Matte coating, coating, sneakers and preparation method of sneakers

Abstract

The invention relates to a matt coating, a coating, sports shoes and a preparation method of the matt coating. The matte coating is prepared from epoxy-acrylic hybrid resin; the epoxy-acrylic hybrid resin is of an alternating structure of an acrylic amorphous region and an epoxy crystalline region. Compared with the prior art, a light dispersion effect similar to diffuse reflection is formed by utilizing the refractive index difference of different phases, so that a low-light matte effect is achieved, a traditional physical matting agent does not need to be used, and the problems of poor combination of the matting agent and a matrix, high coating brittleness, particle aggregation and the like are effectively solved. Microencapsulated isocyanate in the coating releases-NCO groups during hot pressing, the-NCO groups react with resin hydroxyl and the surface of a sole base material to form a covalent bond network, and the stripping force is improved by combining the mechanical chimeric effect of a microphase separation structure.

Description

Technical Field

[0001] This application relates to the field of footwear manufacturing, and particularly to a matte coating, a coating layer, a sports shoe and a preparation method thereof. Background Art

[0002] Matte footwear has been highly favored in the fashion industry in recent years due to its low-key gloss. Traditional matte coatings rely on physical matting agents (such as silica, alumina) or chemical matting resins to achieve low gloss (≤10GU) through the scattering of light by the surface micro-rough structure. However, the interfacial bonding between the matting agent and the resin matrix of the coating itself is poor, which easily causes stress concentration, resulting in an increase in the brittleness of the coating and a decrease in its flexural resistance. In addition, there is a risk of particle agglomeration if the matting agent is not evenly applied.

[0003] In addition, the traditional preparation method of matte footwear is to apply a matte coating to the entire surface of the shoe body, and after drying, the shoe body and the sole are bonded with glue. However, due to the low polarity of the surface of the traditional matte coating, if it is desired to fit with the sole, it is necessary to roughen the bonding part at the bottom edge of the shoe body, otherwise it is easy to cause the embarrassing situation of the shoe body and the sole separating. At the same time, a large amount of dust and waste abrasives are generated during the roughening process, which requires a complex recycling system and does not conform to the trend of green manufacturing, and is likely to cause deformation or a decrease in strength of thin-walled or flexible substrates (such as TPU, ultra-fine fiber). Summary of the Invention

[0004] In view of the above problems, this application provides a matte coating, a coating layer, a sports shoe and a preparation method thereof. The coating and the coating layer use epoxy-acrylic hybrid resin as the main material. In this resin, the epoxy phase and the acrylic phase are micro-phase separated to form an alternating structure of amorphous regions (acrylic) and crystalline-like regions (epoxy). By utilizing the refractive index differences of different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light dispersion effect similar to diffuse reflection is formed, thereby achieving a low-light matte effect, and there is no need to use traditional physical matting agents, effectively solving problems such as poor bonding between the matting agent and the matrix, large brittleness of the coating, and particle agglomeration.

[0005] This application first provides a matte coating, and the matte coating includes epoxy-acrylic hybrid resin; the epoxy-acrylic hybrid resin is an alternating structure of acrylic amorphous regions and epoxy crystalline-like regions.

[0006] Different from the prior art, this coating uses epoxy-acrylic hybrid resin as the main material. In this resin, the epoxy phase and the acrylic phase are micro-phase separated to form an alternating structure of amorphous regions (acrylic) and crystalline-like regions (epoxy). By utilizing the refractive index differences of different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light dispersion effect similar to diffuse reflection is formed, thereby achieving a low-light matte effect, and there is no need to use traditional physical matting agents, effectively solving problems such as poor bonding between the matting agent and the matrix, large brittleness of the coating, and particle agglomeration.

[0007] Furthermore, the size of the acrylic amorphous region is 50 - 200 nm, and the size of the epoxy crystalline region is 50 - 200 nm.

[0008] Furthermore, the preparation of the epoxy - acrylic hybrid resin includes the following steps:

[0009] Generating a prepolymer: Add E - 51 epoxy resin and glycidyl methacrylate into a reaction kettle, heat up to 80 °C, add the catalyst triethylamine, and react to generate a prepolymer containing acrylate side chains;

[0010] Polymerization reaction: Add methyl methacrylate, butyl acrylate, and the initiator azobisisobutyronitrile into the reaction kettle, stir and dissolve, slowly heat up to 85 °C, keep the temperature for 3 hours (to make the conversion rate of methyl methacrylate ≥ 95%), continue to heat up to 110 °C, and react for 1 hour to obtain an epoxy - acrylic polymer;

[0011] Microphase separation: Add a butanone - ethyl acetate solvent into the reaction kettle, cool down to 60 °C, stir, and slowly dropwise add deionized water to induce microphase separation of the epoxy phase and the acrylic phase, forming an alternating structure of acrylic amorphous regions and epoxy crystalline regions; finally, add the inhibitor hydroquinone into the reaction kettle, and obtain the epoxy - acrylic hybrid resin after the reaction kettle is cooled.

[0012] Furthermore, the preparation of the epoxy - acrylic hybrid resin includes the following steps:

[0013] Generating a prepolymer: Add 28 - 40 parts by mass of E - 51 epoxy resin and 6 - 12 parts by mass of glycidyl methacrylate into a reaction kettle, after the reaction kettle is heated up to 80 °C, dropwise add 0.5 - 1.5 parts by mass of the catalyst triethylamine, and react for 2 h. The E - 51 epoxy resin is partially ring - opened, and the epoxy groups of glycidyl methacrylate react to generate a prepolymer containing acrylate side chains;

[0014] Polymerization reaction: Add 15 - 22 parts by mass of methyl methacrylate, 10 - 15 parts by mass of butyl acrylate, and 0.5 - 2 parts by mass of the initiator azobisisobutyronitrile into the reaction kettle, stir and dissolve at 200–400 rpm, slowly heat up to 85 °C, keep the temperature for 3 hours (to make the conversion rate of methyl methacrylate ≥ 95%), continue to heat up to 110 °C, and react for 1 hour to obtain an epoxy - acrylic polymer;

[0015] Microphase separation: Add 20 - 30 parts by mass of a methyl ethyl ketone - ethyl acetate solvent with a mass ratio of 1:1 to the reaction kettle, cool down to 60°C, reduce the stirring rate to 200 rpm, slowly add 5 - 8 parts by mass of deionized water to induce microphase separation between the epoxy phase and the acrylic phase, forming an alternating structure of acrylic amorphous regions and epoxy crystalline regions; finally, add 0.05 - 0.2 parts by mass of the inhibitor hydroquinone to the reaction kettle, and after the reaction kettle is cooled to room temperature, the epoxy - acrylic hybrid resin is obtained.

[0016] Furthermore, the components of the matte coating include 61 - 73 wt% epoxy - acrylic hybrid resin, 12 - 23 wt% propylene glycol methyl ether acetate, 2 - 3 wt% 3 - aminopropyltriethoxysilane, 8 - 10 wt% blocked isocyanate, 0.5 - 1 wt% defoamer, 1 - 2 wt% leveling agent, and 2 - 5 wt% thickener.

[0017] Furthermore, the blocked isocyanate is microencapsulated isocyanate. The subsequent hot - pressing step of the microencapsulated isocyanate can release - NCO groups, react with the resin hydroxyl groups and the surface of the sole substrate to form a covalent bond network, and combined with the mechanical interlocking effect of the microphase - separated structure, the peeling force between the upper and the sole is improved.

[0018] Furthermore, the synthesis of the microencapsulated isocyanate includes the following steps:

[0019] Preparation of the oil phase: Dissolve 20 - 30 parts by mass of isocyanate and 4 - 12 parts by mass of toluene diisocyanate (TDI) in 32 - 45 parts by mass of liquid paraffin to form an oil phase;

[0020] Preparation of the water phase: Dissolve 1 - 3 parts by mass of the emulsifier polyvinyl alcohol (PVA) in 23 - 38 parts by mass of deionized water, heat to 50°C for dissolution, and add 3 - 5 parts by mass of diethylenetriamine (DETA) to form a water phase;

[0021] Emulsification: Slowly add the oil phase to the water phase and emulsify at high speed for 10 min to form a W / O emulsion;

[0022] Polymerization: Heat the W / O emulsion to 60°C and react for 4 hours. Toluene diisocyanate (TDI) and diethylenetriamine (DETA) polymerize at the oil - water interface to form a polyurea wall material, forming a polyurea - encapsulated isocyanate structure;

[0023] Purification: Centrifuge the reaction mixture to collect the microcapsules; wash the microcapsules with water and then dry them under vacuum to obtain the microencapsulated isocyanate.

[0024] Furthermore, the centrifugation speed is 4000 rpm and the time is 15 min.

[0025] Furthermore, the vacuum drying temperature is 40°C and the time is 24 h.

[0026] The second aspect of the present application provides a matte coating, and the matte coating contains an epoxy-acrylic hybrid resin; the epoxy-acrylic hybrid resin has an alternating structure of acrylic amorphous regions and epoxy crystalline regions.

[0027] Furthermore, the preparation method of the matte coating is as follows: printing a matte slurry on the fabric and drying it to form a matte coating; the matte slurry is prepared by mixing the matte coating containing microencapsulated isocyanate according to the first aspect of the present invention with an isocyanate curing agent.

[0028] Different from the prior art, this coating uses an epoxy-acrylic hybrid resin as the main material. In this resin, the epoxy phase and the acrylic phase are microphase-separated to form an alternating structure of amorphous regions (acrylic) and crystalline regions (epoxy). By utilizing the refractive index differences between different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light dispersion effect similar to diffuse reflection is formed, thereby achieving a low-gloss matte effect. Moreover, traditional physical matting agents are not required, effectively solving problems such as poor bonding between the matting agent and the substrate, large brittleness of the coating, and particle agglomeration.

[0029] Furthermore, the components of the matte coating include 61-73 wt% epoxy-acrylic hybrid resin, 12-23 wt% propylene glycol methyl ether acetate, 2-3 wt% 3-aminopropyltriethoxysilane, 8-10 wt% blocked isocyanate, 0.5-1 wt% defoamer, 1-2 wt% leveling agent, and 2-5 wt% thickener.

[0030] Furthermore, the blocked isocyanate is microencapsulated isocyanate.

[0031] The third aspect of the present application provides a pair of matte sports shoes, and the upper of the sports shoes is subjected to matte printing using the matte coating according to the first aspect of the present application.

[0032] Different from the prior art, since the coating of the sports shoes uses an epoxy-acrylic hybrid resin as the main material, the epoxy phase and the acrylic phase in this resin are microphase-separated to form an alternating structure of amorphous regions (acrylic) and crystalline regions (epoxy). By utilizing the refractive index differences between different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light dispersion effect similar to diffuse reflection is formed, thereby achieving a low-gloss matte effect. Moreover, traditional physical matting agents are not required, effectively solving problems such as poor bonding between the matting agent and the substrate, large brittleness of the coating, and particle agglomeration.

[0033] The fourth aspect of the present application provides a preparation method for a pair of matte sports shoes, including the following steps: Preparation of the primer layer: Printing an aqueous polyurethane resin glue on the fabric of the shoe body and drying it to form a polyurethane primer layer.

[0034] Preparation of matte coating: Print the matte slurry above the primer layer and form a matte coating after drying; the matte slurry is prepared by mixing the matte coating containing microencapsulated isocyanate described in the first aspect of the present invention with an isocyanate curing agent;

[0035] Bonding: Brush the edge of the upper surface of the sole with waterborne polyurethane resin glue, and bond it to the bonding part at the bottom edge of the shoe body, and then dry it at 60-70°C;

[0036] Hot pressing: Under the conditions of a temperature of 100-120°C and a pressure of 0.3-0.5 Mpa, press the bonded sole and shoe body, and the pressing time is 30-60 s to obtain the sports shoes with the matte coating.

[0037] Different from the prior art, since the matte coating uses epoxy-acrylic hybrid resin as the main material, the epoxy phase and the acrylic phase are microphase separated to form an alternating structure of amorphous regions (acrylic) and crystalline regions (epoxy). By utilizing the refractive index difference between different phases (epoxy≈1.55, acrylic≈1.48), a light dispersion effect similar to diffuse reflection is formed, and a low-gloss matte effect can be achieved without using traditional physical matting agents. The matte coating of this process has a strong bonding force with the polyurethane matrix of the sole, and there is no need to physically polish the coating to increase the surface roughness, and it can be directly bonded to the polyurethane sole. The microencapsulated isocyanate releases -NCO groups during the hot pressing step, reacts with the resin hydroxyl group and the surface of the sole substrate to form a covalent bond network, and combines with the mechanical interlocking effect of the microphase separation structure to further improve the peel strength. This matte coating can not only reduce the environmental impact during the production process, but also achieve stronger adhesion on different shoe material substrates, meeting the requirements of modern green manufacturing.

[0038] Furthermore, the thickness of the primer layer is 0.06-0.1 mm, and the thickness of the matte coating is 0.1-0.2 mm.

[0039] The above relevant descriptions of the invention content are only an overview of the technical solutions of this application. In order to enable those skilled in the art to more clearly understand the technical solutions of this application, and then can be implemented according to the content recorded in the description, and in order to make the above objects, other objects, features and advantages of this application more easily understood, the following is described in conjunction with the specific implementation manners of this application. Specific Embodiments

[0040] In order to describe in detail the technical content, structural features, achieved purposes and effects of the technical solutions, the following is described in detail with specific embodiments.

[0041] To describe in detail the possible application scenarios, technical principles, specific implementable solutions, achievable objectives and effects of this application, etc., the following will be elaborated in detail with the listed specific embodiments. The embodiments described herein are only used to more clearly illustrate the technical solutions of this application, so they are only examples and cannot be used to limit the protection scope of this application.

[0042] Referring to "embodiments" herein means that the specific features, structures or characteristics described in connection with the embodiments can be included in at least one embodiment of this application. The term "embodiment" appearing at various positions in the specification does not necessarily refer to the same embodiment, nor does it particularly limit its independence or relevance to other embodiments. In principle, in this application, as long as there is no technical contradiction or conflict, the various technical features mentioned in each embodiment can be combined in any way to form corresponding implementable technical solutions.

[0043] Unless otherwise defined, the meanings of the technical terms used herein are the same as those generally understood by those skilled in the technical field to which this application belongs; the use of the relevant terms herein is only for describing specific embodiments and is not intended to limit this application.

[0044] In the description of this application, the term "and / or" is an expression used to describe the logical relationship between objects, indicating that there can be three relationships. For example, A and / or B means: there is A, there is B, and there is both A and B at the same time. In addition, the character " / " in this article generally represents an "or" logical relationship between the associated objects before and after.

[0045] In this application, terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual quantity, primary-secondary or order relationship, etc. between these entities or operations.

[0046] Without more limitations, in this application, the use of the terms "including", "comprising", "having" or other similar expressions in a statement is intended to cover non-exclusive inclusion. These expressions do not exclude that there may be other elements in the process, method or product including the said elements, so that the process, method or product including a series of elements can include not only those defined elements, but also other elements not explicitly listed, or elements inherent to this process, method or product.

[0047] Similar to the understanding in the "Examination Guidelines", in this application, expressions such as "greater than", "less than", and "exceeding" are understood to exclude the base number; expressions such as "above", "below", and "within" are understood to include the base number. In addition, in the description of the embodiments of this application, the meaning of "multiple" is two or more (including two), and similar expressions related to "many" are also understood in this way, such as "multiple groups", "multiple times", etc., unless otherwise specifically defined.

[0048] This application first provides a matte coating, and the matte coating includes an epoxy-acrylic hybrid resin; the epoxy-acrylic hybrid resin has an alternating structure of acrylic amorphous regions and epoxy crystalline regions.

[0049] Different from the prior art, this coating uses an epoxy-acrylic hybrid resin as the main material. In this resin, the epoxy phase and the acrylic phase are microphase-separated to form an alternating structure of amorphous regions (acrylic) and crystalline regions (epoxy). By utilizing the refractive index differences of different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light scattering effect similar to diffuse reflection is formed, thereby achieving a low-gloss matte effect, and there is no need to use traditional physical matting agents, effectively solving problems such as poor binding between the matting agent and the matrix, large brittleness of the coating, and particle agglomeration.

[0050] Further, the size of the acrylic amorphous region is 50 - 200 nm, and the size of the epoxy crystalline region is 50 - 200 nm.

[0051] Further, the preparation of the epoxy-acrylic hybrid resin includes the following steps:

[0052] Generate a prepolymer: Add E-51 epoxy resin and glycidyl methacrylate to a reaction kettle, then heat up to 80 °C, add the catalyst triethylamine, and react to generate a prepolymer containing acrylate side chains;

[0053] Polymerization reaction: Add methyl methacrylate, butyl acrylate, and the initiator azobisisobutyronitrile to the reaction kettle, stir and dissolve, slowly heat up to 85 °C, keep warm for 3 hours (to make the conversion rate of methyl methacrylate ≥ 95%), continue to heat up to 110 °C, and react for 1 hour to obtain an epoxy-acrylic polymer;

[0054] Microphase separation: Add a butanone-ethyl acetate solvent to the reaction kettle, cool down to 60 °C, stir, and slowly dropwise add deionized water to induce microphase separation of the epoxy phase and the acrylic phase, forming an alternating structure of acrylic amorphous regions and epoxy crystalline regions; finally, add the inhibitor hydroquinone to the reaction kettle, and after the reaction kettle cools down, obtain the epoxy-acrylic hybrid resin.

[0055] Further, the preparation of the epoxy-acrylic hybrid resin includes the following steps:

[0056] Preparation of prepolymer: Add 28 - 40 parts by mass of E - 51 epoxy resin and 6 - 12 parts by mass of glycidyl methacrylate into a reaction kettle. After the reaction kettle is heated to 80 °C, 0.5 - 1.5 parts by mass of catalyst triethylamine is added dropwise, and the reaction is carried out for 2 h. Part of the E - 51 epoxy resin is ring - opened, and the epoxy group of glycidyl methacrylate reacts with it to form a prepolymer with acrylate side chains;

[0057] Polymerization reaction: Add 15 - 22 parts by mass of methyl methacrylate, 10 - 15 parts by mass of butyl acrylate and 0.5 - 2 parts by mass of initiator azobisisobutyronitrile into the reaction kettle, stir and dissolve at 200–400 rpm, slowly heat up to 85 °C, keep warm for 3 hours (to make the conversion rate of methyl methacrylate ≥ 95%), continue to heat up to 110 °C, and react for 1 hour to obtain an epoxy - acrylic polymer;

[0058] Microphase separation: Add 20 - 30 parts by mass of a 1:1 butanone - ethyl acetate solvent into the reaction kettle, cool down to 60 °C, reduce the stirring rate to 200 rpm, slowly add dropwise 5 - 8 parts by mass of deionized water to induce microphase separation between the epoxy phase and the acrylic phase, forming an alternating structure of acrylic amorphous regions and epoxy crystalline regions; finally, add 0.05 - 0.2 parts by mass of inhibitor hydroquinone into the reaction kettle. After the reaction kettle is cooled to room temperature, the epoxy - acrylic hybrid resin is obtained.

[0059] Furthermore, the components of the matte coating include 61 - 73 wt% epoxy - acrylic hybrid resin, 12 - 23 wt% propylene glycol methyl ether acetate, 2 - 3 wt% 3 - aminopropyltriethoxysilane, 8 - 10 wt% blocked isocyanate, 0.5 - 1 wt% defoamer, 1 - 2 wt% leveling agent and 2 - 5 wt% thickener.

[0060] Furthermore, the blocked isocyanate is microencapsulated isocyanate. The subsequent hot - pressing step of the microencapsulated isocyanate can release - NCO groups, react with the resin hydroxyl groups and the surface of the sole substrate to form a covalent bond network, and combine with the mechanical interlocking effect of the microphase - separation structure to improve the peeling force between the upper and the sole.

[0061] Furthermore, the synthesis of the microencapsulated isocyanate includes the following steps:

[0062] Preparation of oil phase: Dissolve 20 - 30 parts by mass of isocyanate and 4 - 12 parts by mass of toluene diisocyanate TDI in 32 - 45 parts by mass of liquid paraffin to form an oil phase;

[0063] Preparation of water phase: Dissolve 1 - 3 parts by mass of emulsifier polyvinyl alcohol PVA in 23 - 38 parts by mass of deionized water, heat to 50 °C for dissolution, and add 3 - 5 parts by mass of diethylenetriamine DETA to form a water phase;

[0064] Emulsification: Slowly add the oil phase to the water phase and emulsify at high speed for 10 min to form a W / O emulsion;

[0065] Polymerization: Heat the W / O emulsion to 60 °C and react for 4 hours. Toluene diisocyanate (TDI) and diethylenetriamine (DETA) polymerize at the oil-water interface to form a polyurea wall material, forming a structure in which polyurea encapsulates isocyanate;

[0066] Purification: Centrifuge the reaction mixture (4000 rpm, 15 min) to collect the microcapsules; Wash the microcapsules with water and then dry them under vacuum (40 °C, 24 h) to obtain the microencapsulated isocyanate.

[0067] The second aspect of this application provides a matte coating, and the matte coating contains an epoxy-acrylic hybrid resin; The epoxy-acrylic hybrid resin has an alternating structure of acrylic amorphous regions and epoxy crystalline regions.

[0068] Different from the prior art, this coating uses an epoxy-acrylic hybrid resin as the main material. In this resin, the epoxy phase and the acrylic phase are microphase-separated to form an alternating structure of amorphous regions (acrylic) and crystalline regions (epoxy). By utilizing the refractive index differences between different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light scattering effect similar to diffuse reflection is formed, thus achieving a low-gloss matte effect without the need to use traditional physical matting agents, effectively solving problems such as poor bonding between the matting agent and the matrix, large brittleness of the coating, and particle agglomeration.

[0069] Further, the components of the matte coating include 61 - 73 wt% epoxy-acrylic hybrid resin, 12 - 23 wt% propylene glycol methyl ether acetate, 2 - 3 wt% 3-aminopropyltriethoxysilane, 8 - 10 wt% blocked isocyanate, 0.5 - 1 wt% defoamer, 1 - 2 wt% leveling agent, and 2 - 5 wt% thickener.

[0070] Further, the blocked isocyanate is microencapsulated isocyanate.

[0071] The third aspect of this application provides a pair of matte sports shoes, and the upper of the sports shoes is subjected to matte printing using the matte coating described in the first aspect of this application.

[0072] Different from the prior art, since the coating of the sports shoes uses an epoxy-acrylic hybrid resin as the main material, the epoxy phase and the acrylic phase in this resin are microphase-separated to form an alternating structure of amorphous regions (acrylic) and crystalline regions (epoxy). By utilizing the refractive index differences between different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light scattering effect similar to diffuse reflection is formed, thus achieving a low-gloss matte effect without the need to use traditional physical matting agents, effectively solving problems such as poor bonding between the matting agent and the matrix, large brittleness of the coating, and particle agglomeration.

[0073] The fourth aspect of this application provides a preparation method for a matte sports shoe, including the following steps: Preparation of the primer layer: Print aqueous polyurethane resin glue on the shoe body fabric, and form a polyurethane primer layer after drying;

[0074] Preparation of the matte coating: Print matte slurry above the primer layer, and form a matte coating after drying; The matte slurry is prepared by mixing the matte coating material containing microencapsulated isocyanate described in the first aspect of the present invention with an isocyanate curing agent;

[0075] Bonding: Brush aqueous polyurethane resin glue on the upper surface edge of the sole, and bond it to the bonding part at the bottom edge of the shoe body, and then dry it at 60-70 °C;

[0076] Hot pressing: Under the conditions of a temperature of 100-120 °C and a pressure of 0.3-0.5 Mpa, press the bonded sole and shoe body, and the pressing time is 30-60 s to obtain the sports shoe with a matte coating.

[0077] Different from the prior art, since the matte coating uses epoxy-acrylic hybrid resin as the main material, the epoxy phase and the acrylic phase are microphase-separated to form an alternating structure of amorphous regions (acrylic) and crystalline-like regions (epoxy). By utilizing the refractive index differences of different phases (epoxy ≈ 1.55, acrylic ≈ 1.48), a light dispersion effect similar to diffuse reflection is formed. Without using traditional physical matting agents, a low-gloss matte effect can be achieved. The bonding strength between the matte coating of this process and the polyurethane matrix of the sole is strong. There is no need to physically polish the coating to increase the surface roughness, and it can be directly bonded to the polyurethane sole. Microencapsulated isocyanate releases -NCO groups during the hot pressing step, reacts with resin hydroxyl groups and the surface of the sole substrate to form a covalent bond network, and combined with the mechanical interlocking effect of the microphase-separated structure, the peel strength is further improved. This matte coating can not only reduce the environmental impact during the production process, but also achieve stronger bonding on different shoe material substrates, meeting the requirements of modern green manufacturing.

[0078] Further, the thickness of the primer layer is 0.06-0.1 mm, and the thickness of the matte coating is 0.1-0.2 mm.

[0079] Example 1 A matte coating material, a matte coating and a matte sports shoe

[0080] 1. Synthesis of epoxy-acrylic hybrid resin

[0081] After mixing E-51 epoxy resin (150 g) with glycidyl methacrylate GMA (35 g), the temperature was raised to 80 °C, and triethylamine (3 g), the catalyst, was added dropwise. The reaction was carried out for 2 hours to cause the epoxy groups of GMA to partially ring-open with E-51, generating a prepolymer containing acrylate side chains. Subsequently, methyl methacrylate MMA (70 g) and butyl acrylate BA (50 g) were added to the reaction system, and azobisisobutyronitrile (3 g), the initiator, was added. After stirring and dissolving, the temperature was slowly raised to 85 °C and kept warm for 3 hours, and then further raised to 110 °C for 1 hour to ensure complete polymerization of the residual monomers. 1:1 methyl ethyl ketone / ethyl acetate solvent (120 g) was added, the temperature was lowered to 60 °C, the stirring rate was reduced to 200 rpm, and deionized water (30 g) was slowly added dropwise to induce microphase separation between the epoxy phase and the acrylic phase (forming 50–200 nm microdomains), forming an alternating structure of amorphous regions (acrylic acid) and quasi-crystalline regions (epoxy). Hydroquinone (0.5 g), the inhibitor, was added, and after cooling to room temperature, the epoxy-acrylic hybrid resin was obtained.

[0082] 2. Synthesis of microencapsulated isocyanate

[0083] The isocyanate (150 g) and toluene diisocyanate TDI (30 g) were dissolved in liquid paraffin (230 mL) to form an oil phase. The emulsifier polyvinyl alcohol PVA (12 g) was dissolved in deionized water (260 mL), heated to 50 °C for dissolution, and diethylenetriamine DETA (25 g) was added to obtain an aqueous phase. The oil phase was slowly added to the aqueous phase, and high-speed emulsification was carried out for 10 min to form a W / O emulsion. Subsequently, the emulsion was heated to 60 °C and reacted for 4 hours. Toluene diisocyanate TDI and diethylenetriamine DETA polymerized at the oil-water interface to form a polyurea wall material. The microcapsules were collected by centrifugation (4000 rpm, 15 min), washed with water, and then vacuum dried (40 °C, 24 h) to obtain the microencapsulated isocyanate.

[0084] 3. Preparation of matte coating

[0085] 67% epoxy-acrylic resin and 16% PMA solvent were stirred and mixed evenly at low speed, 2.5% KH-550 was added, and high-speed dispersion (2000 rpm, 20 min) was carried out until there were no particles. Subsequently, 8% microencapsulated isocyanate was added, and low-speed stirring (300 rpm, 15 min) was carried out to avoid capsule rupture. Finally, 1% defoamer, 1.5% leveling agent, and 4% thickener were added, and stirring was continued until evenly mixed to obtain the matte coating.

[0086] 4. Preparation of matte slurry: 100 Kg of the matte coating of Example 1 was mixed with 4 Kg of isocyanate curing agent (manufacturer: Wanhua Chemical, model: HT-100) to obtain the matte slurry;

[0087] Preparation of the primer layer: Screen-print an aqueous primer with a thickness of 0.07 mm (manufacturer: Dongguan Baili High Polymer Technology Co., Ltd., model: L369) on the black shoe body fabric, and dry it at 80 °C until the surface is dry to form the primer layer.

[0088] 5. Preparation of the matte coating: Screen-print the matte slurry on the primer layer with a screen-printing thickness of 0.15 mm, and dry it at 80 °C until the surface is dry to form the matte coating.

[0089] 6. Bonding: Brush the upper surface edge of the sole with an aqueous polyurethane resin adhesive, and bond it to the bonding part at the bottom edge of the shoe body, then dry it at 60 - 70 °C;

[0090] 7. Hot pressing: Under the conditions of a temperature of 100 - 120 °C and a pressure of 0.3 - 0.5 Mpa, press the bonded sole and shoe body, and the pressing time is 30 - 60 s to obtain the sports shoes with the matte coating.

[0091] Comparative Example 1 A kind of matte coating, matte coating and matte sports shoes

[0092] The difference between Comparative Example 1 and Example 1 is that microencapsulated isocyanate and isocyanate curing agent are not added. Comparative Example 2 A kind of matte coating, matte coating and matte sports shoes

[0093] The difference between Comparative Example 2 and Example 1 is that the preparation of the matte coating is different

[0094] The preparation of the matte coating in Comparative Example 2 includes the following steps:

[0095] Mix 65% polyurethane resin and 16% PMA solvent by low-speed stirring until evenly mixed, add 2.5% KH-550, and disperse it at high speed (2000 rpm, 20 min) until there are no particles. Then add 8% microencapsulated isocyanate and stir at low speed (300 rpm, 15 min) to avoid capsule rupture. After stirring evenly, add 2% matting powder, and finally add 1% defoaming agent, 1.5% leveling agent and 4% thickener, and continue to stir evenly.

[0096] Performance test:

[0097] 1. Peel strength test:

[0098] Use a peel tensile testing machine to test the peel strength of the sole and shoe body of the sports shoes obtained in the examples. Referring to the standard GB / T 3903.8-2022, cut the bonded part of the sole and shoe body into specimens with a width of 10 mm, fix them to the testing machine fixture, and perform a 180° peel test at a speed of 10 mm / min. Record the maximum load value during the peeling process and observe the failure mode (coating peeling or substrate tearing). The test results are shown in Table 1.

[0099] Table 1 Peel Strength Test Results

[0100]

[0101] From the peel strength test results in Table 1, it can be seen that the peel strength of the matte coating of the present invention is significantly the highest, and at the same time, the phenomenon of substrate tearing occurs. While in Comparative Example 1 without adding microencapsulated isocyanate, slight delamination of the coating appears.

[0102] 2. Glossiness Test:

[0103] A digital glossiness meter was used to test the glossiness of the printed finished products obtained in the application examples. Referring to the standard ASTM D523, the glossiness of the coating surface was measured at an incident angle of 60°. Five different areas were selected for each sample and averaged to ensure that the test points avoided the edges of the printed patterns. The test results are shown in Table 2.

[0104] Table 2 Glossiness Test Results

[0105]

[0106] From the experimental results in Table 2, it can be seen that the matting effect of the matte coating of the present invention is higher than that of the matte coating with the addition of matting powder, and at the same time, the risk of particle agglomeration is eliminated.

[0107] Through a new type of coating, coating design and preparation process, the present invention significantly improves the adhesion between the matte coating and the substrate, avoids the need for traditional roughening treatment, and avoids dust, waste recycling and potential damage to the substrate in the traditional manufacturing process. By solvent evaporation-induced epoxy-acrylic hybrid resin to form an alternating microphase structure, the matting effect of the coating is achieved by using the refractive index difference of the two resin materials, without using traditional physical matting agents, effectively solving problems such as poor binding between the matting agent and the matrix, large brittleness of the coating and particle agglomeration. In summary, the present invention provides a matte coating without roughening that has excellent adhesion, flexibility and durability. This coating can not only reduce the environmental impact during the production process, but also achieve stronger adhesion on different shoe material substrates, meeting the requirements of modern green manufacturing.

[0108] Finally, it should be noted that although the above embodiments have been described in the text of the specification of the present application, it does not limit the scope of patent protection of the present application. Any technical solutions formed by equivalent structure or equivalent process substitution or modification using the content recorded in the text of the specification of the present application based on the essential concept of the present application, as well as directly or indirectly implementing the technical solutions of the above embodiments in other related technical fields, are included in the scope of patent protection of the present application.

Claims

1. A matte coating, characterized in that, The matte coating includes an epoxy-acrylic hybrid resin; the epoxy-acrylic hybrid resin has an alternating structure of acrylic amorphous regions and epoxy crystalline regions.

2. The matte coating according to claim 1, characterized in that, The size of the acrylic amorphous regions is 50 - 200 nm, and the size of the epoxy crystalline regions is 50 - 200 nm.

3. The matte coating according to claim 1, characterized in that, The preparation of the epoxy-acrylic hybrid resin includes the following steps: Generating a prepolymer: Add E-51 epoxy resin and glycidyl methacrylate into a reaction kettle, heat up to 80 °C, add the catalyst triethylamine, and react to generate a prepolymer containing acrylate side chains. Polymerization reaction: Add methyl methacrylate, butyl acrylate, and the initiator azobisisobutyronitrile into the reaction kettle, stir and dissolve, slowly heat up to 85 °C, keep warm for 3 hours, then continue to heat up to 110 °C and react for 1 hour to obtain an epoxy-acrylic polymer. Microphase separation: Add a butanone-ethyl acetate solvent into the reaction kettle, cool down to 60 °C, stir, and slowly dropwise add deionized water to induce microphase separation of the epoxy phase and the acrylic phase, forming an alternating structure of acrylic amorphous regions and epoxy crystalline regions; finally, add the inhibitor hydroquinone into the reaction kettle, and after the reaction kettle cools down, obtain the epoxy-acrylic hybrid resin.

4. The matte coating according to claim 1, wherein The preparation of the epoxy-acrylic hybrid resin includes the following steps: Generating a prepolymer: Add 28 - 40 parts by mass of E-51 epoxy resin and 6 - 12 parts by mass of glycidyl methacrylate into a reaction kettle, after the reaction kettle is heated up to 80 °C, dropwise add 0.5 - 1.5 parts by mass of the catalyst triethylamine, and react for 2 h. The E-51 epoxy resin partially opens the ring and reacts with the epoxy groups of glycidyl methacrylate to generate a prepolymer containing acrylate side chains. Polymerization reaction: Add 15 - 22 parts by mass of methyl methacrylate, 10 - 15 parts by mass of butyl acrylate, and 0.5 - 2 parts by mass of the initiator azobisisobutyronitrile into the reaction kettle, stir and dissolve, slowly heat up to 85 °C, keep warm for 3 hours, then continue to heat up to 110 °C and react for 1 hour to obtain an epoxy-acrylic polymer. Microphase separation: Add 20 - 30 parts by mass of a 1:1 butanone-ethyl acetate solvent into the reaction kettle, cool down to 60 °C, reduce the stirring rate to 200 rpm, slowly dropwise add 5 - 8 parts by mass of deionized water to induce microphase separation of the epoxy phase and the acrylic phase, forming an alternating structure of acrylic amorphous regions and epoxy crystalline regions; finally, add 0.05 - 0.2 parts by mass of the inhibitor hydroquinone into the reaction kettle, and after the reaction kettle cools down to room temperature, obtain the epoxy-acrylic hybrid resin.

5. The matte coating according to claim 1, characterized in that, The components of the matte coating include 61 - 73 wt% epoxy-acrylic hybrid resin, 12 - 23 wt% propylene glycol monomethyl ether acetate, 2 - 3 wt% 3-aminopropyltriethoxysilane, 8 - 10 wt% blocked isocyanate, 0.5 - 1 wt% defoamer, 1 - 2 wt% leveling agent, and 2 - 5 wt% thickener.

6. The matte coating according to claim 5, wherein The blocked isocyanate is microencapsulated isocyanate.

7. A matte coating, characterized in that, The matte coating contains an epoxy-acrylic hybrid resin; the epoxy-acrylic hybrid resin has an alternating structure of acrylic amorphous regions and epoxy crystalline regions.

8. A matte sports shoe, characterized in that, The upper surface of the sports shoes is subjected to matte printing using the matte coating described in any one of claims 1-6.

9. A method for preparing the matte sports shoes according to claim 8, characterized in that, The preparation method includes the following steps: Preparation of the primer layer: Print aqueous polyurethane resin glue on the shoe body fabric and form a polyurethane primer layer after drying. Preparation of the matte coating: Print the matte slurry above the primer layer and form a matte coating after drying; the matte slurry is prepared by mixing the matte coating described in any one of claims 1-6 with an isocyanate curing agent. Bonding: Brush aqueous polyurethane resin glue on the edge of the upper surface of the sole, bond it with the bonding part at the edge of the bottom of the shoe body, and dry it at 60-70 °C. Hot pressing: Under the conditions of a temperature of 100-120 °C and a pressure of 0.3-0.5 Mpa, press the bonded sole and shoe body, and the pressing time is 30-60 s to obtain the sports shoes with a matte coating.

10. The preparation method according to claim 9, characterized in that, The thickness of the primer layer is 0.06-0.1 mm, and the thickness of the matte coating is 0.1-0.2 mm.

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