Fluoride-free waterproof printed fabric and preparation method thereof

Abstract

The invention relates to a fluoride-free waterproof printed fabric and a preparation method thereof.The preparation method sequentially comprises the following steps that first-time waterproof finishing is conducted, specifically, cloth is subjected to padding with an immersion liquid containing a water-based waterproof agent and then dried, cloth subjected to first-time finishing is obtained, and the water-based waterproof agent contains-OH and-NCO groups; printing: carrying out silk-screen printing on a preset part of the cloth subjected to primary finishing by using a waterborne polyurethane coating containing blocked isoamino acid ester, and drying to obtain a printed cloth; and secondary waterproof finishing: spraying the printed fabric with a finishing liquid containing an oily waterproof agent, and drying to obtain the fluoride-free waterproof printed fabric. Different from the prior art, the technical scheme adopts two waterproof processes, the peel strength of the printed coating is high, the waterproof requirement of the fabric is met, the bonding effect of the fabric and the printed coating is improved, and the process is simple.

Description

Technical Field

[0001] The present application relates to the field of textiles, and particularly to a fluorine-free waterproof printed fabric and a preparation method thereof. Background Art

[0002] In activities such as outdoor adventures, hiking, mountain climbing, cycling, etc., people often encounter wet environments such as rain and dew. Fabrics treated with waterproofing can effectively block the penetration of moisture and keep the inside of the clothing dry. From the perspective of sustainable development, waterproofing treatment can extend the service life of the fabric, reduce the discard of clothing and textiles due to damage caused by moisture, and thus reduce the pressure on the environment.

[0003] Currently, when preparing waterproof printed fabrics, usually after the fabric is waterproofed, coating printing is carried out. However, due to the waterproof treatment of the fabric, the bonding property with the printing coating is reduced, and the situation that the printing coating is easy to fall off will occur. Summary of the Invention

[0004] In view of the above problems, the present application provides a fluorine-free waterproof printed fabric and a preparation method thereof. The preparation method adopts two waterproof finishing processes, uses a fluorine-free waterproof agent which is healthy and environmentally friendly, improves the peel strength of the printing coating while ensuring the waterproof effect, and extends the service life of the waterproof printed fabric.

[0005] The present application provides a preparation method of a fluorine-free waterproof printed fabric, and the preparation method successively includes the following steps:

[0006] First waterproof finishing: The fabric is impregnated and rolled with an immersion liquid containing a water-based waterproof agent and then dried at 160 - 180 °C to obtain the fabric after the first finishing; the water-based waterproof agent contains -OH and -NCO groups;

[0007] Printing: Screen printing is carried out on the predetermined part of the fabric after the first finishing with a water-based polyurethane coating containing blocked isocyanate, and the printed fabric is obtained after drying;

[0008] Second waterproof finishing: The printed fabric is sprayed with a finishing liquid containing an oil-based waterproof agent and then dried to obtain the fluorine-free waterproof printed fabric.

[0009] Different from the prior art, the above technical solution provides a fluorine-free waterproof printed fabric and a preparation method thereof. This method adopts two waterproof processes, has a high peel strength of the printing coating, not only meets the waterproof requirement of the fabric, but also improves the bonding effect between the fabric and the printing coating, has a simple process, and is more environmentally friendly.

[0010] Furthermore, in the first waterproof finishing step, the content of the water-based waterproof agent in the immersion liquid is 6 - 8 wt%, the one-dip-one-roll preparation method is adopted, the impregnation and rolling pressure is 0.3 MPa, and the liquor pickup rate is 50% - 60%.

[0011] Further, in the first waterproof finishing step, the dipping solution further comprises 1.1 - 2.0 wt% of a waterproof and oil-proof enhancer and 0.5 - 1 wt% of a special waterproof penetrant.

[0012] Further, in the first waterproof finishing step, the mass ratio of the aqueous waterproof agent, the waterproof and oil-proof enhancer, and the special waterproof penetrant is 60 - 80:11 - 20:5 - 10.

[0013] Further, in the first waterproof finishing step, after padding, the fabric is first dried at 120 - 150 °C for 30 s and then dried at 160 - 180 °C.

[0014] Further, in the second waterproof finishing step, the finishing solution contains 11 - 15 wt% of an oil-based waterproof liquid; the oil-based waterproof liquid is prepared from 11 - 15 parts by mass of an oil-based waterproof agent and 85 - 89 parts by mass of a polar solvent.

[0015] Further, the polar solvent includes ethyl acetate, heptane or a mixture thereof.

[0016] Further, in the second waterproof finishing step, the finishing solution further comprises 1 - 3 wt% of a trifunctional aziridine cross-linking agent and 1 - 10 wt% of a polycarbodiimide auxiliary agent.

[0017] Further, in the second waterproof finishing step, first, it is shaped and dried at 60 - 80 °C for 30 s, and then dried at 160 - 180 °C.

[0018] Further, it further includes a fabric pretreatment step: the grey fabric is washed to remove oil and then dried to obtain the fabric.

[0019] The present application also provides a fluorine-free waterproof printed fabric, and the fluorine-free waterproof printed fabric is prepared by using the above preparation method.

[0020] Different from the prior art, the above technical solution provides a fluorine-free waterproof printed fabric with good waterproof performance and high peeling strength of the printed coating; it can be applied to the production of textile products with high waterproof requirements such as shoes and outdoor products.

[0021] The above relevant descriptions of the invention content are only an overview of the technical solution of the present application. In order to enable those of ordinary skill in the art to more clearly understand the technical solution of the present application, and thus can be implemented according to the content recorded in the specification, and in order to make the above objects, other objects, features and advantages of the present application more easily understood, the following is described in conjunction with the specific embodiments of the present application. Specific Embodiments

[0022] To describe in detail the technical content, structural features, achieved objectives and effects of the technical solution, the following will be elaborated in detail with specific embodiments.

[0023] 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 solution of this application, so they are only examples and cannot be used to limit the protection scope of this application.

[0024] As used herein, the mention of "embodiment" means that the specific features, structures or characteristics described in connection with the embodiment can be included in at least one embodiment of this application. The term "embodiment" that appears in 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 technical features mentioned in each embodiment can be combined in any way to form corresponding implementable technical solutions.

[0025] 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.

[0026] 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 can exist. 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 " / " herein generally represents an "or" logical relationship between the associated objects before and after.

[0027] 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.

[0028] Without more limitations, in this application, the expressions such as "including", "comprising", "having" or other similar expressions used in the statement are 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 may not only include those defined elements, but also include other elements not explicitly listed, or also include elements inherent to this process, method or product.

[0029] 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.

[0030] This application provides a method for preparing a fluorine-free waterproof printed fabric. The preparation method successively includes the following steps:

[0031] First waterproof finishing: The fabric is impregnated and rolled with an immersion liquid containing a water-based waterproof agent and then dried at 160-180°C to obtain the fabric after the first finishing; the water-based waterproof agent contains -OH and -NCO groups;

[0032] Printing: Screen printing is performed on the predetermined part of the fabric after the first finishing with a water-based polyurethane coating containing blocked isocyanate, and the printed fabric is obtained after drying;

[0033] Second waterproof finishing: The printed fabric is sprayed with a finishing liquid containing an oil-based waterproof agent and then dried to obtain the fluorine-free waterproof printed fabric.

[0034] In the first waterproof finishing step, a first water-based waterproof film is formed on the fabric surface. At the same time, the -OH in the water-based waterproof agent will react with the NCO groups released by the water-based polyurethane coating containing blocked isocyanate at a temperature of 160°C - 180°C, promoting the formation of a three-dimensional network structure of the groups on the fiber surface, providing a linking group for chemical reactions, and improving the peeling strength of the fabric.

[0035] In the printing step, a printed layer is formed through multiple screen printings.

[0036] In the second waterproof finishing step, spraying is used to form a second waterproof film with a relatively uniform thickness on the surface of the printed fabric; at the same time, the printed layer contains polar components such as ink, enhancing the adhesion of the oil-based waterproof film to the printed layer, covering and protecting the printed layer.

[0037] Different from the prior art, the above technical solution provides a fluorine-free waterproof printed fabric and its preparation method. This method uses two waterproof processes, has good process compatibility, and the printed coating has high peeling strength. It not only meets the waterproof performance requirements of the fabric, improves the adhesion effect between the fabric and the printed coating, has a simple process, is convenient for subsequent recycling, and is environmentally friendly.

[0038] Furthermore, in the first waterproof finishing step, the content of the water-based waterproof agent in the immersion liquid is 6-8wt%, the one-dip-one-roll preparation method is adopted, the impregnation and rolling pressure is 0.3MPa, and the liquor pick-up rate is 50%-60%.

[0039] The dosage of the water-based waterproof agent in the dipping solution will affect the peeling strength of the printed coating. If the dosage of the water-based waterproof agent is too high, although the waterproof effect is good, it will affect the bonding between the printed coating and the fabric, resulting in low peeling strength; while if the content of the water-based waterproof agent is too low, the waterproof performance of the fabric will be affected. Therefore, in this application, the content of the water-based waterproof agent in the dipping solution is set to 6-8 wt%.

[0040] In the first waterproof finishing step, the dipping solution further includes 1.1-2.0 wt% of a waterproof and oil-proof enhancer and 0.5-1 wt% of a special waterproof penetrant.

[0041] Furthermore, the waterproof and oil-proof enhancer is a waterproof and oil-proof enhancer containing a silicon-oxygen bond. The silicon-oxygen bond (Si-O) has a high bond energy, the molecular chain is stable and not easily damaged by water molecules, and it can form a tight hydrophobic film on the fabric surface, effectively preventing the penetration of water molecules. Preferably, it is polydimethylsiloxane.

[0042] Furthermore, the special waterproof penetrant is a silicone-based penetrant. Silicone can reduce the surface tension, making the liquid easier to spread and penetrate. This type of penetrant assists the water-based waterproof agent to penetrate into the fabric gaps, enabling the active groups such as -OH in the water-based waterproof agent to undergo a cross-linking reaction with the fabric during the drying process, making the first waterproof film formed by the water-based waterproof agent tightly bonded to the fabric.

[0043] Furthermore, in the first waterproof finishing step, after padding, the fabric is first dried at 120-150 °C for 30 s, and then dried at 160-180 °C.

[0044] The water-based waterproof agent is quickly shaped at 120-150 °C without undergoing a chemical reaction; while the -OH and -NCO groups of the water-based waterproof agent react with the water-based polyurethane coating containing blocked isocyanate at a temperature of 160 °C - 180 °C to release -NH 2 , and the -OH groups will react, promoting the formation of a three-dimensional network structure on the fiber surface, providing a linking group for the chemical reaction and enhancing the peeling strength of the fabric.

[0045] The active groups such as -OH in the water-based waterproof agent undergo a cross-linking reaction with the fabric during the drying process. The higher the temperature, the better the degree of molecular cross-linking reaction. When the drying temperature reaches 160 °C, the cross-linking is sufficient, making the first waterproof film formed by the water-based waterproof agent tightly bonded to the fabric.

[0046] Furthermore, the printing step is carried out within 30-60 s after the first waterproof finishing step.

[0047] The first waterproof finishing is finally dried at 160 - 180°C. The first waterproof film remains at a high temperature while the -OH groups in the water-based waterproofing agent remain active. During the subsequent printing step within 30 - 60 s, the water-based polyurethane coating releases -NH 2 , -OH groups react with -NCO in the water-based waterproofing agent, increasing its crosslinking degree and enhancing the peel strength of the printed coating.

[0048] Furthermore, in the secondary waterproof finishing step, the finishing liquid contains 11 - 15 wt% of an oil-based waterproofing liquid; the oil-based waterproofing liquid is prepared from 11 - 15 parts by mass of an oil-based waterproofing agent and 85 - 89 parts by mass of a polar solvent.

[0049] Furthermore, the polar solvent includes ethyl acetate, heptane or a mixture thereof.

[0050] Furthermore, in the secondary waterproof finishing step, the finishing liquid further includes a trifunctional aziridine crosslinking agent and polycarbodiimide. The addition of the above auxiliaries can improve the adhesion of the oil-based waterproofing agent and increase the compatibility of the first water-based waterproof film, the printed coating and the second oil-based waterproof film.

[0051] Furthermore, the water-based waterproofing agent contains -COOH, -OH, -NCO groups.

[0052] The aziridine crosslinking agent reacts with -COOH in the water-based waterproofing agent to form chemical bonds, connecting linear molecules together to form a network structure, thereby improving the strength and elasticity of the coating. The reaction of polycarbodiimide with -COOH first forms O - acylurea, and O - acylurea rearranges to form N - acylurea; N - acylurea can be converted into amide and isocyanate, and the formed isocyanate can react with -NH 2 or -OH in the water-based polyurethane printing coating structure, especially at the end groups, to form a further crosslinked form.

[0053] Furthermore, the content of the trifunctional aziridine crosslinking agent is 1 - 3 wt%.

[0054] Furthermore, the content of the polycarbodiimide is 1 - 10 wt%, preferably 5.00 - 10 wt%.

[0055] Furthermore, in the secondary waterproof finishing step, it is first shaped and dried at 60 - 80°C for 30 s, and then dried at 160 - 180°C.

[0056] In the secondary waterproof finishing step, the water-based polyurethane coating will continue to release NCO groups at 160°C and react with -OH in the water-based waterproofing agent, increasing its crosslinking degree and enhancing the peel strength of the printed coating.

[0057] Further, it also includes a cloth pretreatment step: washing and degreasing the grey cloth and then drying it to obtain the cloth.

[0058] This application also provides a fluorine-free waterproof printed fabric, which is prepared by the above preparation method.

[0059] Different from the prior art, the above technical solution provides a fluorine-free waterproof printed fabric with good waterproof performance and high peeling strength of the printing coating; it can be applied to the production of textile products with high waterproof requirements such as shoes and outdoor products.

[0060] The water-based waterproof agent in this embodiment is a water-based waterproof agent containing -COOH, -OH, and -NCO groups, namely the water-based waterproof agent 9038 of Fuko New Materials Co., Ltd. The oil-based waterproof agent is pm-3869 of Fuko New Materials Co., Ltd.

[0061] The waterproof and oil-proof enhancer is a polydimethylsiloxane-based waterproof and oil-proof enhancer; the special waterproof penetrant is a silicone-based penetrant; it is purchased from Suzhou Zhiyuan Xinke Chemical Co., Ltd.

[0062] The trifunctional aziridine crosslinking agent and polycarbodiimide auxiliary are purchased from Fuko New Materials Co., Ltd. The water-based polyurethane coating containing blocked isocyanate in this embodiment forms -NCO at 160°C and is purchased from Wanhua Chemical Group Co., Ltd.

[0063] Example 1

[0064] Pretreatment: Immerse the grey cloth in hot water containing detergent at 80 - 100°C for 30 min and stir at a low speed of 400 - 500 r / min for 5 min; after the immersion, rinse it clean and drain the water through a calendar (pressure: 0.3 MPa), and quickly dry it in an oven at 150 - 180°C to obtain the cloth;

[0065] First waterproof finishing: Immerse and roll the cloth with the immersion liquid containing the water-based waterproof agent and then dry it to obtain the cloth after the first finishing; the immersion liquid contains 6.2 wt% of the water-based waterproof agent, 1.6 wt% of the waterproof and oil-proof enhancer, and 0.8 wt% of the special waterproof penetrant; adopt the one-dip-one-roll preparation method, the immersion and rolling pressure is 0.3 MPa, and the pick-up rate is 50% - 60%; after immersion and rolling, the cloth is first dried at 120 - 150°C for 30 s and then dried at 160 - 180°C.

[0066] Printing: Print the cloth after the first finishing with the water-based polyurethane coating containing blocked isocyanate 12 times under a 60-mesh screen to obtain the printed cloth.

[0067] Secondary waterproof finishing: After spraying the printed fabric with a finishing solution containing an oil-based waterproof agent, it is shaped and dried at 60 - 80°C for 30 s by a shaping machine, and then sent to an open oven for drying at 40 - 50°C to obtain a fluorine-free waterproof printed fabric.

[0068] The finishing solution contains an oil-based waterproof liquid, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent is 2.4 wt%, and the content of polycarbodiimide is 6.3 wt%. The oil-based waterproof liquid is prepared from 13.10 wt% of an oil-based waterproof agent and 86.90 wt% of a polar solvent heptane.

[0069] Perform performance testing on the fluorine-free waterproof printed fabric prepared in Example 1:

[0070] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlining", conduct the detection of the adhesion and peel strength of the print, and the detection result is: 9.92 N.

[0071] According to GB / T 4744—2013 "Testing and Evaluation of Waterproof Properties of Textiles - Hydrostatic Pressure Method", conduct the waterproof grade detection, and the result is Grade 4.

[0072] According to GB / T 4745—2012 "Testing and Evaluation of Waterproof Properties of Textiles - Spray Test Method", conduct the waterproof grade detection, and the result is Grade 4.

[0073] Example 2

[0074] The difference between Example 2 and Example 1 is:

[0075] In the first waterproof finishing step, the dipping solution contains 6.3 wt% of an aqueous waterproof agent, 1.61 wt% of a waterproof and oil-proof enhancer, and 0.81 wt% of a special waterproof penetrant.

[0076] In the secondary waterproof finishing step, the finishing solution contains an oil-based waterproof liquid, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent is 2.2 wt%, and the content of polycarbodiimide is 6.1 wt%. The oil-based waterproof liquid is prepared from 13.20 wt% of an oil-based waterproof agent and 86.80 wt% of a polar solvent heptane.

[0077] Perform performance testing on the fluorine-free waterproof printed fabric prepared in Example 2:

[0078] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlining", conduct the detection of the adhesion and peel strength of the print, and the detection result is: 9.56 N.

[0079] The waterproof level was tested in accordance with GB / T 4744—2013 "Textiles - Determination of waterproof properties - Hydrostatic pressure method", and the result was Grade 4.

[0080] The waterproof level was tested in accordance with GB / T 4745—2012 "Textiles - Determination of waterproof properties - Spray test", and the result was Grade 4.

[0081] Example 3

[0082] The difference between Example 3 and Example 1 is as follows:

[0083] In the first waterproof finishing step, the dipping solution contained 6.5 wt% of waterborne waterproof agent, 1.63 wt% of waterproof and oil-proof enhancer, and 0.84 wt% of special waterproof penetrant.

[0084] In the second waterproof finishing step, the finishing solution contained oil-based waterproof liquid, trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of trifunctional aziridine crosslinking agent was 2.0 wt%, and the content of polycarbodiimide was 5.9 wt%. The oil-based waterproof liquid was prepared from 13.40 wt% of oil-based waterproof agent and 86.60 wt% of polar solvent heptane.

[0085] The fluorine-free waterproof printed fabric prepared in Example 3 was subjected to performance testing:

[0086] In accordance with FZ / T 80007.1—2006 "Test method for peel strength of bonded lining used in garments", the adhesion peel strength of the print was tested, and the test result was: 9.32 N.

[0087] The waterproof level was tested in accordance with GB / T 4744—2013 "Textiles - Determination of waterproof properties - Hydrostatic pressure method", and the result was Grade 4.

[0088] The waterproof level was tested in accordance with GB / T 4745—2012 "Textiles - Determination of waterproof properties - Spray test", and the result was Grade 4.

[0089] Example 4

[0090] The difference between Example 4 and Example 1 is as follows:

[0091] In the first waterproof finishing step, the dipping solution contained 6.8 wt% of waterborne waterproof agent, 1.65 wt% of waterproof and oil-proof enhancer, and 0.83 wt% of special waterproof penetrant.

[0092] In the secondary waterproof finishing step, the finishing liquid contains an oil-based waterproof liquid, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent is 1.8 wt%, and the content of polycarbodiimide is 5.5 wt%. The oil-based waterproof liquid is prepared from 13.70 wt% of an oil-based waterproof agent and 86.30 wt% of the polar solvent heptane.

[0093] Perform performance testing on the fluorine-free waterproof printed fabric prepared in Example 4:

[0094] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlinings", conduct the detection of the adhesion and peel strength of the print. The test result is: 9.06 N.

[0095] According to GB / T 4744—2013 "Testing and Evaluation of Waterproof Performance of Textiles - Hydrostatic Pressure Method", conduct the waterproof grade detection, and the result is Grade 4.

[0096] According to GB / T 4745—2012 "Testing and Evaluation of Waterproof Performance of Textiles - Spray Test Method", conduct the waterproof grade detection, and the result is Grade 4.

[0097] Example 5

[0098] The difference between Example 5 and Example 1 is:

[0099] In the first waterproof finishing step, the dipping liquid contains 6 wt% of an aqueous waterproof agent, 1.57 wt% of a waterproof and oil-proof enhancer, and 0.78 wt% of a special waterproof penetrant.

[0100] In the secondary waterproof finishing step, the finishing liquid contains an oil-based waterproof liquid, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent is 1.5 wt%, and the content of polycarbodiimide is 5.0 wt%. The oil-based waterproof liquid is prepared from 13 wt% of an oil-based waterproof agent, 43.5 wt% of ethyl acetate, and 43.5 wt% of heptane.

[0101] Perform performance testing on the fluorine-free waterproof printed fabric prepared in Example 5:

[0102] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlinings", conduct the detection of the adhesion and peel strength of the print. The test result is: 8.56 N.

[0103] According to GB / T 4744—2013 "Testing and Evaluation of Waterproof Performance of Textiles - Hydrostatic Pressure Method", conduct the waterproof grade detection, and the result is Grade 4.

[0104] According to GB / T 4745—2012 "Testing and Evaluation of Waterproof Performance of Textiles - Spray Test Method", conduct the waterproof grade detection, and the result is Grade 4.

[0105] Example 6

[0106] The difference between Example 6 and Example 1 is as follows:

[0107] In the first waterproof finishing step, the dipping solution contains 6 wt% of water-based waterproof agent, 1.57 wt% of waterproof and oil-proof enhancer, and 0.78 wt% of special waterproof penetrant.

[0108] In the second waterproof finishing step, the finishing solution contains oil-based waterproof liquid, trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of trifunctional aziridine crosslinking agent is 1.8 wt%, and the content of polycarbodiimide is 5.5 wt%. The oil-based waterproof liquid is prepared from 13 wt% of oil-based waterproof agent and 87 wt% of ethyl acetate. The fluorine-free waterproof printed fabric prepared in Example 6 was subjected to performance testing:

[0109] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Adhesive Lining Used in Garments", the adhesion and peel strength of the print was tested, and the test result was: 8.71 N.

[0110] According to GB / T 4744—2013 "Testing and Evaluation of Waterproof Property of Textiles - Hydrostatic Pressure Method", the waterproof grade was tested, and the result was Grade 4.

[0111] According to GB / T 4745—2012 "Testing and Evaluation of Waterproof Property of Textiles - Spray Test Method", the waterproof grade was tested, and the result was Grade 4.

[0112] Example 7

[0113] The difference between Example 7 and Example 1 is as follows:

[0114] In the first waterproof finishing step, the dipping solution contains 6 wt% of water-based waterproof agent, 1.57 wt% of waterproof and oil-proof enhancer, and 0.78 wt% of special waterproof penetrant.

[0115] In the second waterproof finishing step, the finishing solution contains oil-based waterproof liquid, trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of trifunctional aziridine crosslinking agent is 1.8 wt%, and the content of polycarbodiimide is 1.0 wt%. The oil-based waterproof liquid is prepared from 15 wt% of oil-based waterproof agent and 85 wt% of heptane.

[0116] The fluorine-free waterproof printed fabric prepared in Example 7 was subjected to performance testing:

[0117] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Adhesive Lining Used in Garments", the adhesion and peel strength of the print was tested, and the test result was: 7.32 N.

[0118] The waterproof grade was tested in accordance with GB / T 4744—2013 "Textiles - Determination of waterproof performance - Hydrostatic pressure method", and the result was grade 5.

[0119] The waterproof grade was tested in accordance with GB / T 4745—2012 "Textiles - Determination of waterproof performance - Spray test", and the result was grade 3.

[0120] Example 8

[0121] The differences between Example 8 and Example 1 are as follows:

[0122] In the first waterproof finishing step, the dipping solution contains 6 wt% of waterborne waterproof agent, 1.48 wt% of waterproof and oil-proof enhancer, and 0.72 wt% of special waterproof penetrant.

[0123] In the second waterproof finishing step, the finishing solution contains oil-based waterproof liquid, trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of trifunctional aziridine crosslinking agent is 1.8 wt%, and the content of polycarbodiimide is 10 wt%. The oil-based waterproof liquid is prepared from 11 wt% of oil-based waterproof agent and 89 wt% of heptane.

[0124] The performance of the fluorine-free waterproof printed fabric prepared in Example 8 was tested:

[0125] In accordance with FZ / T 80007.1—2006 "Test method for peel strength of adhesives used in apparel", the adhesion peel strength of the printing was tested, and the test result was: 10.56 N.

[0126] The waterproof grade was tested in accordance with GB / T 4744—2013 "Textiles - Determination of waterproof performance - Hydrostatic pressure method", and the result was grade 4.

[0127] The waterproof grade was tested in accordance with GB / T 4745—2012 "Textiles - Determination of waterproof performance - Spray test", and the result was grade 4.

[0128] Example 9

[0129] The differences between Example 9 and Example 1 are as follows:

[0130] In the first waterproof finishing step, the dipping solution contains 4 wt% of waterborne waterproof agent, 1.23 wt% of waterproof and oil-proof enhancer, and 0.56 wt% of special waterproof penetrant.

[0131] In the second waterproof finishing step, the finishing solution contains oil-based waterproof liquid, trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of trifunctional aziridine crosslinking agent is 1.8 wt%, and the content of polycarbodiimide is 5 wt%. The oil-based waterproof liquid is prepared from 13 wt% of oil-based waterproof agent and 87 wt% of heptane.

[0132] The fluorine-free waterproof printed fabric prepared in Example 9 was subjected to performance testing:

[0133] In accordance with FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlining", the adhesion and peel strength of the printing was tested, and the test result was: 9.26 N.

[0134] In accordance with GB / T 4744—2013 "Textiles - Determination and evaluation of waterproof properties - Hydrostatic pressure method", the waterproof grade was tested, and the result was Grade 4.

[0135] In accordance with GB / T 4745—2012 "Textiles - Determination and evaluation of waterproof properties - Spray test", the waterproof grade was tested, and the result was Grade 4.

[0136] Example 10

[0137] The difference between Example 10 and Example 1 is:

[0138] In the first waterproof finishing step, the immersion liquid contained 8 wt% of a water-based waterproof agent, 1.78 wt% of a waterproof and oil-proof enhancer, and 0.89 wt% of a special waterproof penetrant.

[0139] In the second waterproof finishing step, the finishing liquid contained an oil-based waterproof liquid, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent was 1.8 wt%, and the content of polycarbodiimide was 5 wt%. The oil-based waterproof liquid was prepared from 13 wt% of an oil-based waterproof agent and 87 wt% of heptane.

[0140] The fluorine-free waterproof printed fabric prepared in Example 10 was subjected to performance testing:

[0141] In accordance with FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlining", the adhesion and peel strength of the printing was tested, and the test result was: 7.12 N.

[0142] In accordance with GB / T 4744—2013 "Textiles - Determination and evaluation of waterproof properties - Hydrostatic pressure method", the waterproof grade was tested, and the result was Grade 5.

[0143] In accordance with GB / T 4745—2012 "Textiles - Determination and evaluation of waterproof properties - Spray test", the waterproof grade was tested, and the result was Grade 4.

[0144] Example 11

[0145] The difference between Example 11 and Example 1 is:

[0146] In the first waterproof finishing step, the immersion liquid contained 4 wt% of a water-based waterproof agent, 1.23 wt% of a waterproof and oil-proof enhancer, and 0.56 wt% of a special waterproof penetrant.

[0147] In the secondary waterproof finishing step, the finishing solution contains an oil-based waterproofing agent, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent is 3 wt%, and the content of polycarbodiimide is 10 wt%. The oil-based waterproofing agent is prepared from 11 wt% of an oil-based waterproofing agent and 89 wt% of ethyl acetate.

[0148] Perform performance testing on the fluorine-free waterproof printed fabric prepared in Example 11:

[0149] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlining", conduct the detection of the adhesion and peel strength of the print. The test result is: 10.89 N.

[0150] According to GB / T 4744—2013 "Textiles - Determination and evaluation of waterproof properties - Hydrostatic pressure method", conduct the waterproof grade detection, and the result is Grade 4.

[0151] According to GB / T 4745—2012 "Textiles - Determination and evaluation of waterproof properties - Spray test", conduct the waterproof grade detection, and the result is Grade 4.

[0152] Example 12

[0153] The difference between Example 12 and Example 1 is:

[0154] In the first waterproof finishing step, the dipping solution contains 8 wt% of an aqueous waterproofing agent, 1.82 wt% of a waterproof and oil-proof enhancer, and 0.91 wt% of a special waterproof penetrant.

[0155] In the secondary waterproof finishing step, the finishing solution contains an oil-based waterproofing agent, a trifunctional aziridine crosslinking agent, and polycarbodiimide; the content of the trifunctional aziridine crosslinking agent is 1 wt%, and the content of polycarbodiimide is 1 wt%. The oil-based waterproofing agent is prepared from 15 wt% of an oil-based waterproofing agent and 85 wt% of ethyl acetate.

[0156] Perform performance testing on the fluorine-free waterproof printed fabric prepared in Comparative Example 1:

[0157] According to FZ / T 80007.1—2006 "Test Method for Peel Strength of Garments Using Adhesive Interlining", conduct the detection of the adhesion and peel strength of the print. The test result is: 5.36 N.

[0158] According to GB / T 4744—2013 "Textiles - Determination and evaluation of waterproof properties - Hydrostatic pressure method", conduct the waterproof grade detection, and the result is Grade 5.

[0159] According to GB / T 4745—2012 "Textiles - Determination and evaluation of waterproof properties - Spray test", conduct the waterproof grade detection, and the result is Grade 3.

[0160] As can be seen from Example 9 and Example 10, the dosage of the aqueous waterproofing agent affects the adhesion and peeling strength of the printing. Although a large dosage can increase the waterproof property, the peeling strength of the printing will decrease.

[0161] As can be seen from the above examples, if the contents of the waterproof and oil-proof enhancer and the special waterproof penetrant are too high, the adhesion and peeling strength between the printing coating and the fabric will decrease, because it will make the waterproof property of the first-step aqueous waterproofing agent too high, which is not conducive to the printing of the subsequent aqueous polyurethane coating. In addition, if the content of the trifunctional aziridine crosslinking agent is too low, the adhesion and peeling strength between the printing coating and the fabric will decrease. Because the content is too low, the crosslinking reaction with the polyurethane aqueous coating is insufficient, affecting its peeling strength. The reaction of polycarbodiimide with -COOH will form O-ureide, and O-ureide will rearrange to form N-ureide; N-ureide can be converted into amide and isocyanate, and the formed isocyanate can react with -NH 2 or -OH in the structure of the aqueous polyurethane printing coating, especially at the end group, to form a further crosslinked form, increasing the peeling strength. The content of the trifunctional aziridine crosslinking agent is preferably 3%; the content of polycarbodiimide is preferably 10%.

[0162] Finally, it should be noted that although the above embodiments have been described in the text of the specification of this application, the patent protection scope of this application cannot be limited thereby. Any technical solutions obtained by equivalent structure or equivalent process substitution or modification based on the essential concept of this application and using the content recorded in the text of the specification of this application, as well as directly or indirectly implementing the technical solutions of the above embodiments in other related technical fields, etc., are all included in the patent protection scope of this application.

Claims

1. A method for preparing a fluorine-free waterproof printed fabric, characterized in that: The preparation method comprises the following steps in sequence: First waterproof finishing: the fabric is dipped into a liquid containing an aqueous waterproofing agent and then dried at 160-180° C. to obtain the first finished fabric; the aqueous waterproofing agent contains -OH, -NCO groups; Printing: Screen printing is performed on the predetermined part of the fabric after the primary finishing with a water-based polyurethane coating containing blocked isocyanate, and the printed fabric is obtained after drying; Secondary waterproof finishing: spraying the printed fabric with a finishing liquid containing an oily waterproof agent and then drying it to obtain the fluorine-free waterproof printed fabric.

2. The preparation method according to claim 1, characterized in that: In the first waterproof finishing step, the amount of the water-based waterproofing agent in the immersion liquid is 6-8wt%, and a one-immersion-one-rolling preparation method is adopted, the immersion-rolling pressure is 0.3MPa, and the rolling rate is 50%-60%.

3. The preparation method according to claim 1, characterized in that: In the first waterproof finishing step, the immersion liquid also includes 1.1-2.0 wt % of a waterproof and oil-proof enhancer and 0.5-1 wt % of a special waterproof penetrant.

4. The preparation method according to claim 1, characterized in that: In the first waterproof finishing step, the fabric after padding is first dried at 120-150° C. for 30 seconds and then dried at 160-180° C.

5. The preparation method according to claim 1, characterized in that: In the secondary waterproof finishing step, the finishing liquid contains 11-15 wt % of an oily waterproof liquid, and the oily waterproof liquid is prepared from 11-15 parts by weight of an oily waterproof agent and 85-89 parts by weight of a polar solvent.

6. The preparation method according to claim 4, characterized in that: The polar solvent includes ethyl acetate, heptane or a mixture thereof.

7. The preparation method according to claim 6, characterized in that: The finishing liquid also includes 1-3 wt % of a trifunctional aziridine cross-linking agent and 1-10 wt % of a polycarbodiimide auxiliary agent.

8. The preparation method according to claim 1, characterized in that: In the secondary waterproof finishing step, the molding is first dried at 60-80°C for 30 seconds, and then dried at 160-180°C.

9. The preparation method according to claim 1, characterized in that: The method also includes a cloth pretreatment step: washing, degreasing and drying the grey cloth to obtain the cloth.

10. A fluorine-free waterproof printed fabric, characterized in that: The fluorine-free waterproof printed fabric is prepared by the preparation method described in any one of claims 1 to 9.