Environment-friendly multifunctional treating agent and bonding method using same

Abstract

The invention relates to a novel environment-friendly multifunctional treating agent which comprises modified polyurethane resin, an acid agent, a chlorination donor compound, a surfactant and a carrier, and the carrier is water, an organic solvent or a combination thereof. The environment-friendly multifunctional treating agent disclosed by the invention can replace a treating agent and an adhesive in the traditional shoemaking field, so that the steps of a shoemaking procedure are simplified. The invention further relates to a method for bonding shoe materials using the environmentally friendly multifunctional treatment agent.

Description

Technical Field

[0001] The present invention relates to a novel environmentally friendly multifunctional treatment agent, which is particularly suitable for use in the field of shoemaking as a multifunctional treatment agent for shoe materials, and can replace the treatment agents and adhesives used in the field of traditional shoemaking, thereby simplifying the steps of the shoemaking process. The present invention also relates to a method for bonding shoe materials using the environmentally friendly multifunctional treatment agent. Background Art

[0002] The traditional shoemaking method involves shoe materials of different materials such as uppers, midsoles and outsoles, and procedures for processing and combining the shoe materials. In the process of bonding the shoe materials, the shoe materials usually need to be subjected to multiple chemical treatments to achieve the desired bonding effect. The chemical treatments include using a detergent to clean the surface of the shoe materials, applying a treatment agent to modify the surface of the shoe materials, applying an adhesive or glue on the surface of the shoe materials, and other treatments involving chemical agents. This multi-step bonding method not only increases costs, but also seriously reduces the efficiency of shoemaking. However, due to the great variation in the material and shape of the shoe materials, and the necessary order or occasional mutual exclusion between the effects to be achieved in each step or the chemicals used, it is generally believed in the art that the multi-step bonding method is difficult to be further simplified. For example, since the materials of various 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 polarity of conventional glues, so the shoe materials cannot be directly bonded to each other; in addition, during the manufacturing or storage of the shoe materials, the surface may be contaminated with impurities or coated with anti-stick agents or other chemicals that help preserve the shoes, so they usually need to be further cleaned before bonding.

[0003] In the field of shoemaking, the process of bonding shoe materials must first treat the surface of the shoe materials with a treatment agent, and then apply glue after the treatment agent is dried, so that the combination and bonding can be carried out. Taking the rubber outsole as an example, the prior art needs to first apply a treatment agent to change the properties of the surface of the rubber base material, so that the material surface is similar in polarity to the oily or water-based polyurethane glue, and then the subsequent gluing and bonding process can be completed. In addition to the role of modification, the treatment agent can also have a cleaning function to remove impurities and chemical agents on the surface of the shoe material to be bonded, thereby avoiding affecting the effect of subsequent shoe material bonding. In addition, if it is a vulcanized shoe process, after the glue agent is applied to the bonding surface of the shoe material and bonded, it must be subjected to a high temperature of 110 to 130 degrees and a sulfurization reaction of about 50 to 70 minutes, so that the agent (such as sulfurized glue) and the material of the shoe material complete a chemical reaction before the bonding process can be completed. When the process of vulcanized shoes does not go through the appropriate temperature and time conditions, the finished product usually does not have sufficient bonding performance. In the assembly line production process, the traditional follow-up process requires more than two people to complete the operation of an assembly line, which is extremely labor-intensive.

[0004] Since the treatment agent has a modification effect, when the treatment agent is mixed with an adhesive (such as glue), it will cause the glue to be delaminated and affect the stability of the glue; and because of the solubility characteristics of the adhesive component (such as polyurethane glue) in the adhesive, the effective ingredient or active ingredient in the treatment agent will be shielded, resulting in the reaction not meeting expectations, making the treatment effect worse. Therefore, in the traditional operation of 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 both of them have good compatibility. If the compatibility of the treatment agent and the glue is not good, it will affect or even deteriorate the bonding effect, so the selection of the treatment agent must be coordinated with the material properties of each shoe material, the purpose of treatment and the type of glue applied later. In addition, different treatment agents and glues will also produce different additional processing requirements, which not only increases the cost of shoemaking but also reduces production efficiency. For example, some treatment agents and adhesives require an activation step, and if the treatment agent or adhesive is water-based, it may be necessary to add equipment such as an oven in the shoemaking step for additional drying steps.

[0005] However, the multi-step method of applying a treatment agent and glue on the shoe material and then laminating the shoe material and the lack of compatibility between the treatment agent and the glue often cause the shoe material to fail to laminate or become unstable. This problem also causes material waste in the process and additional costs required to reduce production yield.

[0006] At the same time, there are still many demands for improvement in the shoemaking process in the current field, for example, it is expected to reduce or avoid additional activation and drying steps, or reduce volatile organic compounds (VOCs) to avoid problems affecting the environment and personnel health. Reducing VOC emissions involves adjusting the entire process of shoemaking, including using solvent-free treatment agents and adhesives, which will further increase the cost of the shoemaking process. Therefore, for the shoemaking industry, balancing environmental protection requirements and reasonable profits has become a major problem.

[0007] In view of this, there is still a need to develop a shoemaking method that can solve the above problems, simplify the bonding process, be environmentally friendly and effectively reduce production costs. On the other hand, it is also necessary to develop a treatment agent with a wide range of applications, suitable for a variety of materials, compatible with various types of glue, environmentally friendly and effectively reduce production costs to meet current market needs. Summary of the invention

[0008] On this basis, one of the objectives of the present invention is to provide a multifunctional treatment agent that can provide both modification and adhesion functions without sacrificing or reducing the effectiveness of any of its functions and has good properties, so that the product maintains good adhesion and storage stability. At the same time, it can flexibly adjust the balance between cost control and environmental protection requirements in response to different product and production line requirements.

[0009] Another object of the present invention is to simplify the operations or steps required for bonding shoe materials in the shoe manufacturing method, and further reduce manpower and production cost consumption and improve production efficiency.

[0010] According to the above objectives, the present invention provides a novel environmentally friendly multifunctional treating agent, which includes 5.0 to 40.0 parts by weight of a modified polyurethane resin, 0.4 to 4.0 parts by weight of a chlorine donor compound, 0.05 to 1.0 parts by weight of an acid agent, 0.01 to 3.0 parts by weight of a surfactant, and 60 to 95 parts by weight of a carrier, wherein the carrier is water, an organic solvent or a combination thereof.

[0011] The multifunctional treatment agent of the present invention can be divided into water-based, semi-aqueous and solvent-based according to the content of water and organic solvent in the carrier. The carrier in the water-based multifunctional treatment agent only includes water; the carrier in the semi-aqueous multifunctional treatment agent includes 5 to 55 parts by weight of water and 5 to 90 parts by weight of organic solvent; the carrier in the solvent-based multifunctional treatment agent only includes organic solvent.

[0012] The multifunctional treatment agent of the present invention can provide the functions of modification and adhesion at the same time. It can replace and serve as the treatment agent and / or adhesive in the process of shoe material bonding, and can especially replace the treatment agent and / or adhesive of rubber shoe materials. The use of the multifunctional treatment agent of the present invention allows the modified shoe materials to be directly bonded with other shoe materials of different materials without further coating with adhesives (such as glue). Since the multifunctional treatment agent of the present invention can be divided into aqueous, semi-aqueous, solvent-based and other forms according to different carriers, it can be widely applied to different materials. Based on the above characteristics, the multifunctional treatment agent of the present invention has the advantages of simplified operation, reduced manpower requirements, shortened processing time and reduced costs. At the same time, due to the reduction in the use of adhesives, the emission of VOCs in the process can be greatly reduced, meeting the requirements of environmental friendliness.

[0013] According to the above objectives, the present invention further provides a method for bonding a shoe material, which comprises coating the multifunctional treatment agent of the present invention on a bonding surface of the shoe material, and directly bonding the coated bonding surface of the shoe material to a bonding surface of another shoe material. In one aspect of the method for bonding a shoe material of the present invention, the bonding surface of the shoe material may not include other treatment agents or adhesives other than the multifunctional treatment agent of the present invention.

[0014] When the shoe material bonding process is performed, the bonding method of the present invention can reduce the steps of applying the treatment agent, adhesive and / or other agents to the shoe material, that is, reduce the coating of the treatment agent, adhesive and / or other agents, specifically reduce the coating of the treatment agent and / or adhesive, and can also reduce the processing steps for the coating, such as activation, drying and other steps, so that it has the advantages of simplified operation, reduced gluing steps, reduced manpower requirements, improved production efficiency and shortened processing time, and ultimately can reduce production costs. At the same time, due to the reduction in the use of chemicals (such as glue), the emission of VOC, residues or by-products can be greatly reduced, meeting the requirements of environmental friendliness. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In the following, the invention is further explained based on an embodiment example schematically shown in the drawings. Figure 1A and Figure 1B The following is a comparison between the prior art and the shoemaking and laminating process using the multifunctional treatment agent of the present invention. Figure 1A The following is an example of the bonding process of the shoemaking method in the prior art. Figure 1B The simplified shoe manufacturing and subsequent laminating process using the multifunctional treating agent of the present invention is illustrated (taking rubber outsole as an example). DETAILED DESCRIPTION

[0016] In this document, unless otherwise specified, the singular forms "a", "an" and "the" also include the plural forms. Any and all embodiments and exemplary terms ("for example" and "such as") herein are intended only to highlight the present invention and are not intended to limit the scope of the present invention. The terms in this specification should not be considered to imply that any unrequested methods and conditions may constitute necessary features for implementing the present invention.

[0017]

[0013] 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.).

[0018] Unless otherwise indicated, all numbers as used herein should be deemed to be modified by the term "about".

[0019] The term "preferred" in the embodiments of the present invention indicates that certain benefits may be provided in certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. In addition, the reference to one or more preferred embodiments does not mean that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the present invention.

[0020] In this article, "shoe materials" refer to the commonly known components of shoes, such as midsoles, outsoles, uppers, and welts.

[0021] In this article, "chemical treatment" refers to the step of applying a chemical to the surface of the shoe material to be bonded before bonding different or identical shoe materials in the bonding method in the shoemaking field; the "chemical" includes chemicals such as cleaning agents, treatment agents, adhesives (including glue), etc. Such chemical treatment may directly or indirectly affect, enhance or provide bonding effects.

[0022] In this article, "pretreatment" or "pre-treatment" refers to all necessary or optional treatments of the shoe material before the chemical treatment, including but not limited to cleaning, roughening, polishing, washing, drying, shearing and reinforcement. The cleaning treatment can be any conventional cleaning method, such as washing, dust removal, etc. The drying treatment can be any conventional drying method, such as baking, air drying, etc. The roughening or polishing treatment can be any conventional roughening or polishing method, such as using sandpaper, grinder, etc., to make the surface of the shoe material reach the desired roughness or smoothness. The reinforcement treatment can be any conventional reinforcement method, such as coating a reinforcing agent, fixing a reinforcing component, etc. The purpose of the pretreatment includes but is not limited to further enhancing the subsequent bonding effect.

[0023] In this article, "shoe materials to be bonded" refers to shoe materials that have been prepared and can be treated with chemicals or bonded with other shoe materials. The shoe materials to be bonded can be pre-treated or non-pre-treated shoe materials.

[0024] The multifunctional treatment agent of the present invention can simultaneously meet the requirements of shoe material modification and bonding of two shoe materials, thereby reducing the steps of applying reagents in the traditional shoe material bonding process, so that the traditional multi-step process involving at least coating of treatment agents, adhesives, etc., is simplified to only coating the multifunctional treatment agent of the present invention, and can meet the performance requirements for shoe material modification and adhesion strength.

[0025] In general, the shoe material bonding process in shoemaking requires the application of a treatment agent to change the properties of the shoe material surface, so that the material surface is close in polarity to the oily or water-based glue, before the subsequent gluing and laminating process can be completed. In addition, it is believed in the prior art that if the active ingredient in the treatment agent is added to an adhesive (e.g., a glue comprising a polyurethane resin), the adhesive component that provides viscosity and the active ingredient in the treatment agent will interfere with each other's functions and inhibit the performance of both. For example, the solubility characteristics (or dispersibility) of the adhesive will shield the active ingredient in the treatment agent, causing the active ingredient in the treatment agent to be difficult to act and unable to perform its function, and unable to achieve effective modification, and affecting the strength and stability of the shoe material bonding. Without being limited to theory, it is believed that the combination of the treatment agent and the adhesive will affect the concentration or amount of the active ingredient in the treatment agent on the surface of the shoe material, and indirectly affect the reaction of the active ingredient in the treatment agent on the surface of the shoe material, thereby causing the reaction to be inconsistent with expectations, resulting in subsequent abnormal bonding. However, if the ratio of the active ingredient of the treatment agent to the adhesive in the composition is increased, the adhesiveness of the bonding is significantly weakened due to the reduction of the adhesive ratio, making it difficult to complete the subsequent bonding operation, or the adhesive is precipitated due to excessive active ingredients (such as acid agents, etc.) and cannot be used, which is difficult to meet market needs. Therefore, it is generally believed in the technical field to which the present invention belongs that it is impossible to combine the treatment agent and the adhesive into a single agent, such as combining the active ingredient of the treatment agent with the adhesive component, so it is impossible to use a single agent to meet the requirements of the modification treatment and bonding, and it is impossible to simplify the bonding process of multi-step agent treatment.

[0026] The applicant of this case found that the specific modified polyurethane resin can be compatible with the active ingredient of the treatment agent without interfering with each other's functions. Therefore, the composition can include the specific modified polyurethane resin and the active ingredient of the treatment agent at the same time, and can provide two effects of modification and adhesion, and will not cause the adverse effects caused by the aforementioned mixed adhesive and active ingredient (including ineffective modification, weakened touch adhesion, reduced adhesion stability, etc.). In more detail, the applicant of this case found that the use of polyfunctional alcohol or polyether resin or a combination of the two to modify the polyurethane resin can make the modified polyurethane resin have good compatibility with the active ingredient of the treatment agent, and the active ingredient of the treatment agent can be added to the adhesive including the modified polyurethane resin, or the content of the active ingredient of the treatment agent can be increased in the composition including the modified polyurethane resin to achieve the desired treatment and modification effect, while not affecting the functions provided by the modified polyurethane resin. Furthermore, the applicant of this case has discovered that forming a composition by forming a component that provides adhesion in an adhesive (such as a conventional polyurethane resin) with a polyurethane resin modified by a multifunctional alcohol or a polyether resin can not only provide sufficient adhesion, but also allow the active ingredients of a treatment agent to be additionally added to the composition without affecting the adhesion or treatment activity. The composition can therefore provide both the effects of modification and adhesion at the same time.

[0027] Without being bound by theory, the applicant believes that the use of polyfunctional alcohols or polyether resins to modify polyurethane resins, that is, the introduction of polyfunctional alcohols or polyether resins into polyurethane resins can produce structural changes, thereby changing the dispersion behavior of the modified polyurethane resin in the carrier, effectively changing the interaction between the polyurethane resin and the active ingredients of the treatment agent, and reducing the aforementioned negative effects; and the modified polyurethane resin can make the active ingredients of the treatment agent more likely to remain on the surface of the material to be treated, and less likely to be dispersed with the volatilization of the carrier, so that the reaction concentration is better maintained. Therefore, the modified polyurethane resin can make the reaction between the active ingredients of the treatment agent and the surface of the material reach a level at least equivalent to the conventional general bonding process (at least one treatment agent and one glue). In addition, the applicant found that the polyurethane resin modified by polyfunctional alcohols or polyether resins has good compatibility with solvents (or carriers) of different polarities, and thus has adjustment flexibility and can be suitable for different applications.

[0028] The multifunctional alcohol used to modify the polyurethane resin is a chain aliphatic diol, a cyclic aliphatic diol, an aromatic diol, an alcohol amine or a combination thereof, including 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, diethanolamine, triethanolamine, methyldiethanolamine, C9-C18 alkanolamine, N-methyldiethanolamine or a combination thereof, preferably 1,4-butanediol, 1,6-hexanediol, triethanolamine, C9-C18 alkanolamine, N-methyldiethanolamine or a combination thereof, more preferably 1,6-hexanediol, triethanolamine, C9-C18 alkanolamine. The polyether resin used for modifying the polyurethane resin is polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, alkyl polyethylene glycol amine, alkyl polypropylene glycol, alkyl polyethylene glycol / polypropylene glycol amine or a combination thereof, including polyethylene glycol (preferably having a weight average molecular weight (MW): 500-8000), polytetramethylene ether glycol (preferably having a MW: 500-3000), terminal alkyl polyethylene glycol amine (preferably having a MW: 500-3000), terminal alkyl polyethylene glycol / polypropylene glycol amine (preferably MW: 500-2000) or a combination thereof, preferably polyethylene glycol (preferably MW: 500-8000), terminal alkyl polyethylene glycol amine (preferably MW: 500-3000), terminal alkyl polyethylene glycol / polypropylene glycol amine (preferably MW: 500-2000) or a combination thereof, more preferably polyethylene glycol (preferably MW: 1000-3000), terminal alkyl polyethylene glycol amine (preferably MW: 1000-2000).

[0029] The modified polyurethane resin suitable for the multifunctional treatment agent of the present invention may include polyester polyurethane resin, polycarbonate polyurethane resin or a combination thereof. The modified polyurethane resin suitable for the multifunctional treatment agent of the present invention is selected from polyester polyurethane resin, polycarbonate polyurethane resin or a combination thereof. The modified polyurethane resin suitable for the multifunctional treatment agent of the present invention can be obtained by modifying one or more polyurethane resins selected from the group consisting of polyester polyurethane resins and polycarbonate polyurethane resins. The modified polyurethane resin provides the multifunctional treatment agent of the present invention with adhesion and tactile adhesiveness. If adhesion is considered, it is preferably selected from polyester polyurethane resin; if weather resistance is considered, it is preferably selected from polycarbonate polyurethane resin. The polyester polyurethane resin is preferably selected from polycaprolactone, aliphatic polyester, aromatic polyester or a combination thereof, and is more preferably selected from polycaprolactone, aliphatic polyester or a combination thereof; the polycarbonate polyurethane resin is preferably selected from polycarbonate polyurethane resins of the type of 1,2-propylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol or a combination thereof, and is more preferably selected from polycarbonate polyurethane resins of the type of 1,6-hexanediol, 1,5-pentanediol or a combination thereof.

[0030] The multifunctional treatment agent of the present invention may include 3.0 to 40.0 parts by weight of a modified polyurethane resin, preferably 5.0 to 30.0 parts by weight, and more preferably 7.0 to 20.0 parts by weight. If the modified polyurethane resin includes both a polyester polyurethane resin and a polycarbonate polyurethane resin, the preferred proportion is 4.0 to 25.0 parts by weight of the polyester polyurethane resin and 1.0 to 5.0 parts by weight of the polycarbonate polyurethane resin. The above values ​​may include any smaller range of values ​​within the range or may have any value.

[0031] The applicant has also found that adding a suitable surfactant and a suitable solvent to the aforementioned composition including the modified polyurethane resin and the active ingredient of the treatment agent can cause the active ingredient of the treatment agent to remain on the surface of the shoe material for reaction, thereby effectively modifying the surface properties of the shoe material while maintaining the adhesion of the composition, and maintaining good stability after the shoe material is attached. The applicant of this case has further found that adding a suitable amount of the specific surfactant can further improve the reaction between the active ingredient of the treatment agent and the surface of the shoe material, and can be adjusted according to the aqueous, semi-aqueous and solvent-based formulations of the multifunctional treatment agent of the present invention.

[0032] The multifunctional treatment agent of the present invention can be divided into water-based, semi-aqueous and solvent-based formulations according to the choice of carrier. The carrier in the water-based multifunctional treatment agent includes only water; the carrier in the semi-aqueous multifunctional treatment agent includes 5 to 55 parts by weight of water and 5 to 90 parts by weight of organic solvent, preferably 15 to 40 parts by weight of water and 20 to 80 parts by weight of organic solvent, more preferably 20 to 35 parts by weight of water and 40 to 60 parts by weight of organic solvent; the carrier in the solvent-based multifunctional treatment agent includes only organic solvent. The above values ​​can all include smaller ranges of any values ​​within the range or have any values.

[0033] The multifunctional treatment agent of the present invention can adjust the composition of the carrier according to the user's VOC emission specifications, the properties of the shoe material and the overall shoemaking process requirements. The appropriate VOC formula can be selected in response to environmental protection and process requirements, and the interface matching between different materials can be taken into account. For example, for some shoe materials with low polarity and difficult to wet (such as rubber substrates), the multifunctional treatment agent of the present invention can achieve better bonding performance by increasing the solvent ratio (adjusting the water content). In addition, according to the other components of the multifunctional treatment agent of the present invention, the water and solvent ratio can be adjusted to ensure that each component is evenly dispersed in the carrier, so that the modification and bonding effects are stable and uniform. Deionized water is a carrier suitable for the multifunctional treatment agent of the present invention. Organic solvents suitable for use as carriers of the multifunctional treating agent of the present invention include ketones, esters, ethers or combinations thereof, preferably ketones, esters, ethers or combinations thereof having a carbon number of less than 7, more preferably acetone, butanone, diacetone alcohol, N-ethylpyrrolidone, methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol butyl ether or combinations thereof.

[0034] The surfactant suitable for the multifunctional treatment agent of the present invention is used as an emulsifier and a wetting aid, and can be selected from one or more of the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants, preferably selected from nonionic surfactants. Suitable nonionic surfactants include alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, alkylamide polyoxyethylene ethers, fatty acid polyoxyethylene ethers, polysorbates and their polyoxyethylene derivatives, fatty amine polyoxyethylene ethers, polyoxyethylene polyoxypropylene copolymers or combinations thereof, suitable anionic surfactants include alkyl carboxylates, alkyl sulfates, alkyl sulfonates, alkyl phosphates or combinations thereof, and suitable cationic surfactants include alkyl trimethylamine salts, dialkyl dimethylamine salts, alkyl dimethyl benzylamine salts or combinations thereof. The preferred surfactant has a hydrophobic chain with an alkyl group having 5 to 20 carbon atoms, such as dodecyl polyoxyethylene ether and sodium dodecylbenzene sulfonate, and more preferably an alkyl group having 9 to 18 carbon atoms or combinations thereof.

[0035] The multifunctional treatment agent of the present invention may include 0.01 to 3.0 parts by weight of a surfactant, preferably 0.1 to 2.0 parts by weight, and more preferably 0.5 to 1.5 parts by weight. The above values ​​may include any smaller range of any value within the range or have any value. If an excessive amount of surfactant is used, the adhesion will be significantly reduced, and if the content of the surfactant is too low, the wettability to the material will be insufficient.

[0036] Acid agents can improve the bonding strength of the multifunctional treatment agent of the present invention, mainly by providing acid groups to enhance the overall active ingredients and the surface reaction of the material, and by better reaction conditions to make the surface modification of the material more perfect. Acid agents suitable for the present invention include carboxylic acids, hydroxy acids or combinations thereof, preferably selected from carboxylic acids with a carbon number of less than 7, hydroxy acids with a carbon number of less than 7 or combinations thereof, and more preferably selected from formic acid, acetic acid, benzoic acid, oxalic acid, malic acid, salicylic acid or combinations thereof. The multifunctional treatment agent of the present invention may include 0.05 to 1.0 parts by weight of acid agents, preferably 0.2 to 0.7 parts by weight, and more preferably 0.3 to 0.5 parts by weight. The above values ​​can all include a smaller range of any value within the range or have any value.

[0037] The chlorinated donor compound can provide the multifunctional treatment agent of the present invention to react on the unsaturated part of the material surface, effectively improving the polarity of the material. The chlorinated donor compound suitable for the multifunctional treatment agent of the present invention includes chlorine nitrogen compounds, N-chloro aromatic sulfonamides, N-chloro heterocyclic amides, and chloroacetic acid, preferably selected from 1,3-dichloro-5,5-dimethylhydantoin, tetrachloroglycoluril, trichloroacetic acid, sodium dichloroisocyanurate, trichloroisocyanuric acid, N-chlorosuccinimide, N,N-dichloro-p-toluenesulfonamide or a combination thereof, and a more preferred chlorinated donor compound includes trichloroacetic acid, sodium dichloroisocyanurate, trichloroisocyanuric acid or a combination thereof. The content of the chlorinated donor compound in the multifunctional treatment agent of the present invention is 0.4 to 4.0 parts by weight, preferably 0.6 to 3.0 parts by weight, and more preferably 1.0 to 2.5 parts by weight. The above values ​​can all include a smaller range of any value within the range or have any value.

[0038] The multifunctional treatment agent of the present invention preferably further comprises a chlorinated resin. The chlorinated resin can enhance the tensile performance of the multifunctional treatment agent of the present invention; the chlorinated resin suitable for the present invention includes chlorinated rubber, chloroacetic acid resin or a combination thereof; the multifunctional treatment agent of the present invention may comprise 0.1 to 1.0 parts by weight of the chlorinated resin, preferably 0.3 to 0.8 parts by weight, and more preferably 0.4 to 0.7 parts by weight.

[0039] The multifunctional treatment agent of the present invention may further include additives as needed, such as but not limited to stabilizers, adhesion promoters, detergents, and cosolvents, etc. The total content of the additives included in the multifunctional treatment agent of the present invention is about 0.01 to about 2.0 parts by weight, preferably about 0.03 to about 1.5 parts by weight.

[0040] The use of the multifunctional treatment agent of the present invention can simplify the steps of the bonding process, reduce or avoid the use of other agents, while still effectively maintaining or even improving the strength of the bonding of the shoe materials. In the field of shoemaking, a tensile test is generally used to evaluate the adhesion strength of shoe materials, such as outsoles and midsoles, after bonding. There are two different evaluation methods. One is that the two shoe materials must be able to withstand a tensile force of at least 7.5 kilograms per inch (kgf / inch) without peeling off from each other, which means that the adhesion between the shoe materials must be greater than 7.5 kilograms per inch; the other is that the tensile force pulls the shoe materials to damage but the two shoe materials still do not peel off from each other, which means that the adhesion between the shoe materials is greater than the stress of the bonding shoe material itself, resulting in material damage. The multifunctional treatment agent of the present invention can provide an adhesion of at least 8 kg / inch between shoe materials or until the shoe materials are damaged; depending on the material of the shoe material, the multifunctional treatment agent of the present invention can provide an adhesion of preferably at least 8.5 kg / inch between the outsole and the midsole (such as polyurethane material or foam material) or the outsole and the upper material (such as artificial leather or mesh), and more preferably at least 10 kg / inch. For example, it can provide an adhesion of at least 12 kg / inch between a rubber substrate and a foam material (such as ethylene-vinyl acetate copolymer (EVA)), and provide an adhesion of at least 9 kg / inch between a rubber substrate and a polyurethane material (such as PU artificial leather).

[0041] The present invention further provides a method for bonding shoe materials, which comprises bonding two shoe materials together using the multifunctional treatment agent of the present invention. Specifically, the method for bonding shoe materials of the present invention comprises the following steps:

[0042] (a) providing a first shoe material, and coating the multifunctional treating agent of the present invention on the bonding surface of the first shoe material;

[0043] (b) heating and activating the first shoe material coated with the multifunctional treatment agent of the present invention;

[0044] (c) providing a second shoe material; and

[0045] (d) directly bonding the bonding surface of the first shoe material that has been activated by heat to the bonding surface of the second shoe material.

[0046] The shoe material bonding method of the present invention can achieve satisfactory bonding effect without using additional adhesives. Referring to Figure 1, it takes the rubber outsole as an example to illustrate the difference between the conventional shoe material bonding process and the shoe material bonding method of the present invention. The general bonding process of the prior art is to first perform a front-end treatment on the shoe material, then apply a treatment agent on the bonding surface of the shoe material, dry the shoe material coated with the treatment agent, apply an adhesive (or glue) on the bonding surface of the shoe material coated with the treatment agent, and then dry the shoe material coated with the adhesive, and the dried shoe material is subsequently bonded with other shoe materials that have been treated with a pharmaceutical agent. That is, the bonding process of the prior art requires at least two steps of pharmaceutical treatment steps for each shoe material to be bonded before the bonding of the shoe material can be performed. In comparison, the shoe material bonding method of the present invention only needs to apply the multifunctional treatment agent of the present invention on the bonding surface of the shoe material, and it can be used for subsequent bonding and bonding steps after heating and activation. In other words, the shoe material bonding method of the present invention can reduce the steps of treating the shoe materials to be bonded with the reagents; further, the shoe material bonding method of the present invention reduces the step of coating at least one treatment agent or adhesive and its corresponding drying, activation and other processes in the conventional shoe material bonding procedure; further, the shoe material bonding method of the present invention reduces the step of coating at least one treatment agent or adhesive and its corresponding drying, activation and other processes on one or more surfaces to be bonded. Therefore, the shoe material bonding method of the present invention can reduce the steps of gluing, reduce the use of manpower, improve production efficiency, reduce the amount of glue used, and ultimately reduce production costs.

[0047] The present invention finds that it is not necessary to apply both the treatment agent and the adhesive on all the bonding surfaces of the shoe materials to be bonded in order to achieve a satisfactory bonding effect. The bonding method of the shoe materials of the present invention finds that by coating the multifunctional treatment agent of the present invention on the bonding surface of a shoe material to be bonded, and then bonding the shoe material with other shoe materials to be bonded, good adhesion and stability can be exhibited. The present invention further finds that if the bonding method of the shoe materials of the present invention is adopted, only the multifunctional treatment agent of the present invention is coated on the bonding surface of a shoe material to be bonded, the shoe material can be endowed with the properties of affinity and bonding, and can be directly bonded with the bonding surface of another shoe material to be bonded, and the shoe materials can still show good adhesion and stability after bonding. The present invention further finds that by coating only one layer of the multifunctional treatment agent of the present invention on the bonding surface of a shoe material to be bonded, the shoe material can still show good adhesion and stability after bonding with other shoe materials to be bonded.

[0048] Therefore, in the method for bonding shoe materials of the present invention, before the operation of bonding the first shoe material and the second shoe material in step (d), the bonding surface of the first shoe material may only be coated with the multifunctional treatment agent of the present invention, and no other treatment agent or adhesive other than the multifunctional treatment agent of the present invention may be included. Further, before the bonding operation in step (d), the bonding surface of the first shoe material may only include the multifunctional treatment agent of the present invention. Further, before the bonding operation in step (d), the bonding surface of the first shoe material may only include a layer of the multifunctional treatment agent of the present invention.

[0049] According to the shoe material bonding method of the present invention, a person with ordinary knowledge in the technical field of the present invention can determine the number of coating layers of any agent on the surface of any shoe material to be bonded, such as one layer, two layers, three layers, preferably one layer, according to the desired bonding effect or corresponding processing steps. According to the shoe material bonding method 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 included between the two layers does not exceed five layers, preferably does not exceed three layers.

[0050] In the method for bonding shoe materials of the present invention, the heating activation temperature of step (b) is 40 to 80° C., preferably 45 to 70° C., more preferably 50 to 60° C. The heating activation time of step (b) is 2 to 5 minutes, preferably 150 to 270 seconds, more preferably 180 to 250 seconds. The method for bonding shoe materials of the present invention is particularly suitable for producing cold-bonded shoes.

[0051] The method for bonding a shoe material according to the present invention further comprises at least one of the following steps:

[0052] Before the step (a), the bonding surface of the first shoe material is pretreated.

[0053] Before the step (c), the bonding surface of the second shoe material is pretreated.

[0054] Before the step (c), a treatment agent is applied to the connecting surface of the second shoe material.

[0055] Before the step (c), the bonding surface of the second shoe material is light-cured or heat-activated.

[0056] Before the step (c), an adhesive is applied to the bonding surface of the second shoe material, and

[0057] After the step (d), the bonded first shoe material and the second shoe material are pressurized.

[0058] In the shoe material bonding method of the present invention, the multifunctional treatment agent of the present invention may be applied to the bonding surface of the second shoe material, depending on the shoe material type and process requirements. In some aspects, only the multifunctional treatment agent of the present invention may be applied to the bonding surface of the second shoe material, and the bonding surface does not include other treatment agents or adhesives other than the multifunctional treatment agent of the present invention.

[0059] In the shoe material bonding method of the present invention, in order to further enhance the bonding effect, after the bonding surface of the shoe material to be bonded is coated with the multifunctional treatment agent, treatment agent or adhesive of the present invention, the surface may be subjected to other treatment steps, such as drying, wherein the drying step may adopt various conventional drying methods, such as natural drying, oven heating drying, etc.; or activation, wherein the activation step may adopt various conventional activation methods, such as oven heating activation, light activation, etc. For example, if the bonding surface of a shoe material to be bonded is coated with an adhesive, it may be placed in an oven for activation. In addition, the shoe material bonding method of the present invention may also include a step of further processing the bonded shoe material after the bonding step, such as, but not limited to, drying the bonded shoe material, compacting the bonded shoe material, and repeated pressing, etc. The above-mentioned further processing steps may be selected according to the type of shoe material and the process requirements, and the operation sequence may be determined according to the needs.

[0060] In the shoe material bonding method of the present invention, the first shoe material and the second shoe material can be the same or different shoe materials, for example, but not limited to the following shoe materials: midsole, outsole, upper and banding; wherein, the first shoe material is preferably outsole or midsole, and the second shoe material is preferably upper or midsole. In addition, the first shoe material and the second shoe material can have different or the same materials, including rubber materials, vulcanized rubber materials, foaming materials, synthetic fiber materials and natural fiber materials; preferably, the first shoe material includes rubber, and further, preferably, the bonding surface of the first shoe material includes rubber. The materials that can form the outsole and the midsole of the shoe generally include but are not limited to rubber materials, vulcanized rubber materials, polyurethane materials and foam materials; the materials that can form the upper generally include but are not limited to synthetic fiber materials, natural fiber materials, synthetic leather and leather, for example: PU synthetic leather, genuine leather, cotton fiber materials and polyester fiber cloth; and the materials that form the strips generally include but are not limited to unvulcanized rubber and vulcanized rubber, for example: raw rubber and semi-raw rubber that is not fully vulcanized.

[0061] The following examples are provided to illustrate the implementation of the present invention and to explain the technical features of the present invention, and are not intended to limit the scope of protection of the present invention. Any changes or equivalent arrangements that can be easily completed by a person familiar with the technology belong to the scope claimed by the present invention, and the scope of protection of the present invention shall be subject to the scope of the attached patent application.

[0062] Examples:

[0063] Example 1 and Comparative Examples 1 and 2

[0064] A. Test piece preparation

[0065] Cut rubber, EVA, PU artificial leather and mesh materials into 1 inch x 2 inch test pieces. The test pieces are ready for use after the pre-treatment is completed according to the material. The pre-treatment of the rubber test piece includes: grinding the rubber test piece and heating the rubber test piece to a surface temperature of 55-65°C. The pre-treatment of the EVA test piece includes: coating the EVA light-type treatment agent (Dadong resin, 258H) on the bonding surface of the test piece, using UV light curing (E=0.6J / cm2) after drying, and then coating the cured bonding surface with glue (Dadong resin, GE01 or Dadong resin, 98NH+4%348), and then drying and activating to a surface temperature of 50-60°C. The front-end treatment of the PU artificial leather test piece includes: coating the polyurethane treatment agent (Dadong resin, 311NT) on the bonding surface of the test piece, and then coating the glue (Dadong resin, GE01 or Dadong resin, 98NH+4%348) on the bonding surface after drying, and then drying and activating to a surface temperature of 50-60° C. The front-end treatment of the mesh material test piece includes: mixing the upper treatment agent (Dadong resin, 312NT) and 4% by weight of the hardener (Dadong resin, 348), coating the mixed agent on the bonding surface of the test piece, and then coating the glue (Dadong resin, GE01 or Dadong resin, 98NH+4%348) on the bonding surface after drying, and then drying and activating to a surface temperature of 50-60° C.

[0066] B.VOC measurement

[0067] The VOC value determination method used in this case is to use the resin composition and water content in the example to make a calculation, and the calculation method is as follows:

[0068] VOC (Wt%) = 100 - Water (Wt%) - Solid content (Wt%) - Non-volatile content (Wt%)

[0069] C. Tensile test

[0070] A tensile test machine (GT-7010-D2E, Gaotie Technology Co., Ltd.) was used to perform a tensile test on the comparative example or the embodiment to illustrate the bonding effect of the present invention. Two clamps were used to fix the two sides of the part to be tested, and the two sides were pulled apart at a fixed test speed. When the bonding interface between the substrate test piece and the other material test piece was peeled off, the tensile value was recorded. In the present embodiment and comparative example, the bonded test piece was tested at a test speed of 8 cm / min, and the average value of the three tensile test values ​​was taken.

[0071] D. Examples

[0072] The tensile test of the test piece is used to illustrate the effectiveness of the multifunctional treatment agent of the present invention in reducing the bonding steps, being applicable to different shoe materials, and having good adhesion compared to the conventional treatment agents and adhesives on the market. In this embodiment, the rubber test piece that has been treated in the previous stage is used as the base material, and the multifunctional treatment agent of the present invention with different formulations (see Table 1) is coated on the bonding surface of the rubber base material, and after heating and activation, it is bonded to the bonding surface of the test pieces of different materials prepared above.

[0073]

[0074] Table 1

[0075] E. Comparative Example

[0076] In order to clearly illustrate the difference between the present invention and the prior art and the technical problems overcome by the multifunctional treatment agent of the present invention, the comparative examples are divided into A. The treatment agent and the adhesive are separately coated on the bonding surface of the test piece in sequence according to the conventional bonding process, and B. The treatment agent and the adhesive are mixed and then coated on the bonding surface of the test piece. Comparative Examples A and B also use the rubber test piece that has been treated in the previous stage as the substrate. Comparative Example A first coats the rubber treatment agent on the bonding surface of the rubber substrate, and then coats the polyurethane glue on the bonding surface coated with the rubber treatment agent after drying, and then dries and activates to a surface temperature of 50-60°C, and then bonds with the bonding surface of the test piece of different materials prepared above; Comparative Example B mixes the rubber treatment agent and the polyurethane glue in a ratio of 1:1, coats it on the bonding surface of the rubber substrate, dries and activates to a surface temperature of 50-60°C, and then bonds with the bonding surface of the test piece of different materials prepared above. The solvent-based polyurethane adhesive (Dadong resin, 98NH) needs to be mixed with 4 wt% of a hardener (Dadong resin, 348). Table 2 shows the commercially available products and their codes used in the preparation of Comparative Examples A and B in this case.

[0077] Water-based rubber treatment agent Dadong resin, 6006AB Solvent-based rubber treatment agent Dadong resin, 001AB Water-based polyurethane adhesive Dadong resin, GE01 Solvent-based polyurethane adhesive Dadong resin, 98NH Oil hardener Dadong Resin, 348

[0078] Table 2

[0079] F. Test Results

[0080] Tables 3 to 5 show the VOC test results of the embodiments of the present invention and the comparative examples and the tensile test results of different materials. Table 3 is a comparison using a water-based formulation, Table 4 is a comparison using a semi-aqueous formulation, and Table 5 is a comparison using a solvent-based formulation.

[0081]

[0082] Table 3

[0083]

[0084] Table 4

[0085]

[0086] Table 5

[0087] Note 1. The above data with an * after the number indicates that the material has been completely damaged.

[0088] Note 2.NA means this process cannot be operated or executed

[0089] In addition, Tables 3 to 5 clearly show that compared to Comparative Examples A1 to A4, which use a general process of separately coating the treatment agent and the adhesive, the embodiments using the multifunctional treatment agent of the present invention, whether using a water-based, semi-aqueous or solvent-based formula, all have similar or better adhesion. If the method of Comparative Examples B1 to B4 is adopted, the conventional treatment agent and the adhesive are directly mixed in the market, and the polyurethane resin and the active ingredients of the treatment agent will interact with each other, inhibiting the main functionality of each other, not only the adhesion is significantly reduced, but even the coating cannot be completed to complete the bonding process. Compared with Comparative Examples B1 to B4, Examples 1 to 3 use modified polyurethane resins to reduce the degree of mutual interference between the polyurethane resin and the active ingredients of the treatment agent, so that the bonding performance can be at least equivalent to that of A1 to A4 of the conventional process. This experiment shows that the multifunctional treatment agent of the present invention can adjust the water-based or oil-based formula according to different materials and needs, and the multifunctional treatment agents of the present invention with different formulas can show good treatment results and adhesion. At the same time, the use of the multifunctional treatment agent of the present invention can reduce the coating steps and corresponding treatment steps of the agent, simplifying the bonding process while still maintaining satisfactory or even excellent adhesion.

Claims

1. An environmentally friendly multifunctional treatment agent, comprising: 5.0 to 40.0 parts by weight of a modified polyurethane resin, wherein the modified polyurethane resin is modified with a polyfunctional alcohol and / or a polyether resin, Acid 0.05 to 1.0 parts by weight, Chlorinated donor compound 0.4 to 4.0 parts by weight 0.01 to 3.0 parts by weight of a surfactant, and 60 to 95 parts by weight of carrier, The carrier is water, an organic solvent or a combination thereof. 2 . The environmentally friendly multifunctional treating agent according to claim 1 , wherein the modified polyurethane resin comprises a polyester polyurethane resin, a polycarbonate polyurethane resin or a combination thereof.

3. The environmentally friendly multifunctional treatment agent according to claim 1, wherein the multifunctional alcohol is selected from the group consisting of linear aliphatic diols, cyclic aliphatic diols, aromatic diols and alcohol amines, and the polyether resin is selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, alkyl polyethylene glycol amine, alkyl polypropylene glycol and alkyl polyethylene glycol / polypropylene glycol amine.

4. The environmentally friendly multifunctional treating agent according to any one of claims 1 to 3, wherein when the carrier comprises a combination of water and an organic solvent, the ratio thereof is 5 to 55 parts by weight of water and 5 to 90 parts by weight of the organic solvent.

5. The environmentally friendly multifunctional treating agent according to any one of claims 1 to 3, wherein the chlorinated donor compound is selected from the group consisting of 1,3-dichloro-5,5-dimethylhydantoin, tetrachloroglycoluril, trichloroacetic acid, sodium dichloroisocyanurate, trichloroisocyanuric acid, N-chlorosuccinimide, and N,N-dichloro-p-toluenesulfonamide.

6. The environmentally friendly multifunctional treatment agent according to any one of claims 1 to 3, wherein the surfactant is selected from one or more of the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.

7. The environmentally friendly multifunctional treating agent according to any one of claims 1 to 3, further comprising 0.1 to 1.0 parts by weight of a chlorinated resin.

8. The environmentally friendly multifunctional treating agent according to claim 7, wherein the chlorinated resin is chlorinated rubber or chloroacetic acid resin.

9. The environmentally friendly multifunctional treatment agent according to any one of claims 1 to 3, wherein the acid agent is one or more selected from the group consisting of carboxylic acids or hydroxy acids having a carbon number of 7 or less.

10. The environmentally friendly multifunctional treating agent according to any one of claims 1 to 3, wherein the organic solvent is one or more selected from the group consisting of ketones, esters, and ethers.

11. A method for bonding shoe materials, comprising the following steps: Providing a first shoe material, and coating a bonding surface of the first shoe material with an environmentally friendly multifunctional treatment agent according to any one of claims 1 to 10; Heating and activating the first shoe material coated with the environmentally friendly multifunctional treatment agent; Provide second shoe material; and The bonding surface of the first shoe material activated by heating is directly bonded to the bonding surface of the second shoe material.

12. The bonding method according to claim 11, wherein before the bonding operation of step (d) is performed, no treatment agent or adhesive other than the environmentally friendly multifunctional treatment agent according to any one of claims 1 to 10 is included on the bonding surface of the first shoe material.

13. The bonding method according to claim 11, wherein the bonding surface of the first shoe material comprises rubber.

14. The method according to any one of claims 11 to 13, further comprising at least one of the following steps: Before the step (a), the bonding surface of the first shoe material is pretreated. Before the step (c), the bonding surface of the second shoe material is pretreated. Before the step (c), a treatment agent is applied to the connecting surface of the second shoe material. Before the step (c), the bonding surface of the second shoe material is light-cured or heat-activated. Before the step (c), an adhesive is applied to the bonding surface of the second shoe material, and After the step (d), the bonded first shoe material and the second shoe material are pressurized.

15. The bonding method according to any one of claims 11 to 13, wherein the heating activation temperature of step (b) is 40 to 80°C, and the heating activation time is 2 to 5 minutes.

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