Aqueous Pressure Transformation Agent for Synthetic Leather and its Preparation Method

Abstract

This invention discloses a water-based pressure change agent for synthetic leather, belonging to the technical field of treatment agents for synthetic leather. The water-based pressure change agent for synthetic leather comprises, by weight, the following components: 30-50 parts of water-based silicone-fluorine grafted block polyurethane emulsion, 10-20 parts of deionized water, 0.5-1 part of organosilicon wetting agent, 0.5-1 part of leveling agent, 0.3-0.8 parts of defoamer, 2-3 parts of thickener, 4-6 parts of water-based fluorocarbon resin, 20-40 parts of high-density oxidized polyethylene wax dispersion, and 2-5 parts of titanium dioxide. When the water-based pressure change agent for synthetic leather provided by this invention is used for pressing artificial leather, there is no need for hot water washing (water kneading) and drying. The pressure change treatment can be completed directly by hot pressing after treatment with the agent, simplifying the processing procedure and reducing costs.

Description

Technical Field

[0001] This invention belongs to the technical field of synthetic leather treatment agents, specifically relating to a water-based pressure transformation treatment agent for waterproof and oil-resistant synthetic leather and its preparation method. Background Technology

[0002] Heat transfer color change agent is a special coating agent used for heat-pressing and color-changing on garment leather, shoe leather, and bag leather. The base color of the leather becomes visible after heat transfer color change agent treatment, facilitating shaping. Traditional heat transfer color change agent application requires first applying the agent to the surface of the synthetic leather, followed by hot water washing, drying, and finally hot pressing. This process is cumbersome, and the treated areas are prone to discoloration when exposed to water or oil. Chinese invention patent CN105273395A discloses a synthetic leather heat transfer color change powder comprising nylon powder, aluminum distearate, and silica. Using this powder to prepare the synthetic leather heat transfer color change agent eliminates the water-rubbing and drying steps in the heat transfer process, saving processing costs and resulting in leather with better color stability and a higher yield. However, as it is a powder, it still requires the addition of an industrial solvent formulation to prepare the synthetic leather heat transfer color change agent before use, making the application process cumbersome. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a water-based compression molding agent that can be used directly without water washing to perform compression molding on synthetic leather.

[0004] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows: a water-based pressure change treatment agent for synthetic leather, comprising the following components by weight:

[0005] The composition includes 30-50 parts of waterborne silicone-fluorine grafted block polyurethane emulsion, 10-20 parts of deionized water, 0.5-1 part of silicone wetting agent, 0.5-1 part of leveling agent, 0.3-0.8 parts of defoamer, 2-3 parts of thickener, 4-6 parts of waterborne fluorocarbon resin, 20-40 parts of high-density oxidized polyethylene wax dispersion, and 2-5 parts of titanium dioxide.

[0006] The beneficial effects of the present invention are as follows: When the water-based pressure change treatment agent provided by the present invention is used to treat artificial leather, there is no need to wash (rub) with hot water and dry it. After treatment with the treatment agent, the pressure change treatment can be completed directly by hot pressing, which simplifies the treatment process. Moreover, the water-based pressure change treatment agent can be used directly without adding solvents or other liquids for preparation. At the same time, the pressure-treated area has good waterproof and oil-proof properties and is not easy to discolor. Attached Figure Description

[0007] Figure 1The image shows synthetic leather after undergoing compression molding treatment with an aqueous compression molding agent, as described in Example 1.

[0008] Figure 2 The image shows synthetic leather after being treated with a commercially available compression modifier. Detailed Implementation

[0009] To explain in detail the technical content, objectives, and effects of the present invention, the following description is provided in conjunction with the embodiments and accompanying drawings.

[0010] The most crucial concept of this invention lies in its innovative provision of a water-based pressure transformation agent that allows for direct hot pressing without the need for hot water washing and drying, for use in pressure transformation treatment of synthetic leather.

[0011] The water-based pressure change agent for synthetic leather of the present invention comprises, by weight, the following components:

[0012] The composition includes 30-50 parts of waterborne silicone-fluorine grafted block polyurethane emulsion, 10-20 parts of deionized water, 0.5-1.5 parts of organosilicon wetting agent, 1-2 parts of leveling agent, 0.3-1 part of defoamer, 2-3 parts of thickener, 4-6 parts of waterborne fluorocarbon resin, 20-40 parts of high-density oxidized polyethylene wax dispersion, and 2-5 parts of titanium dioxide.

[0013] As can be seen from the above description, the beneficial effects of the present invention are as follows: When the synthetic leather water-based pressure change treatment agent provided by the present invention is used to perform pressure treatment on artificial leather, it is not necessary to wash (rub) with hot water. After treatment with the treatment agent, it can be directly hot-pressed to complete the process, which simplifies the treatment process. Moreover, the synthetic leather water-based pressure change treatment agent can be used directly without adding solvents or other liquids for preparation. At the same time, the pressure-treated area has good waterproof and oil-proof properties and is not easy to discolor.

[0014] Furthermore, the silicone wetting agent is silok-8000.

[0015] Furthermore, the leveling agent is Tego-450.

[0016] Furthermore, the solid content of the waterborne silicone-fluorine grafted block polyurethane emulsion is 30-40%, preferably 35%.

[0017] Further, the preparation method of waterborne silicone-fluorine grafted block polyurethane emulsion is as follows: reactive organosilicon with single-terminal dihydroxyl groups, fluorinated alcohol, PCD (polycarbonate diol), DMPA (2,2-dimethylolpropionic acid) and DMAC (N,N-dimethylacetamide) are mixed and stirred; then the temperature is raised to 60~65℃, H12MDI (dicyclohexylmethane-4,4 diisocyanate), IPDI (isophorone diisocyanate) and catalyst are added, and the temperature is raised to 85~95℃ (preferably 90℃) and kept at that temperature for 3h. Then the NCO% is measured to reach the theoretical value (3.3~3.5%) (the formula for calculating the theoretical value of NCO% is shown in formula (1)). Then the temperature is lowered to 45~55℃ (preferably 50℃), triethylamine is added, and the mixture is stirred to obtain the prepolymer.

[0018] w(NCO)% =[n(NCO)-n(OH)]x42 / m Formula (1)

[0019] In equation (1), m is the total mass of the added raw materials.

[0020] The prepolymer was added to deionized water while stirring. Ethylenediamine was added dropwise during the process of adding the prepolymer. After the addition of ethylenediamine was completed, stirring was continued and the reaction was continued for 4 hours. The mixture was then filtered to obtain an aqueous silicone-fluorine grafted block polyurethane emulsion.

[0021] Furthermore, the stirring rate when adding the prepolymer to deionized water is 1200~1500 r / min, and the stirring rate after the addition of ethylenediamine is completed is 500 r / min.

[0022] Furthermore, the catalyst is an organic bismuth catalyst.

[0023] Furthermore, the deionized water is cold-processed deionized water at a temperature of 8~10℃.

[0024] As can be seen from the above description, hot water reacts with -NCO, affecting subsequent chain extension.

[0025] Furthermore, the preparation method of the waterborne silicone-fluorine grafted block polyurethane emulsion is as follows: [The emulsion is then applied to a 3.8m...] 3100-120 kg of reactive organosilicon with a number average molecular weight of 2000 and single-terminated dihydroxyl groups, 50-60 kg of fluoroethanol, 500-609 kg of PCD 2000, 30.3-45 kg of 2,2-dimethylolpropionic acid (DMPA), and 180-200 kg of dimethylacetamide (DMAC) were added to a reactor. The mixture was stirred at 500 r / min for 20 minutes. While stirring, the temperature was raised to 65℃ and 182-200 kg of dicyclohexylmethane-4,4-diisocyanate (H12MDI), 56.8-65 kg of IPDI, and 0.15 kg of organic bismuth catalyst were added. The temperature was then raised to 90℃ and held for 3 hours. After the NCO% reached the theoretical value of 3.3-3.5%, the temperature was lowered to 50℃ and 18-22 kg of triethylamine was added. The mixture was stirred at 500 r / min for 10 minutes and then discharged to obtain the prepolymer.

[0026] Prepolymer was slowly added to a dispersion vessel containing pre-cooled deionized water at 8°C (cold-prepared deionized water) while stirring at a high speed of 1200~1500 r / min. During the dispersion process, 19.5 kg of ethylenediamine was slowly added dropwise. After the addition was completed, the stirring speed was reduced to 500 r / min, and the reaction was continued for 4 hours. The mixture was then filtered to obtain an aqueous silicone-fluorine grafted block polyurethane emulsion.

[0027] This invention provides a method for preparing a water-based pressure transformation agent for synthetic leather, comprising the following steps:

[0028] S1. Mix 30-50 parts of waterborne silicone-fluorine grafted block polyurethane emulsion, 10-20 parts of deionized water, 0.5-1.5 parts of silok-8000, 1-2 parts of leveling agent, 0.3-1 part of defoamer, 4-6 parts of waterborne fluorocarbon resin, 20-40 parts of high-density oxidized polyethylene wax dispersion and titanium dioxide, and stir at high speed for 30-40 minutes.

[0029] S2. After reducing the stirring speed, add the thickener and adjust the viscosity to 1500~2000cps / 25℃;

[0030] S3, after filtration and packaging, yields a water-based pressure change treatment agent for synthetic leather.

[0031] Furthermore, the stirring rate in S1 is 1300~1800 r / min, preferably 1500 r / min; the stirring rate in S2 is 500-800 r / min, preferably 600 r / min.

[0032] Furthermore, the S3 uses a 180-mesh filter for filtration.

[0033] As can be seen from the above description, in the preparation process, the reaction system in S1 has a high viscosity and requires a high stirring rate to ensure sufficient dispersion. In S2, the main reaction is chain extension, which has a lower viscosity and requires low-speed stirring to ensure sufficient flow of the raw materials. High-speed stirring is not allowed.

[0034] Example 1

[0035] S1. Preparation of waterborne silicone-fluorine grafted block polyurethane emulsion: [The emulsion is then applied to a 3.8m...] 3 100 kg of reactive organosilicon with a number average molecular weight of 2000 and single-terminated dihydroxyl groups, 60 kg of fluoro alcohol, 609 kg of PCD2000, 30.3 kg of DMPA, and 200 kg of DMAC were added to a reactor. The mixture was stirred at 500 r / min for 20 minutes. While stirring, the temperature was raised to 65℃ and 182 kg of H12MDI, 56.8 kg of IPDI, and 0.15 kg of organobismuth catalyst were added. The temperature was then raised to 90℃ and held for 3 hours. After the NCO% reached the theoretical value of 3.5%, the temperature was lowered to 50℃, 22 kg of triethylamine was added, and the mixture was stirred at 500 r / min for 10 minutes before being discharged to obtain the prepolymer.

[0036] Prepolymer was slowly added to a dispersion vessel containing pre-cooled deionized water (cold-prepared deionized water) at 8°C while stirring at 1500 r / min. During the dispersion process, 19.5 kg of ethylenediamine was slowly added dropwise. After the addition was completed, the stirring speed was reduced to 500 r / min, and the reaction was continued for 4 hours. The mixture was then filtered to obtain an aqueous silicone-fluorine grafted block polyurethane emulsion.

[0037] S2, towards 4.5m 3 Add 1000 kg of waterborne silicone-fluorine grafted block polyurethane emulsion obtained from S1, 300 kg of deionized water, 15 kg of silok-8000, 20 kg of Tego-450, 10 kg of defoamer, 100 kg of waterborne fluorocarbon resin, 800 kg of high-density oxidized polyethylene wax dispersion and 100 kg of titanium dioxide to a biaxial dispersion vessel, and stir at 1500 r / min for 40 min until uniformly dispersed;

[0038] S3. After reducing the stirring speed to 600 r / min, add the thickener and adjust the viscosity to 1800 cps / 25℃.

[0039] S4, after being filtered through a 180-mesh filter and packaged, yields a water-based pressure change treatment agent for synthetic leather.

[0040] Example 2

[0041] A method for preparing a water-based pressure transformation agent for synthetic leather includes the following steps:

[0042] S1. Preparation of waterborne silicone-fluorine grafted block polyurethane emulsion: [The emulsion is then applied to a 3.8m...] 3120 kg of reactive organosilicon with a number average molecular weight of 2000 and single-terminated dihydroxyl groups, 55 kg of fluoroethanol, 500 kg of PCD2000, 40 kg of DMPA, and 180 kg of DMAC were added to a reactor. The mixture was stirred at 500 r / min for 20 minutes. While stirring, the temperature was raised to 60℃ and 200 kg of H12MDI, 60 kg of IPDI, and 0.15 kg of organic bismuth catalyst were added. The temperature was then raised to 90℃ and held for 3 hours. The NCO% was measured and found to be 3.3% of the theoretical value. The temperature was then lowered to 50℃ and 20 kg of triethylamine was added. The mixture was stirred at 500 r / min for 10 minutes and then discharged to obtain the prepolymer.

[0043] Prepolymer was slowly added to a dispersion vessel containing pre-cooled deionized water at 10°C (cold deionized water) while stirring at a high speed of 1200 r / min. During the dispersion process, 19 kg of ethylenediamine was slowly added dropwise. After the addition was completed, the stirring speed was reduced to 500 r / min, and the reaction was continued for 4 hours. The mixture was then filtered to obtain an aqueous silicone-fluorine grafted block polyurethane emulsion.

[0044] S2, towards 4.5m 3 Add 600 kg of waterborne silicone-fluorine grafted block polyurethane emulsion obtained from S1, 200 kg of deionized water, 10 kg of silok-8000, 10 kg of Tego-450, 6 kg of defoamer, 80 kg of waterborne fluorocarbon resin, 400 kg of high-density oxidized polyethylene wax dispersion and 40 kg of titanium dioxide to a biaxial dispersion vessel, and stir at 1500 r / min for 30 min until uniformly dispersed;

[0045] S3. After reducing the stirring speed to 600 r / min, add the thickener and adjust the viscosity to 1500 cps / 25℃.

[0046] S4, after being filtered through a 180-mesh filter and packaged, yields a water-based pressure change treatment agent for synthetic leather.

[0047] Example 3

[0048] A method for preparing a water-based pressure transformation agent for synthetic leather includes the following steps:

[0049] S1. Preparation of waterborne silicone-fluorine grafted block polyurethane emulsion: Preparation of waterborne silicone-fluorine grafted block polyurethane emulsion: to 3.8m 3110 kg of reactive organosilicon with a number average molecular weight of 2000 and single-terminated dihydroxyl groups, 50 kg of fluoroethanol, 552 kg of PCD2000, 45 kg of DMPA, and 190 kg of DMAC were added to a reactor. The mixture was stirred at 500 r / min for 20 minutes. While stirring, the temperature was raised to 63℃ and 192 kg of H12MDI, 65 kg of IPDI, and 0.15 kg of organic bismuth catalyst were added. The temperature was then raised to 90℃ and held for 3 hours. The NCO% was measured and found to be 3.4% of the theoretical value. The temperature was then lowered to 50℃ and 22 kg of triethylamine was added. The mixture was stirred at 500 r / min for 10 minutes and then discharged to obtain the prepolymer.

[0050] Prepolymer was slowly added to a dispersion vessel containing pre-cooled deionized water at 9°C (cold-prepared deionized water) while stirring at a high speed of 1400 r / min. During the dispersion process, 20 kg of ethylenediamine was slowly added dropwise. After the addition was completed, the stirring speed was reduced to 500 r / min, and the reaction was continued for 4 hours. The mixture was then filtered to obtain an aqueous silicone-fluorine grafted block polyurethane emulsion.

[0051] S2, towards 4.5m 3 Add 900 kg of waterborne silicone-fluorine grafted block polyurethane emulsion obtained from S1, 400 kg of deionized water, 20 kg of silok-8000, 12 kg of Tego-450, 16 kg of defoamer, 120 kg of waterborne fluorocarbon resin, 700 kg of high-density oxidized polyethylene wax dispersion and 60 kg of titanium dioxide to a biaxial dispersion vessel, and stir at 1500 r / min for 38 min until uniformly dispersed;

[0052] S3. After reducing the stirring speed to 600 r / min, add the thickener and adjust the viscosity to 2000 cps / 25℃.

[0053] S4, after being filtered through a 180-mesh filter and packaged, yields a water-based pressure change treatment agent for synthetic leather.

[0054] Example 4

[0055] A method for preparing a water-based pressure transformation agent for synthetic leather includes the following steps:

[0056] S1, towards 4.5m 3 Add 1000 kg of the aqueous silicone-fluorine grafted block polyurethane emulsion obtained in Example 1 (S1), 320 kg of deionized water, 12 kg of silok-8000, 15 kg of Tego-450, 12 kg of defoamer, 100 kg of aqueous fluorocarbon resin, 800 kg of high-density oxidized polyethylene wax dispersion, and 80 kg of titanium dioxide to a biaxial dispersion vessel, and stir at 1500 r / min for 35 min until uniformly dispersed;

[0057] S2. After reducing the stirring speed to 600 r / min, add the thickener and adjust the viscosity to 1750 cps / 25℃.

[0058] S3, after being filtered through a 180-mesh filter and packaged, yields a water-based pressure change treatment agent for synthetic leather.

[0059] The same batch of synthetic leather was cut into 50 samples of 30x30cm each, and randomly divided into 5 groups of 10 samples each, named Group A, Group B, Group C, Group D and Group E.

[0060] Group A used the water-based heat transfer agent from Example 1 for heat transfer treatment. The steps were as follows: first, the water-based heat transfer agent was applied to the surface of the synthetic leather, and then the logo was heat-pressed using a small manual tabletop leather hot stamping machine with a copper mold at a temperature of 150°C.

[0061] Groups B and C used commercially available water-based pressure change agents for pressure change treatment. Group B's procedure involved first applying the commercially available water-based pressure change agent to the surface of the synthetic leather, then washing the synthetic leather with 60°C hot water, followed by drying with 40°C hot air, and finally pressing the logo onto the leather using the same method as Group A. Group C's treatment method was the same as Group A.

[0062] Groups D and E underwent voltage transformation treatment using commercially available oil-based water-washed whitening agent. The treatment method for Group D was the same as that for Group B, and the treatment method for Group E was the same as that for Groups A and C.

[0063] 1. Waterproof Test: Place a drop of room temperature water on the treated synthetic leather and observe whether it forms a freely sliding lotus leaf-shaped bead. After 1 minute, check if the leather surface color darkens. If a freely sliding lotus leaf-shaped bead forms and the leather surface color does not darken after 1 minute, the waterproof effect is the best, level 1. If a freely sliding lotus leaf-shaped bead forms, but the leather surface color darkens after 1 minute, the waterproof effect is average, level 2. If a freely sliding lotus leaf-shaped bead does not form, and the leather surface color darkens immediately after the water droplet, the waterproof effect is very poor, level 3.

[0064] 2. Oil Repellency Test: Drip sewing machine oil onto the treated synthetic leather and observe whether the leather surface darkens where the oil remains. If the leather surface does not darken and there are virtually no oil stains after wiping with a cloth, the oil repellency is at least Grade 1 (best). If the leather surface does not darken and there are noticeable oil stains after wiping with a cloth, the oil repellency is relatively good (Grade 2). If the leather surface darkens immediately after the oil remains, the oil has completely penetrated the leather, and the oil repellency is average (Grade 3).

[0065] 3. Pressure Change Effect Test: If the surface color darkens and the logo of the model becomes more obvious after hot pressing, it indicates that the pressure change effect is obvious.

[0066] Group A synthetic leather that passed the waterproof and oil-resistant test. Figure 1 As shown, the synthetic leather in Group B that passed the waterproof and oil-resistant test is shown. Figure 2 As shown, Figure 2 The dark dot above the logo is where sewing machine oil was dripped during the oil resistance test. Figure 2 The darker color on the logo indicates the addition of room temperature water.

[0067] It can be seen that the water-based pressure transducer provided by this invention can achieve good pressure transducer effect without hot water washing and drying steps, and has better waterproof and oil-proof properties after treatment, which is superior to commercially available water-based pressure transducer. Although commercially available oil-based pressure transducer has good waterproof and oil-proof properties, if hot water washing, drying and then hot pressing are not performed, the pressure transducer effect will be not obvious.

[0068] This invention provides a water-based silicone-fluorine grafted block polyurethane emulsion. When using a water-based pressure change agent (PCA) for synthetic leather, this PCA treatment eliminates the need for hot water washing (water rubbing). The treated leather can be directly hot-pressed after PCA treatment to complete the process, significantly simplifying the process and reducing costs. Furthermore, this PCA treatment agent is ready to use without the need for solvents or other liquids, making it convenient and environmentally friendly. The treated areas of the synthetic leather exhibit excellent waterproof and oil-proof properties and are less prone to discoloration.

[0069] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification and drawings, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A water-based pressure change treatment agent for synthetic leather, characterized in that, By weight, it includes the following components: The composition includes 30-50 parts of waterborne silicone-fluorine grafted block polyurethane emulsion, 10-20 parts of deionized water, 0.5-1 part of organosilicon wetting agent, 0.5-1 part of leveling agent, 0.3-0.8 parts of defoamer, 2-3 parts of thickener, 4-6 parts of waterborne fluorocarbon resin, 20-40 parts of high-density oxidized polyethylene wax dispersion, and 2-5 parts of titanium dioxide. The preparation method of the waterborne silicone-fluorine grafted block polyurethane emulsion is as follows: reactive organosilicon with single-terminal dihydroxyl groups, fluoroalcohol, PCD, DMPA and DMAC are mixed and stirred; then the temperature is raised to 60~65℃, H12MDI, IPDI and catalyst are added, and the temperature is raised and kept for 3h. Then the NCO% is measured and the theoretical value is reached. The temperature is lowered, triethylamine is added, and the mixture is stirred to obtain the prepolymer. The prepolymer was added to deionized water while stirring. Ethylenediamine was added dropwise during the process of adding the prepolymer. After the addition of ethylenediamine was completed, stirring was continued and the reaction was continued. The mixture was then filtered to obtain an aqueous silicone-fluorine grafted block polyurethane emulsion.

2. The water-based pressure change agent for synthetic leather according to claim 1, characterized in that, The solid content of the waterborne silicone-fluorine grafted block polyurethane emulsion is 30-40%.

3. The water-based pressure change agent for synthetic leather according to claim 1, characterized in that, The stirring rate for adding the prepolymer to deionized water was 1200~1500 r / min, and the stirring rate for the end of the ethylenediamine addition was 500 r / min.

4. The water-based pressure change treatment agent for synthetic leather according to claim 1, characterized in that, The catalyst is an organic bismuth catalyst.

5. The water-based pressure change treatment agent for synthetic leather according to claim 1, characterized in that, The deionized water is cold-processed deionized water with a temperature of 8~10℃.

6. The aqueous compression molding agent for synthetic leather according to claim 1, characterized in that, The leveling agent is Tego-450.

7. The method for preparing the aqueous pressure change agent for synthetic leather according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Mix 30-50 parts of waterborne silicone-fluorine grafted block polyurethane emulsion, 10-20 parts of deionized water, 0.5-1.5 parts of organosilicon wetting agent, 1-2 parts of leveling agent, 0.3-1 part of defoamer, 4-6 parts of waterborne fluorocarbon resin, 20-40 parts of high-density oxidized polyethylene wax dispersion and titanium dioxide, and stir at high speed for 30-40 minutes. S2. After reducing the stirring speed, add the thickener and adjust the viscosity to 1500~2000cps / 25℃; S3, after filtration and packaging, yields a water-based pressure change treatment agent for synthetic leather.

8. The method for preparing the water-based pressure transformation agent for synthetic leather according to claim 7, characterized in that, The stirring rate in S1 is 1300~1800 r / min; the stirring rate in S2 is 400~500 r / min.

9. The method for preparing the water-based pressure transformation agent for synthetic leather according to claim 8, characterized in that, The S3 uses a 180-mesh filter for filtration.

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