.0 kg/cm, preferably more than 4.0 kg/cm, more preferably more than 5.0 kg/cm between the shoe upper and the skirt; and can Provide an adhesive force of more than 3.0 kg/cm, preferably more than 4.0 kg/cm, and more preferably more than 5.0 kg/cm, between the outsole and the surround.

Simultaneously, because the bonding method for vulcanized shoes of the present invention and the multifunctional treatment agent of the present invention can effectively reduce the number of coating layers of the processing agent and the adhesive on the bonding surface of the shoe material, it can effectively reduce the The thickness of the adhesive layer after the combination of glue and treatment agent between the material bonding surfaces can not only avoid the occurrence of glue overflow when the shoe materials are bonded, but also benefit the appearance and weight of the shoes, speed up the production rate and reduce the production cost. It also contributes to the tightness between shoe materials.

The following examples illustrate the implementation of the present invention and illustrate the technical features of the present invention, but are not intended to limit the protection scope of the present invention. Any changes or equivalence arrangements that can be easily accomplished by those familiar with the technology fall within the scope of the present invention, and the scope of protection of the rights of the present invention should be based on the scope of the attached patent application. [ Example ] Embodiment 1 and Comparative Examples 1 and 2 A. Tensile test

Using a tensile machine (Gaotie Technology Co., Ltd.; GT-7010-D2E) to perform tensile tests on the shoe bodies or test pieces prepared in Comparative Examples 1 and 2 and Example 1 to illustrate the adhesive effect of the present invention. Use two clips to fix the two sides of the part to be tested, and pull it to both sides at a fixed test speed. When the bonding interface between the girdle and the upper, the girdle and the sole, and the bonding interface between the upper and the sole is peeled off, record The pull value. B. Test piece preparation and tensile test results

In the traditional vulcanized shoe bonding process, the shoe material treated with the treatment agent needs to be coated with a layer of vulcanized glue (as shown in Figure 1), but the multifunctional treatment agent of the present invention can provide sufficient adhesion, so There is no need to reapply vulcanizate (as illustrated in Figure 2). The tensile test of the test piece is hereby used to illustrate the effectiveness of the multi-functional treatment agent of the present invention in reducing the use of vulcanizate and having good adhesion compared with the traditional treatment agent on the market. In the test of the test piece, the raw rubber material is used as the first shoe material and the cotton fiber material is used as the second shoe material, that is, the surrounding bar is only coated with a single layer of commercially available or the treatment agent of the present invention, The shoe upper is coated with treatment agent and vulcanized rubber in sequence according to the traditional manufacturing process. Table 1 shows the commercially available products used to prepare the test pieces of Comparative Examples 1 and 2 and Example 1, the multifunctional treatment agent of the present invention and its code comparison. The components of the multifunctional treatment agent V277 of the present invention used in this case example include: natural rubber (15 parts), modified phenolic resin (5 parts), hydrogenated petroleum resin (4 parts), vulcanizing agent (0.3 parts), oxidation Zinc (0.5 parts), stearic acid (0.8 parts) and antioxidant (0.5 parts), after kneading the above components, add a hydrocarbon solvent (200 parts) as a solvent, wherein the hydrocarbon solvent contains methylcyclohexane 110 70 parts, 70 parts of butanone and 20 parts of ethyl acetate were dissolved and balanced to obtain the multifunctional treatment agent V277 of the present invention. Water-based treatment agent for shoe uppers Dadong Resin, 6001L Oily rubber treatment agent Nanbao Resin, P515 Oily rubber treatment agent Dadong Resin, 299A The multifunctional treatment agent of the present invention Dadong Resin, V277 Water-based vulcanized rubber for shoe uppers Dadong resin, 6127T hardener Dadong resin, 366S Table 1

Test piece preparation : firstly treat the surface of the upper to be bonded with 6001L treatment agent added with 5% by weight of 366S hardener, and then apply a single layer of 6127T, and then put the upper into an oven for activation at a temperature of 70°C Standby for 3 minutes; On the surface to be bonded, coat the commercially available or the treatment agent of the present invention as shown in Table 2 respectively; Fit the vamp and the surround; The press pressurizes with 5 kg for 5 seconds; vulcanize the bonded skirt and shoe upper for 70 minutes at a temperature of 120°C, and finally cut it into test pieces with a length of 7 cm and a width of 2 cm for tension test. fence fence treatment agent Comparative example 1 P515 Comparative example 2 299A Example 1 V277 Table 2

Tensile test of the test piece: test the prepared test piece at a test speed of 20 cm/min. The tensile test was repeated four times in Comparative Examples 1 and 2 and Example 1. The test results of the shoe upper-raw rubber surround are shown in Table 3 shown. It can be known from Table 3 that the test piece of the embodiment using the multifunctional treatment agent of the present invention has far better adhesion than the test piece of the comparative example using a commercially available traditional treatment agent, and the test piece of the embodiment can even withstand a higher The test piece of the comparative example reached 16 times the tensile force. This experiment shows that if the multifunctional treatment agent of the present invention is used, it can still have satisfactory or even excellent adhesion while reducing the use of vulcanizate. Audition Tensile test result (kg/cm) Comparative example 1 0.3 1.1 0.6 0.4 Comparative example 2 1.7 3.4 0.6 1.1 Example 1 4.8 5.2 5.1 4.6 Table 3 Example 2 and Comparative Example 3 C. shoe body preparation and tensile test results

This test shows that the multifunctional treatment agent of the present invention can be applied to different types of shoe materials, and all of them can maintain good adhesion. In the shoe body test, a complete shoe body (as shown in Figure 3) is made with a cotton fiber upper, a rubber outsole and a raw rubber surround, and the shoe body is subjected to a tensile test. The shoe bodies of Comparative Examples and Examples were prepared in the following ways.

Preparation of Comparative Example 3 : Table 4 below is the commercially available product and its code name used in the preparation of Comparative Example 3. The shoe body of Comparative Example 3 is made according to the following processes (as shown in Figure 4): Apply 299A treatment agent with 5% 299B vulcanization aid on the surface to be bonded, and after natural drying for 30 seconds to 1 minute, coat the treated surface with 5% V99NTB vulcanization aid and 5% 366S V99NTA vulcanized rubber with hardening agent, and then dry naturally for 30 seconds to 1 minute for later use; 2. Upper: Apply 6001L treatment agent with 5% 366S hardener on the surface of the upper to be bonded, put it in an oven for 60 After drying for 2 minutes to 2 minutes and 30 seconds at a temperature of ℃ to 65℃, apply 6127TC vulcanizate on the treated surface, and then place the upper in an oven to activate at a temperature of 55℃ to 60℃ for 2 minutes to 2 minutes and 30 seconds 3. Shoe outsole: Coat the surface of the shoe outsole to be bonded with 299A treatment agent added with 5% 299B sulfur additive, put it in an oven and dry it at a temperature of 55°C to 60°C for 2 minutes to 2 After 30 seconds, apply 6127TC vulcanizate on the treated surface, and then place the outsole of the shoe in an oven at a temperature of 55°C to 60°C for 2 minutes to 2 minutes and 30 seconds for later use; 4. Bonding: bonding For shoe uppers, shoe outsoles and skirts, the shoe body formed by lamination is compacted by a cross press with a pressure of 22 kg for 4 seconds, and then vulcanized at a temperature of 120°C for 70 minutes.

Preparation Example 2 : Table 5 below is the commercially available products used in Preparation Example 2 and their code comparison table. The shoe body of Example 2 is produced according to the following process (as shown in Figure 5): 1. Raw rubber surround: in Coat the V277 treatment agent of the present invention with 5% 632R hardener added on the surface of the bar to be bonded, and then dry naturally for 30 seconds to 1 minute for later use; 6001L treatment agent with 5% 366S hardener, place the coated shoe upper in an oven at a temperature of 60 to 65°C for 2 minutes to 2 minutes and 30 seconds, and then coat the treated surface with 6127T3 vulcanization 3. Outsole: apply 6299W treatment agent on the surface of the outsole to be bonded, and apply the After the coated shoe outsole is activated in an oven at a temperature of 55 to 60°C for 2 minutes to 2 minutes and 30 seconds, apply 6127T3 vulcanized rubber on the treated surface, and then put the shoe outsole into an oven for 55 Activation at a temperature of 60°C for 2 minutes to 2 minutes and 30 seconds for later use; 4. Fitting: Fitting the vamp, shoe outsole and surrounding strips, and the shoe body formed by the bonding is passed through a press at 22 kg for 4 seconds. Compact under pressure, then add sulfur at 120°C for 70 minutes. Water-based treatment agent for shoe uppers Dadong Resin, 6001L The multifunctional treatment agent of the present invention V277 Water-based vulcanized rubber for shoe uppers Dadong resin, 6127T3 Outsole rubber water-based treatment agent Dadong resin, 6299W hardener Dadong Resin, 632R hardener Dadong resin, 366S table 5

Shoe body tension test: cut the outer side of the shoe body in a circle, and obtain a sample test piece with a total length of 30 cm and a width of 1 cm. The samples of the comparative example and the embodiment are taken at every 3 cm in length (a total of 3 cm). Obtain about 10 point values), test the manufactured shoe body at a test speed of 100 cm/min, the test results are shown in Table 6 and Table 7. It can be seen from Table 6 and Table 7 that the shoe body of Example 2 using the multifunctional treatment agent of the present invention, no matter whether it is the bonding between the upper and the skirt or between the outsole and the skirt, the adhesion performance is the same. Better than using Comparative Example 3. This shows that the multi-functional treatment agent and adhesive bonding method of the present invention can be widely used in adhesive bonding between different shoe materials, and it performs well on shoe materials of different materials, even surpassing traditional processing agents and adhesive bonding methods. Adhesiveness of sulfur glue and bonding method. shoe body Tensile testing of shoe uppers and skirts 1 2 3 4 5 6 7 8 9 10 average Comparative example 3 3.6 3.1 2.6 3.6 3.4 3.3 3.1 3.6 3.9 3.6 3.4 Example 2 7.2 4.4 4.2 3.9 3.7 4.3 3.6 3.6 4.6 4.6 4.4 Table 6 shoe body Tensile test of shoe outsole and apron 1 2 3 4 5 6 7 8 9 10 average Comparative example 3 4.8 4.6 5.4 5.8 4.7 4.2 7.3 5.0 3.8 3.6 4.9 Example 2 6.1 10.3 5.6 5.3 5.6 4.9 4.5 4.8 3.7 3.8 5.5 Table 7

1: fence 2: Treatment agent 2': multifunctional treatment agent of the present invention 3: vulcanized glue 4: Vulcanized glue 5: Reinforcing agent for shoe upper 6: upper material 7: Fitting operation 12: Upper 14: Outsole 16: Wrap

In the following, the invention is further elucidated on the basis of an embodiment example schematically shown in the accompanying drawings, in which Fig. 1 illustrates the bonding procedure in the vulcanized shoe manufacturing process in the prior art; Fig. 2 illustrates the bonding procedure in the simplified vulcanized shoe manufacturing process using the multifunctional treatment agent of the present invention; Fig. 3 is the schematic diagram of the shoe body that the embodiment of this case makes; Figure 4 is a schematic flowchart of Comparative Example 3 of this case; and Fig. 5 is a schematic flowchart of Embodiment 2 of the present case.

1: fence

2': multifunctional treatment agent of the present invention

4: Vulcanized glue

5: Reinforcing agent for shoe upper

6: upper material

7: Fitting operation

Claims (14)

A bonding method for vulcanized shoes, which comprises, before the step of bonding, providing chemical treatment to the surface to be bonded of one or more shoe materials to be bonded, wherein the chemical treatment comprises a multifunctional treatment agent , the multifunctional treatment agent includes: rubber, tackifying resin and hydrocarbon solvent, wherein the solid content of the multifunctional treatment agent is 5% to 15% by weight, and wherein the surface to be bonded by the agent treatment is not at the same time Contains treatment agent and adhesive. The bonding method according to claim 1, which includes the following steps: (a) providing the chemical treatment on the first surface of the first shoe material; (b) coating the treatment agent on the first surface of the second shoe material or the adhesive; and (c) directly bonding the first surface of the first shoe material to the first surface of the second shoe material. The bonding method of claim 2, wherein the total number of layers of the treatment agent and the adhesive coated on the first surface of the first shoe material and the first surface of the second shoe material is not more than three floors. The bonding method of claim 2, wherein the adhesive is vulcanized glue. The bonding method of claim 2, wherein the material of the first shoe material is a rubber-like material without vulcanization or a vulcanized semi-finished product, and the material of the second shoe material is a non-rubber material. The following laminating method according to claim 2, wherein the first shoe material is a raw rubber apron, and the second shoe material is a shoe upper or a shoe sole. The bonding method according to claim 1, wherein the multifunctional treatment agent has the following proportions of components other than hydrocarbon solvents: synthetic rubber: 10 to 20 parts by weight; and tackifying resin: 1 to 10 parts by weight. A multifunctional treatment agent, which includes: rubber, tackifying resin and hydrocarbon solvent, wherein the solid content of the multifunctional treatment agent is 5% to 15% by weight. The multifunctional treatment agent according to claim 8, wherein the components in the multifunctional treatment agent except hydrocarbon solvents have the following proportions: rubber: 10 to 20 parts by weight; and tackifying resin: 1 to 10 parts by weight. Such as the multifunctional treatment agent of claim 8 or 9, wherein the rubber is selected from the group consisting of natural rubber, synthetic rubber, modified natural rubber and combinations thereof, and the tackifying resin is selected from petroleum resin, terpene phenolic or A group consisting of phenolic modified resin, rosin, rosin modified resin and combinations thereof. The multifunctional treatment agent as claimed in claim 8 or 9, wherein the multifunctional treatment agent can further include one or more of zinc compounds, saturated fatty acids with 12 to 24 carbons, vulcanizing agents and vulcanization accelerators 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 with 12 to 24 carbons is selected from lauric acid, myristic acid, The group consisting of 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 benzothiazolyl-2-cyclohexylsulfenamide (CBS), zinc dibutyldithiocarbamate (BZ), diphenylguanidine (DPG), 2-mercaptobenzene The group consisting of thiazole (MBT), zinc dibenzyldithiocarbamate (ZBEC) and combinations thereof. The multifunctional treatment agent according to claim 8 or 9, wherein the hydrocarbon solvent is selected from the group consisting of benzene solvents, ketone solvents, alkanes solvents and combinations thereof. The multifunctional treatment agent according to claim 8 or 9, further comprising 1 to 8% by weight of a hardener based on the total weight of the multifunctional treatment agent. A use of the multifunctional treatment agent according to any one of claims 8 to 13 as an adhesive.

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