Finishing liquid for waterproof and soft one-bath treatment of microfibers and application of finishing liquid

Abstract

The invention belongs to the technical field of after-finishing of microfiber synthetic leather, and particularly discloses a finishing liquid for waterproof softening one-bath and application of the finishing liquid, the finishing liquid comprises one or more liquid additive components, and the finishing liquid comprises the following components in percentage by weight: 5-25% of a waterproof agent, 0.5-2% of a microfiber softening agent, 1-5% of a cross-linking agent, 0.01-0.2% of a pH regulator and the balance of water, the waterproof agent is a fluoride-free waterproof agent, and the softening agent is a microfiber softening agent. Before waterproof and soft one-bath finishing, a waterproof pretreating agent needs to be adopted for a pretreatment process. The microfiber synthetic leather can be used for waterproof and soft one-bath finishing, the process is shortened, the waterproof effect is good, the hand feeling is soft, the environmental protection concept is met, and the ideal static and dynamic anti-siphon quality requirements are met.

Description

Technical Field

[0001] The invention belongs to the technical field of finishing of ultra-fiber synthetic leather, and more specifically, relates to a finishing liquid for waterproofing and softening ultra-fiber in one bath and application thereof. Background Art

[0002] Microfiber is the abbreviation of ultrafine fiber synthetic leather (Note: nylon / polyurethane (PA / PU)). Microfiber synthetic leather has a wide range of uses and is widely used in sports shoes, automotive interiors, luggage and other industries. It is required to have better waterproof properties. For example, in shoe applications, it must have both good static anti-siphon effect and good dynamic anti-siphon effect, as well as excellent soft and elastic feel. However, in the current industrial production process, softening finishing and waterproofing finishing are two independent processes. Softening finishing is performed first, and then waterproofing finishing is performed, that is, a two-bath two-step processing method is adopted, which results in a longer processing flow, time-consuming, and high energy consumption.

[0003] In the early application field of fluorine-containing waterproofing agents, such as the fluorine-containing waterproof finishing agent (note: the fluorocarbon chain length is 8) for textile waterproofing and oil repellency disclosed in patent document CN100545344C, the waterproof effect is good, but the perfluorocarbon chain compound with a fluorocarbon chain length of 8 is stable in nature, but in the production process, by-products such as PFOA (perfluorooctanoic acid ammonium), PFOS (perfluorooctane sulfonate), and PFAS (perfluorooctane sulfonate) are produced, which accumulate in the environment and the human body, are difficult to biodegrade for a long time, and are harmful to the environment and organisms.

[0004] At present, in the latest application areas of waterproofing agents, hexacarbon waterproofing agents and fluorine-free waterproofing agents are mainly used to comply with the latest environmental protection requirements such as the EU REACH regulations and the ZDHC (Zero Discharge of Toxic and Hazardous Chemicals) Alliance. Compared with hexacarbon waterproofing agents, fluorine-free waterproofing agents do not contain fluorine elements, which makes them more environmentally friendly and more acceptable to the public. They are the main direction and trend of future development. However, since the application performance and durability of fluorine-free waterproofing agents are inferior to those of fluorine-containing waterproofing agents, their application is subject to certain restrictions. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a finishing liquid for waterproofing and softening microfibers in one bath and its application, aiming to solve the problems of the existing waterproofing and softening finishing two-bath two-step method, which has cumbersome process, high energy consumption and unsatisfactory effect.

[0006] To achieve the above-mentioned purpose, the present invention provides a finishing liquid for waterproofing and softening microfibers in one bath and its application, wherein the finishing liquid comprises one or more liquid auxiliary components, which are as follows by weight: 8% to 25% of a waterproofing agent, 0.5% to 2% of a softening agent, and 0.01% to 0.2% of a pH adjusting agent, and the rest is water.

[0007] The waterproofing agent in the finishing liquid is a fluorine-free waterproofing agent, which comprises, by weight percentage, 5% to 15% octadecyl acrylate, 10% to 30% polyurethane isocyanate ester and 1% to 8% emulsifier, and the rest is deionized water.

[0008] Preferably, the softener in the finishing liquid is a softener for ultra-fine fibers, which is one or more of polyether polysiloxane, amino-modified multi-block silicone oil, multi-block copolymer silicone oil, and polyurethane-modified multi-block silicone oil.

[0009] Furthermore, the ultra-fiber softener in the finishing liquid is selected from multi-block copolymer silicone oil with good hand feeling and good compounding stability.

[0010] Preferably, the pH regulator in the finishing liquid is one or more of formic acid, acetic acid, sodium dihydrogen phosphate, and citric acid.

[0011] Furthermore, the pH regulator in the finishing liquid is selected from one or more of acetic acid and citric acid.

[0012] Preferably, the emulsifier used in conjunction with the waterproofing agent is one or more of isopropyl alcohol, propylene glycol, fatty alcohol polyoxyethylene ether, and ethylene glycol butyl ether.

[0013] Preferably, the solid content of the ultra-fiber softener is 15% to 30%.

[0014] Preferably, the amount of the cross-linking agent is 10% to 20% of the amount of the waterproofing agent.

[0015] Furthermore, before the waterproof and soft one-bath finishing, a pretreatment process must be carried out using a waterproof pretreatment agent.

[0016] Preferably, the waterproof pretreatment agent is one or more of aromatic sulfonates, lignin sulfonates, and fatty alcohol polyoxyethylene ether substances.

[0017] Preferably, the waterproof pretreatment agent process is: treatment temperature 40°C to 60°C, time 15min to 25min, then washing, dehydrating, and drying for standby use.

[0018] Preferably, the waterproof and soft finishing liquid is applied to the base fabric, and the application process is as follows: a) Prepare working fluid: Fluorine-free waterproofing agent 8% to 25% Softener for microfiber 0.5%~2% Crosslinking agent 1%~5% pH adjuster 0.01%~0.2%; b) Padding working fluid: rolling rate 40%-60%; c) Baking: heat treatment at 130-170°C for 60s-10min.

[0019] Preferably, the base fabric is immersed in the finishing liquid for padding, and then shaped and baked once, and can be directly processed into a finished product.

[0020] Preferably, the base fabric is microfiber synthetic leather.

[0021] Compared with the prior art, the present invention has the following five beneficial effects.

[0022] The finishing liquid of the present invention utilizes a fluorine-free waterproof agent and a softener for ultra-fiber to be compounded in the same bath, has good compounding property and high stability, and can achieve the effect of waterproof and better softness of the finished product after the same bath finishing and baking. Compared with the traditional two-bath two-step method, the process is simple, and a step of shaping and baking process is omitted, which saves more than 25% of time, saves more than 30% of energy consumption, saves energy and reduces emissions, improves production efficiency, and reduces production costs.

[0023] The waterproofing agent selected by the present invention is a fluorine-free waterproofing agent, which is safe and environmentally friendly. The raw materials thereof are selected from two components of specific octadecyl acrylate and polyurethane isocyanate for effective compounding, rather than using a single component of a separate alkyl acrylate or polyurethane isocyanate. The emulsifier is optimized and assisted by the network cross-linking effect of the cross-linking agent, so that the cross-linking bonding of the base fabric is more sufficient and firm, and a better and more lasting waterproofing effect can be obtained.

[0024] The softener selected in the present invention is a specific softener for ultra-fiber, rather than conventional dimethyl silicone oil, common amino silicone oil or amino-modified softener, etc., and the composite stability thereof is higher, and the softener can be compounded with the fluorine-free waterproof agent in the same bath to form a finishing liquid, without problems such as demulsification, oil bleaching, and stratification. After the base fabric is dipped and baked, it not only has a soft feel and elasticity, but also has relatively good waterproof and anti-siphoning effects, and basically has no effect on the waterproof effect of the fluorine-free waterproof agent, thereby meeting the requirements of the same-bath finishing.

[0025] The present invention selects a specific waterproof pretreatment agent to pretreat the microfiber base cloth before waterproof and soft same-bath finishing. Since the microfiber (PA / PU) base cloth is usually dyed at high temperature with acidic or neutral dyes, a large amount of acidic leveling agents, penetrants, sodium sulfate, etc., as well as auxiliary substances such as acidic color fixing agents used for color fixation are often added to the dyeing bath. Most of the auxiliary agents are anionic, while waterproofing agents such as polyurethane isocyanate esters and fluorocarbon hydrogen structures are mostly cationic. If the dyeing auxiliary agent still has a certain residue after washing with water, it will affect the cross-linking and film-forming reaction of the waterproofing agent on the base cloth, and the stability of the finishing liquid, etc., which will further affect the waterproof effect, so it must be thoroughly cleaned before waterproof finishing. The present invention selects a specific waterproof pretreatment agent with excellent dispersibility, permeability and emulsification, which can thoroughly clean the residual auxiliary components and minimize the impact on the waterproofing agent, thereby obtaining a better and more stable waterproofing effect.

[0026] The waterproof and soft one-bath finishing of the present invention comprises the following steps: immersing the microfiber base fabric in the one-bath finishing liquid for rolling, and then performing one-time shaping and baking to directly process the finished product. The process has good versatility, shortens the process, improves efficiency, and saves production costs. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments.

[0029] In the following description, a large number of specific details are provided to provide a more thorough understanding of the present invention. However, it is apparent to those skilled in the art that the present invention can be implemented without one or more of these details. In other examples, in order to avoid confusion with the present invention, some technical features well known in the art are not described.

[0030] The present invention will be further described below in conjunction with the embodiments. The examples of the embodiments are intended to explain the present invention. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0031] The present invention provides a finishing liquid for waterproofing and softening microfibers in one bath and its application. The finishing liquid comprises one or more liquid auxiliary agent components, which are as follows by weight: 8% to 25% of a fluorine-free waterproofing agent, 0.5% to 2% of a softening agent for microfibers, 1% to 5% of a cross-linking agent, and 0.01% to 0.2% of a pH regulator, and the rest is water.

[0032] As a preferred embodiment, the fluorine-free waterproofing agent in the finishing liquid includes, by weight percentage, 5% to 15% octadecyl acrylate, 10% to 30% polyurethane isocyanate and 1% to 8% emulsifier, and the rest is deionized water, such as the fluorine-free waterproofing agent FOREX-W8693 (produced by Fuyu Chemical).

[0033] The liquid microfiber softener is one or more of polyether polysiloxane, amino-modified multi-block silicone oil, multi-block copolymer silicone oil, and polyurethane-modified multi-block silicone oil. As a preferred embodiment, the solid content of the microfiber softener is 25% to 30%, such as the microfiber softener FOREX-8952 (produced by Fuyu Chemical).

[0034] As a preferred embodiment, the pH regulator in the finishing liquid is one or more of acetic acid and citric acid.

[0035] As a preferred embodiment, the emulsifier is one or more of isopropyl alcohol, propylene glycol, and ethylene glycol butyl ether.

[0036] As a preferred embodiment, the waterproof pretreatment agent is selected from aromatic sulfonate.

[0037] The present invention also includes the use of the finishing liquid in the waterproof and soft one-bath finishing of the microfiber base cloth.

[0038] The traditional two-bath two-step solution for waterproofing and softening is: Pre-treatment - vat dyeing - color fixing - washing - drying - softening - shaping and baking - waterproofing - shaping and baking - finished product.

[0039] The current waterproof and soft one-bath finishing solution is: Pre-treatment - vat dyeing - color fixing - washing - waterproof pre-treatment - drying - waterproof and soft bath - shaping and baking - finished product.

[0040] As a preferred embodiment, the padding working solution has a rolling rate of 45%-55%.

[0041] As a preferred embodiment, baking: heat treatment at 150-160° C. for 120 s-9 min.

[0042] As a preferred embodiment, the waterproof and soft one-bath finishing is more suitable for microfiber base fabrics. The microfiber base fabrics are immersed in the finishing liquid for rolling, and then shaped and baked once, and can be directly processed into finished products, shortening the processing steps and saving time and cost.

[0043] Example 1

[0044] The fluorine-free waterproofing agent 1 comprises, by weight percentage: 8% octadecyl acrylate, 14% polyurethane isocyanate ester and 2% emulsifier, and the rest is deionized water, and the solid content of the waterproofing agent is 24%.

[0045] The solid content of the ultra-fine fiber softener FOREX-8952 is 30%, and it is a multi-block copolymer silicone oil. The pH regulator in the finishing liquid is acetic acid, and the emulsifier is isopropyl alcohol.

[0046] The waterproof pretreatment agent is aromatic sulfonate, and the waterproof pretreatment process of the microfiber base fabric after color fixation is: treatment temperature 40°C, time 15min.

[0047] The waterproof and soft finishing liquid is applied to the base fabric. The application process is as follows: a) Prepare working fluid: Fluorine-free water repellent 1 18% Microfiber softener FOREX-8952 1.0% Crosslinker 3.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 50%; c) Baking: heat treatment at 150°C for 6 minutes.

[0048] Example 2

[0049] The fluorine-free waterproofing agent 2 comprises, by weight percentage: 10% octadecyl acrylate, 15% polyurethane isocyanate ester and 5% emulsifier, and the rest is deionized water. The solid content of the waterproofing agent is 30%.

[0050] The solid content of the ultra-fine fiber softener FOREX-8952 is 30%, and it is a multi-block copolymer silicone oil. The pH regulator in the finishing liquid is citric acid, and the emulsifier is isopropyl alcohol and ethylene glycol butyl ether.

[0051] The waterproof pretreatment agent is aromatic sulfonate, and the waterproof pretreatment process of the microfiber base fabric after color fixation is: treatment temperature 50°C, time 15min.

[0052] The waterproof and soft finishing liquid is applied to the base fabric. The application process is as follows: a) Prepare working fluid: Fluorine-free water repellent 2 18% Microfiber softener FOREX-8952 1.0% Crosslinker 3.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 55%; c) Baking: heat treatment at 150°C for 7 minutes.

[0053] Example 3

[0054] The fluorine-free waterproofing agent 2 comprises, by weight percentage: 12% octadecyl acrylate, 20% polyurethane isocyanate ester and 6% emulsifier, and the rest is deionized water. The solid content of the waterproofing agent is 38%.

[0055] The solid content of the ultra-fine fiber softener FOREX-8952 is 30%, and it is a multi-block copolymer silicone oil. The pH regulator in the finishing liquid is acetic acid, and the emulsifier is isopropyl alcohol and ethylene glycol butyl ether.

[0056] The waterproof pretreatment agent is aromatic sulfonate, and the waterproof pretreatment process of the microfiber base fabric after color fixation is: treatment temperature 50°C, time 20min.

[0057] The waterproof and soft finishing liquid is applied to the base fabric. The application process is as follows: a) Prepare working fluid: Fluorine-free water repellent 3 18% Microfiber softener FOREX-8952 1.5% Crosslinker 3.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 55%; c) Baking: heat treatment at 155°C for 8 minutes.

[0058] Comparative Example 1

[0059] Fluorine-free water repellent ECO PLUS (commercially available).

[0060] Softener 8801 (produced by Fuyu Chemical), solid content is 30%, amino modified silicone oil. The pH regulator in the finishing liquid is acetic acid.

[0061] The finishing liquid with softener is applied to the base fabric, and the application process is as follows: a) Prepare working fluid: Softener 8801 1.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 55%; c) Baking: heat treatment at 150°C for 6 minutes.

[0062] The finishing liquid with waterproofing agent is applied to the base fabric, and the application process is as follows: a) Prepare working fluid: Fluorine-free water repellent ECO PLUS 18% Crosslinker 3.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 55%; c) Baking: heat treatment at 150°C for 6 minutes.

[0063] Comparative Example 2

[0064] Fluorine-free waterproofing agent Zelan R3 (commercially available), with a solid content of 30%.

[0065] Softener 8805 (produced by Fuyu Chemical), solid content is 30%, amino modified polyether silicone oil. The pH regulator in the finishing liquid is acetic acid.

[0066] The finishing liquid with softener is applied to the base fabric, and the application process is as follows: a) Prepare working fluid: Softener 8805 1.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 55%; c) Baking: heat treatment at 150°C for 6 minutes.

[0067] The finishing liquid with waterproofing agent is applied to the base fabric, and the application process is as follows: a) Prepare working fluid: Fluorine-free water repellent Zelan R3 18% Crosslinker 3.5% pH adjuster 0.05%; b) Padding working solution: rolling rate 55%; c) Baking: heat treatment at 150°C for 6 minutes.

[0068] Test method for waterproof fabrics: The water-repellent performance test refers to AATCC 22-2005 "Test method for water repellency of textiles: spray method" test, and is rated against the standard sample. The waterproof grade is rated as follows: completely wet with the worst score of 0 points, and completely not wet with the highest score of 100 points.

[0069] The specific method of static anti-siphon test is: cut the fabric that has been fluorine-free waterproof finished into a sample of 150mm×25mm size, hang the sample vertically in an immersion dish filled with a colored solution (such as: red ink solution), and the length of the part immersed in water is 10mm (a straight line can be drawn 10mm at one end of the long side of the sample as a marking line); take it out after standing for 2h, and observe the climbing height of the liquid above the sample marking line. The qualified requirement is that the climbing height is ≤10mm.

[0070] The dynamic anti-siphonage S2 test is tested according to the QB / T 4044-2010 synthetic leather standard for protective shoes. The specific method is: cut the fluorine-free waterproof finished fabric into a sample of 75mm×60mm in size, record the mass W1, immerse the sample completely in water to simulate the wearing state, conduct a bending test on the machine for 1 hour, take it out, record the mass W2, and calculate the water absorption rate, that is, water absorption rate / %=(W2-W1) / W1×100. The qualified requirement is water absorption rate ≤30%.

[0071] Before the water repellent performance test, the dry waterproof fabric was allowed to recover moisture for 4 hours at 23±2°C and a relative humidity of 50-70%. Before the static / dynamic anti-siphon test, the dry waterproof fabric was allowed to recover moisture for 6 hours at 23±2°C and a relative humidity of 50-70%.

[0072] For the hand feel evaluation, professionals were selected to judge, with level 1 being the worst and level 5 being the best.

[0073] Table 1 Evaluation of waterproof performance and hand feel of the microfiber base fabrics after finishing of Examples 1-3 and Comparative Examples 1-2.

[0074] serial number Water repellent grade / points Static anti-siphon (unit, mm) Water absorption (unit, %) Feel / Grade Example 1 90 7 29.4 4-5 Example 2 100 3 28.2 4-5 Example 3 100 0 27.5 4-5 Comparative Example 1 90 6 32.3 4 Comparative Example 2 100 2 30.5 4-5 It can be seen from Table 1 that, under the same dosage of the fluorine-free waterproofing agent, compared with Comparative Examples 1-2, Examples 1-3 all have better hand feel, and the static anti-siphon and dynamic anti-siphon effects also meet the requirements, saving process steps, saving time and energy, and improving production efficiency. The difference between Examples 1-2 and Example 3 is that the solid content of the fluorine-free waterproofing agent is different, and the baking temperature, rolling rate, pH regulator, waterproof pretreatment conditions, etc. are slightly different. The difference between Comparative Example 1 and Comparative Example 2 is that different softeners and fluorine-free waterproofing agents (commercially available, with different component structures) are selected, and the results obtained in terms of water repellency level, dynamic anti-siphon effect, hand feel, etc. are quite different.

[0075] The above descriptions are only some embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the specification of the present invention, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A finishing liquid for waterproofing and softening microfibers and its application, characterized in that: The finishing liquid comprises one or more liquid auxiliary components, which are as follows: 8% to 25% of a waterproofing agent, 0.5% to 2% of a softening agent, 1% to 5% of a cross-linking agent, and 0.01% to 0.2% of a pH regulator, and the rest is water.

2. The finishing liquid according to claim 1, characterized in that: The waterproofing agent in the finishing liquid is a fluorine-free waterproofing agent, which comprises, by weight percentage, 5% to 15% octadecyl acrylate, 10% to 30% polyurethane isocyanate ester and 1% to 8% emulsifier, and the rest is deionized water.

3. The finishing solution according to claim 1, characterized in that: The softener in the finishing liquid is a softener for ultra-fine fibers, which is one or more of polyether polysiloxane, amino-modified multi-block silicone oil, multi-block copolymer silicone oil, and polyurethane-modified multi-block silicone oil.

4. The finishing liquid according to claim 1, characterized in that: The pH regulator in the finishing liquid is one or more of formic acid, acetic acid, sodium dihydrogen phosphate and citric acid.

5. The waterproofing agent according to claim 2, characterized in that: The emulsifier is one or more of isopropanol, propylene glycol, fatty alcohol polyoxyethylene ether, and ethylene glycol butyl ether.

6. The ultra-fiber softener according to claim 3, characterized in that: The solid content of the ultra-fiber softener is 15% to 30%.

7. The finishing liquid according to claim 1, characterized in that: Before the waterproof and soft one-bath finishing, a waterproof pretreatment agent must be used for pretreatment.

8. The waterproof pretreatment agent according to claim 7, characterized in that: The waterproof pretreatment agent is one or more of aromatic sulfonates, lignin sulfonates, and fatty alcohol polyoxyethylene ether substances.

9. Use of the finishing liquid according to any one of claims 1 to 8 in waterproofing and softening a base fabric in one bath, characterized in that: The application process is as follows: a) Working fluid: 8% to 25% fluorine-free waterproofing agent Softener for microfiber 0.5%~2% Crosslinking agent 1%~5% pH adjuster 0.01%~0.2%; b) Padding working fluid: rolling rate 30%-70%; c) Baking: heat treatment at 130-170°C for 60s-10min.

10. The use according to claim 9, characterized in that: The method comprises the steps of immersing the base fabric into the finishing liquid for impregnation and then performing shaping and baking once, so that the base fabric can be directly processed into a finished product.

11. The use according to claim 10, characterized in that: The base fabric is microfiber synthetic leather.