Wear-resistant printing paste, cloth and preparation method of wear-resistant printing paste

Abstract

The invention relates to wear-resistant printing paste, cloth and a preparation method thereof. The invention provides wear-resistant printing paste on the first aspect. The wear-resistant printing paste is prepared from 60%-70% of waterborne polyurethane, 5%-15% of waterborne organic silicon resin, 5%-10% of waterborne silica sol, 4%-8% of modified microspheres and 1%-3% of fine fibers. Different from the prior art, the wear-resistant printing paste with a specific component content formula provided by the technical scheme forms a wear-resistant printing coating which takes fine fibers to support a spatial framework, takes modified microspheres to fill the spatial framework to provide elastic buffering and takes waterborne polyurethane and waterborne organic silicon resin as main bodies; the water-based silica sol can further connect the modified microspheres and the resin, so that the crosslinking property and compactness of the coating are improved, and the coating achieves more stable and wear-resistant effects.

Description

Technical Field

[0001] The present application relates to the field of textiles, and in particular to wear-resistant printing paste, cloth and a preparation method thereof. Background Art

[0002] At present, the general method to improve the wear resistance of fabrics is to use wear-resistant fibers for weaving. Wear-resistant particles are generally added to wear-resistant fibers, and to ensure spinnability, the amount of wear-resistant particles added is limited. High wear resistance cannot be achieved, and adding too many wear-resistant particles to the fibers will affect the wearing comfort of the woven clothing.

[0003] Although the method of coating the fabric with a coating containing a wear-resistant component will not affect the wearing comfort, since the coating itself is an integrated wear-resistant and relatively hard structure, when subjected to a strong impact, the stress points are prone to breakage, which affects the service life of the wear-resistant fabric. Summary of the invention

[0004] In view of the above problems, the present invention provides a wear-resistant printing paste, a fabric and a preparation method thereof that can resist strong impact, have high wear resistance and have buffering properties. The wear-resistant printing paste provided by the present invention has high applicability and can be printed on the surface of various fabrics to form a wear-resistant coating. Its high wear resistance and buffering protection can be used in the preparation of high-end shoe uppers, and has great market prospects.

[0005] To achieve the above purpose, the first aspect of the present invention provides a wear-resistant printing paste, which includes the following components in percentage by mass: 60%-70% of aqueous polyurethane, 5%-15% of aqueous silicone resin, 5%-10% of aqueous silica sol, 4%-8% of modified microspheres and 1-3% of fine fibers; the modified microspheres do not deform under a pressure of 25 MPa, have a particle size D50 of 10-90 um, and a true density of 0.05-0.40 g / cm 3 Hollow plastic sphere.

[0006] Different from the prior art, the wear-resistant printing paste with a specific component content formula provided by the above technical solution forms a space skeleton supported by fine fibers on the surface of the coated fabric, and modified microspheres are filled in the space skeleton to provide elastic buffering, while the wear-resistant printing coating is mainly composed of water-based polyurethane and water-based silicone resin; the water-based silica sol can further connect the microspheres and the resin, improve the cross-linking and density of the coating, so that the coating achieves a more stable and wear-resistant effect.

[0007] The modified microspheres do not deform under a pressure of 25MPa, that is, the maximum compressive pressure can reach 25MPa. They have great elasticity and can provide good cushioning. When the wear-resistant printed coating is subjected to lateral shear or strong positive impact caused by friction, the modified microspheres in the coating can deform to a certain extent and play a good cushioning role. In order to avoid the modified microspheres appearing on the surface of the coating, they are mainly distributed in the middle of the coating and filled in the space skeleton formed by fine fibers. The particle size and density of the plastic microspheres are controlled, and the particle size D50 of the modified microspheres is controlled at 10-90um and the true density is controlled at 0.05-0.40g / cm 3 .

[0008] Furthermore, the surface of the modified microspheres is covered with calcium-containing compounds. The surface of the modified microspheres is fully or partially covered with calcium-containing compounds, which can be combined with silica sol, so that the modified microspheres are better combined with the resin through the silica sol, the crosslinking density of the entire coating is increased, and the wear resistance is further enhanced.

[0009] Furthermore, the waterborne polyurethane is a waterborne polyurethane with hydroxyl groups.

[0010] Furthermore, the water-based silicone resin is silicone-modified polyether polyurethane.

[0011] Furthermore, the particle size of the aqueous silica sol particles is 5-10 nm.

[0012] Furthermore, the wear-resistant printing paste further comprises 0.5%-1.0% of fumed silica; the fumed silica is hydrophilic silica with a BET specific surface area of ​​130-300 m 2 / g.

[0013] Furthermore, the fine fibers are polyester fibers with a length of 20-300 um.

[0014] Furthermore, the wear-resistant printing paste also includes 0.5-1.0% of a dispersant, 0.3-0.5% of a pH regulator, 0.2-1.5% of a thickener, and 5-10% of a cross-linking agent.

[0015] The second aspect of the present invention provides a method for preparing a wear-resistant printing paste. The wear-resistant printing paste of the first aspect of the present invention is weighed according to components and mass, and stirred evenly at 800-1000r / min to obtain the wear-resistant printing paste.

[0016] The third aspect of the present invention provides a method for preparing a wear-resistant printed fabric, wherein the wear-resistant printing slurry described in the first aspect of the present invention is applied to a base fabric by screen printing or thick coating with a hollow screen to obtain a printing layer of 0.3-4.0 mm; after the printing layer is dried, the wear-resistant printed fabric is obtained.

[0017] A fourth aspect of the present invention provides a wear-resistant printed fabric, which is prepared by the preparation method described in the third aspect of the present invention.

[0018] The above-mentioned records related to the invention content are only an overview of the technical solution of the present application. In order to enable ordinary technicians in the field to more clearly understand the technical solution of the present application, and then implement it according to the written contents of the specification, and to make the above-mentioned purpose and other purposes, features and advantages of the present application easier to understand, the specific implementation mode and drawings of the present application are explained below. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The drawings are only used to illustrate the principles, implementation methods, applications, characteristics and effects of the specific embodiments of the present application and other related contents, and shall not be considered as limitations of the present application.

[0020] In the drawings of the specification:

[0021] Figure 1 is an enlarged view of the surface of the modified microsphere (after calcification treatment) in the embodiment;

[0022] Figure 2 This is a partial picture of the sample effect produced by screen printing as described in Example 2.

[0023] Figure 3 This is a partial picture of the sample effect of the method of coating the hollow screen in one layer as described in Example 3;

[0024] Figure 4 1 is a schematic diagram of the structure of the coating according to the embodiment. Among them, 1 orange mark represents the base fabric; 2 green mark represents the nano-scale silica sol particles; 3 blue mark represents the modified microspheres; 4 red mark represents the fine fibers; 5 gray mark represents the main film-forming material composed of water-based polyurethane and water-based silicone resin. DETAILED DESCRIPTION

[0025] In order to explain in detail the possible application scenarios, technical principles, specific schemes that can be implemented, and the purposes and effects that can be achieved, the following is a detailed description of the specific embodiments listed in conjunction with the accompanying drawings. The embodiments described herein are only used to more clearly illustrate the technical solutions of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.

[0026] Reference to "embodiment" herein means that the specific features, structures or characteristics described in conjunction with the embodiment may be included in at least one embodiment of the present application. The term "embodiment" appearing in various places in the specification does not necessarily refer to the same embodiment, nor does it particularly limit its independence or association with other embodiments. In principle, in the present application, as long as there is no technical contradiction or conflict, the various technical features mentioned in the embodiments can be combined in any way to form a corresponding implementable technical solution.

[0027] Unless otherwise defined, the technical terms used in this document have the same meanings as those generally understood by those skilled in the art to which this application belongs; the use of relevant terms in this document is only for describing specific embodiments and is not intended to limit this application.

[0028] In the description of this application, the term "and / or" is an expression used to describe the logical relationship between objects, indicating that three relationships may exist, for example, A and / or B, which means: A exists, B exists, and A and B exist at the same time. In addition, the character " / " in this article generally indicates that the objects before and after are in an "or" logical relationship.

[0029] In the present application, terms such as “first” and “second” are merely used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship of quantity, priority or sequence between these entities or operations.

[0030] Without further limitations, in this application, the words "include", "comprises", "has" or other similar expressions used in the sentences are intended to cover non-exclusive inclusion. These expressions do not exclude the presence of additional elements in the process, method or product including the elements, so that the process, method or product including a series of elements may include not only those limited elements, but also other elements not explicitly listed, or also include elements inherent to such process, method or product.

[0031] Similar to the understanding in the Examination Guidelines, in this application, expressions such as "greater than", "less than", "exceed" and the like are understood to exclude the number itself; expressions such as "above", "below", "within" and the like are understood to include the number itself. In addition, in the description of the embodiments of this application, "multiple" means more than two (including two), and similar expressions related to "multiple" are also understood in this way, such as "multiple groups", "multiple times", etc., unless otherwise clearly and specifically limited.

[0032] The first aspect of the present invention provides a wear-resistant printing paste, which comprises the following components in percentage by mass: 60%-70% of aqueous polyurethane, 5%-15% of aqueous silicone resin, 5%-10% of aqueous silica sol, 4%-8% of modified microspheres and 1-3% of fine fibers; the modified microspheres do not deform under a pressure of 25 MPa, have a particle size D50 of 10-90 um, and a true density of 0.05-0.40 g / cm 3 Hollow plastic sphere.

[0033] Different from the prior art, the wear-resistant printing paste with a designed formula provided by the above technical solution forms a space skeleton supported by fine fibers on the surface of the coated fabric, and the modified microspheres are filled in the space skeleton to provide elastic buffering, while the wear-resistant printing coating is mainly composed of water-based polyurethane and water-based silicone resin; the water-based silica sol can further connect the modified microspheres and the resin, improve the cross-linking and density of the coating, and make the coating more stable and wear-resistant. The structural diagram of the coating is shown in the figure below. Figure 4 shown.

[0034] The modified microspheres do not deform under a pressure of 25MPa, that is, the maximum compressive pressure can reach 25MPa. They have great elasticity and can provide good cushioning. When the wear-resistant printed coating is subjected to lateral shear or strong positive impact caused by friction, the modified microspheres in the coating can deform within a certain range due to their hollow elastic plastic ball structure, thus playing a good cushioning role. At the same time, in order to avoid the modified microspheres appearing on the surface of the coating, they are mainly distributed in the middle of the coating and filled in the space skeleton formed by fine fibers. The particle size and density of the modified microspheres are controlled, and the particle size D50 of the modified microspheres is controlled at 10-90um and the true density is controlled at 0.05-0.40g / cm 3 .

[0035] Using fine fibers as the skeleton means that after being coated with water-based resin in the coating, the fine fibers will have a certain hardness.

[0036] Furthermore, the surface of the modified microspheres is covered with calcium-containing compounds. The surface of the modified microspheres is fully or partially covered with calcium-containing compounds, which can be combined with silica sol, so that the modified microspheres are better dissolved in the resin / coating through the silica sol, the crosslinking density of the entire coating is increased, and the wear resistance is further enhanced.

[0037] Furthermore, the waterborne polyurethane is a waterborne polyurethane with hydroxyl groups. The waterborne polyurethane with hydroxyl groups has a hydroxyl structure that can better combine with a crosslinking agent, thereby improving the overall crosslinking property while taking into account the softness.

[0038] Furthermore, the waterborne organosilicon resin is a polyether polyurethane modified by organosilicon. The waterborne organosilicon resin has good slipperiness and can reduce the friction of the coating; at the same time, the resin has good flexibility and can improve the softness of the coating. The waterborne organosilicon-modified polyether polyurethane can interact with the waterborne polyurethane through polar bonds (such as urethane bonds), enhance crosslinking, and increase crosslinking density.

[0039] Furthermore, the particle size of the aqueous silica sol and the silica sol particles is 5-10nm. The silica sol particles with a particle size of 5-10nm are relatively small and have strong wettability, and can quickly disperse the particles in the system; they have good permeability and can fully penetrate into the various components of the coating, including the surface of the plastic microspheres; the silica sol will combine with the calcium compound sites on the surface of the microspheres under alkaline conditions (the coating system is alkaline), and also make the surface of the microspheres more adhered to the silica sol, so that it can better combine with the resin, and the overall cross-linking density of the coating is improved, which increases the wear resistance.

[0040] Furthermore, the wear-resistant printing paste further comprises 0.5%-1.0% of fumed silica; the fumed silica is hydrophilic silica with a BET specific surface area of ​​130-300 m 2 The addition of the fumed silica can increase the thixotropy and improve the storage stability of the slurry.

[0041] Furthermore, the fine fibers are polyester fibers with a length of 20-300 um. The fine fibers can be prepared by crushing recycled fabrics.

[0042] Furthermore, the wear-resistant printing paste also includes 0.5-1.0% of a dispersant, 0.3-0.5% of a pH regulator, 0.2-1.5% of a thickener, and 5-10% of a cross-linking agent.

[0043] The pH value of the slurry is adjusted by adding a pH adjuster so that the pH value of the slurry is controlled at 7.5-9.0, making the coating system alkaline.

[0044] The addition of dispersant can better disperse the particles in the slurry system and improve the storage stability of the slurry. The addition of thickener can adjust the viscosity, making the coating easier to construct and increasing the stability of the slurry. The cross-linking agent can increase the cross-linking density of the slurry components and increase the water resistance and wear resistance of the coating.

[0045] Furthermore, the thickener is an alkali swellable thickener or a polyurethane thickener.

[0046] Furthermore, the crosslinking agent is an isocyanate crosslinking agent. The isocyanate crosslinking agent and water generate polyurea, which further improves the crosslinking entanglement of the coating components, increases the crosslinking density and wear resistance.

[0047] The second aspect of the present invention provides a method for preparing a wear-resistant printing paste. The wear-resistant printing paste of the first aspect of the present invention is weighed according to components and mass, and stirred evenly at 800-1000r / min to obtain the wear-resistant printing paste.

[0048] The third aspect of the present invention provides a method for preparing a wear-resistant printed fabric, wherein the wear-resistant printing slurry described in the first aspect of the present invention is applied to a base fabric by screen printing or thick coating with a hollow screen to form a printing layer of 0.3-4.0 mm; after the printing layer is dried, the wear-resistant printed fabric is obtained.

[0049] Furthermore, the base fabric includes but is not limited to polyester, nylon, and spandex.

[0050] Furthermore, the printing layer is dried at a temperature of 50-70°C for 48-72 hours.

[0051] A fourth aspect of the present invention provides a wear-resistant printed fabric, which is prepared by the preparation method described in the third aspect of the present invention.

[0052] The waterborne polyurethane used in this embodiment is 2757 from Covestro; the waterborne silicone resin is 1089R3 from Silco; the waterborne silica sol is AD507 waterborne silica sol solution from Guangdong Jindong New Materials Technology Co., Ltd.; the dispersant is BYK-190 from BYK; the pH adjuster is AMP-95 from Dow; the fumed silica is A200 from Evonik; the thickener is Dow ASE60; and the crosslinker is Wanhua Aquolin270 isocyanate type crosslinker.

[0053] The fine fibers used in this embodiment are made from crushed polyester cloth, have a length of 20-300 um, and are in the shape of long strips.

[0054] In this embodiment, the modified microspheres are selected from Figure 1 The EMC series modified microspheres shown are from Japan Fellite Co., Ltd. They do not deform under a pressure of 25 MPa. The surface is covered with calcium compounds. The particle size D50 is 10-90 um and the true density is 0.05-0.40 g / cm 3 Hollow plastic spheres. In Examples 1 and 4, EMC-40B with a particle size D50 of 47-59 um is used; in Example 2, EMC-20B with a particle size D50 of 17-33 um is used; and in Example 3, EMC-80B with a particle size D50 of 50-90 um is used.

[0055] The performance testing method used in this embodiment includes:

[0056] 1. Abrasion resistance test: Test instrument: Martindale abrasion tester; Based on the standard: ASTMD4966-2010 "Fabric Abrasion Resistance Test Martindale Abrasion Tester" issued by the American Materials Association; Test method: A circular specimen is rubbed against a fabric of the same material under a given pressure in a Lissajous graphic motion trajectory. After reaching the specified number of revolutions, the pilling and abrasion grade of the specimen is evaluated.

[0057] Embodiment 1 A wear-resistant printing paste and printed fabric

[0058] S1: Weigh and weigh the raw material components according to 70% of waterborne polyurethane, 5% of waterborne silicone resin, 5% of waterborne silica sol (D50 is 10nm), 7% of modified microspheres (EMC-40B), 0.8% of fumed silica, 1% of fine fibers (length is 300um), 0.5% of dispersant, 0.3% of pH adjuster, 0.4% of thickener, and 10% of crosslinking agent, and set aside;

[0059] S2: Mixing: After mixing the above components, stir at 800-1000 r / min to disperse them uniformly; obtaining the wear-resistant printing slurry;

[0060] S3: Printing, transferring the wear-resistant printing slurry to the polyester cloth by hollow plate printing to form a coating with a thickness of 0.5 mm, and drying at 50° C. for 56 hours to obtain wear-resistant printed cloth. The cloth was tested for wear resistance, and the number of wear resistance was 65784 times.

[0061] Embodiment 2 A wear-resistant printing paste and printed fabric

[0062] S1: Weigh and weigh the raw material components according to 67.5% of waterborne polyurethane, 6.2% of waterborne silicone resin, 6.8% of waterborne silica sol (D50 is 8nm), 8% of modified microspheres (EMC-20B), 1.0% of fumed silica, 1.8% of fine fibers (length is 150um), 1.0% of dispersant, 0.5% of pH adjuster, 0.2% of thickener, and 7% of crosslinking agent, and set aside;

[0063] S2: Mixing: After mixing the above components, stir at 800-1000 r / min to disperse them uniformly; obtaining the wear-resistant printing slurry;

[0064] S3: Printing, transferring the wear-resistant printing slurry to nylon by screen printing to form a printing coating with a thickness of 1.0 mm, and drying at 70° C. for 48 h to obtain Figure 2 The wear-resistant printed fabric shown. The fabric was tested for wear resistance and the number of wear times was 84523.

[0065] Embodiment 3 A wear-resistant printing paste and printed fabric

[0066] S1: Weigh and weigh the raw material components according to 63.4% of waterborne polyurethane, 11.1% of waterborne silicone resin, 8.8% of waterborne silica sol (D50 is 5nm), 4% of modified microspheres (EMC-80B), 0.5% of fumed silica, 3% of fine fibers (length is 20um), 0.8% of dispersant, 0.4% of pH adjuster, 1.5% of thickener, and 6.5% of crosslinking agent, and set aside;

[0067] S2: Mixing: After mixing the above components, stir at 800-1000 r / min to disperse them uniformly; obtaining the wear-resistant printing slurry;

[0068] S3: Printing, transferring the wear-resistant printing slurry to the polyester cloth by thick coating with a hollow screen to form a coating with a thickness of 1.5 mm, and drying at 60° C. for 72 h to obtain Figure 3 The wear-resistant printed fabric shown. The fabric was tested for wear resistance and the number of wear times was 89956.

[0069] Embodiment 4 A wear-resistant printing paste and printed fabric

[0070] S1: Weigh and weigh the raw material components according to 60% of waterborne polyurethane, 15% of waterborne silicone resin, 10% of waterborne silica sol (D50 is 6nm), 5.6% of modified microspheres (EMC-40B), 0.7% of fumed silica, 1.1% of fine fibers (length is 80um), 1.0% of dispersant, 0.5% of pH adjuster, 1.1% of thickener, and 5% of crosslinking agent, and set aside;

[0071] S2: Mixing: After mixing the above components, stir at 800-1000 r / min to disperse them uniformly; obtaining the wear-resistant printing slurry;

[0072] S3: Printing, transferring the wear-resistant printing slurry to the polyester cloth by screen printing to form a coating with a thickness of 3.0 mm, and drying at 70° C. for 72 hours to obtain wear-resistant printed cloth. The cloth was tested for wear resistance, and the number of wear resistance was 110984 times.

[0073] Finally, it should be noted that although the above embodiments have been described in the specification and drawings of this application, this does not limit the scope of patent protection of this application. All technical solutions generated by replacing or modifying equivalent structures or equivalent processes based on the essential concept of this application using the contents recorded in the specification and drawings of this 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 this application.

Claims

1. A wear-resistant printing paste, characterized in that: The wear-resistant printing paste comprises the following components in percentage by mass: 60%-70% of waterborne polyurethane, 5%-15% of waterborne silicone resin, 5%-10% of waterborne silica sol, 4%-8% of modified microspheres and 1-3% of fine fibers; the modified microspheres do not deform under a pressure of 25 MPa, have a particle size D50 of 10-90 um, and a true density of 0.05-0.40 g / cm 3 Hollow plastic sphere.

2. The wear-resistant printing paste according to claim 1, characterized in that: The surface of the modified microspheres is covered with a calcium-containing compound.

3. The wear-resistant printing paste according to claim 1, characterized in that: The waterborne polyurethane is a waterborne polyurethane with hydroxyl groups, and the waterborne silicone resin is a silicone-modified polyether polyurethane.

4. The wear-resistant printing paste according to claim 1, characterized in that: The aqueous silica sol has a particle size of 5-10 nm.

5. The wear-resistant printing paste according to claim 1, characterized in that: The wear-resistant printing paste also includes 0.5%-1.0% fumed silica; the fumed silica is hydrophilic silica with a BET specific surface area of ​​130-300m 2 / g.

6. The wear-resistant printing paste according to claim 1, characterized in that: The fine fibers are polyester fibers with a length of 20-300 um.

7. The wear-resistant printing paste according to claim 1, characterized in that: The wear-resistant printing paste also includes 0.5-1.0% of a dispersant, 0.3-0.5% of a pH regulator, 0.2-1.5% of a thickener, and 5-10% of a cross-linking agent.

8. A method for preparing a wear-resistant printing paste, characterized in that: The wear-resistant printing paste according to any one of claims 1 to 7 is weighed according to components and mass, and stirred evenly at 800 to 1000 r / min to obtain the wear-resistant printing paste.

9. A method for preparing a wear-resistant printed fabric, characterized in that: The wear-resistant printing paste of any one of claims 1 to 7 is applied to a base fabric by screen printing or thick coating with a hollow screen to form a printing layer of 0.3 to 4.0 mm; after the printing layer is dried, the wear-resistant printed fabric is obtained.

10. A wear-resistant printed fabric, characterized in that: The wear-resistant printed fabric is prepared by the preparation method described in claim 9.

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