Composite material for artificial leather and preparation method of hydrophobic carbon black color paste of composite material

Abstract

The invention relates to the technical field of water-based paint, and discloses a composite material for artificial leather, the composite material comprises the following components by weight: 20-50 parts of hydrophobic modified carbon black, 5-10 parts of a dispersant, 0.1-0.5 part of an antifoaming agent, 0.1-0.2 part of a preservative, 0.1-0.5 part of a wetting agent, 0.3-0.5 part of a lubricant, 3-5 parts of DMF, 10-15 parts of deionized water, and 20-50 parts of zirconium beads. The preparation method of the hydrophobic carbon black color paste of the composite material for artificial leather comprises the following steps: step 1, weighing a certain mass of carbon black, dissolving the carbon black in N, N-dimethylformamide (DMF), and carrying out ultrasonic treatment to obtain a carbon black suspension; compared with the prior art, the hydrophobic water-based carbon black color paste for the artificial leather has the advantages that the hydrophobic water-based carbon black color paste for the artificial leather is obtained by carrying out hydrophobic modification on carbon black through a copolymer [p (GMA-CO-MMA)] of hydrophobic GMA and MMA, so that the artificial leather has better antifouling, waterproof and self-cleaning properties in daily life.

Description

Technical Field

[0001] The present invention relates to the technical field of waterborne coatings, and particularly to a composite material for artificial leather and a preparation method of a hydrophobic carbon black paste thereof. Background Art

[0002] Due to its advantages such as safety and environmental friendliness, waterborne coatings are widely used in polyurethane (PU) and polyvinyl chloride (PVC), and can be used in artificial leather, automotive interiors, automotive topcoats, floors, etc. Traditional waterborne carbon black pastes are generally hydrophilic, and hydrophilic carbon black pastes are easy to achieve good storage stability. The need for self-cleaning ability in daily life limits the application of waterborne color pastes.

[0003] Herein, to solve the above problems, we propose a composite material for artificial leather and a preparation method of a hydrophobic carbon black paste thereof. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the above technical difficulties and provide a composite material for artificial leather and a preparation method of a hydrophobic carbon black paste thereof. The present invention uses a hydrophobic polymer to modify carbon black, and auxiliary agents such as a dispersant, an antioxidant, and an antifoaming agent can make the color paste have a certain hydrophobicity on the premise of ensuring that the various properties of the color paste (such as blackness, coloring power, storage stability, etc.) remain unchanged and do not affect the normal use of the color paste.

[0005] To solve the above technical problems, the technical solution provided by the present invention is as follows:

[0006] A composite material for artificial leather, the composite material comprising the following components in parts by weight: 20 - 50 parts of hydrophobic modified carbon black, 5 - 10 parts of a dispersant, 0.1 - 0.5 parts of an antifoaming agent, 0.1 - 0.2 parts of a preservative, 0.1 - 0.5 parts of a wetting agent, 0.3 - 0.5 parts of a lubricant, 3 - 5 parts of DMF, 10 - 15 parts of deionized water, and 20 - 50 parts of zirconium beads.

[0007] Further, the dispersant is one of sodium polyacrylate, poly maleic anhydride, or ammonium acrylate - polyethylene copolymer.

[0008] Further, the antifoaming agent is one of polydimethylsiloxane, ethylene glycol siloxane, or polydimethylsiloxane.

[0009] Further, the preservative is one or more of benzisothiazolinone and octyl isothiazolinone.

[0010] Further, the wetting agent is one of polyether - modified trisiloxane and ethoxylated tetramethyl decynediol.

[0011] Further, the lubricant is one of sodium stearate, calcium stearate, and pentaerythritol stearate.

[0012] A method for preparing a hydrophobic carbon black paste of the composite material for artificial leather includes the following steps:

[0013] Step 1: Weigh a certain mass of carbon black and dissolve it in N,N-dimethylformamide (DMF), and obtain a carbon black suspension after ultrasonic treatment;

[0014] Step 2: Add GMA and MMA to the carbon black suspension in a certain proportion, heat and stir while dropping an initiator, add an inhibitor after the heating and stirring are completed to obtain a polymerization product, and then add water for precipitation and filtration to obtain hydrophobic polymer-modified carbon black;

[0015] Step 3: Mix a dispersant, an antifoaming agent, a preservative, a wetting agent, a lubricant, DMF, deionized water, and hydrophobic modified carbon black, add zirconium beads to the mixture for ball milling, perform centrifugal defoaming on the ball-milled product, and filter out the zirconium beads to obtain a hydrophobic aqueous carbon black paste.

[0016] Further, in Step 1, the particle size of the carbon black is 2000 - 2500 mesh, the DMF is of analytical grade, and the ultrasonic time is 40 - 60 min.

[0017] Further, in Step 2, the molar ratio of GMA to MMA is 4 - 4.5:1; it needs to be heated to 60 - 80 °C and stirred and reacted at a speed of 200 - 400 r / min for 6 - 12 h; the initiator is azobisisobutyronitrile (AIBN), and the inhibitor is hydroquinone.

[0018] Further, in Step 3, the particle size of the zirconium beads is 50 - 70 mesh, the ball milling time is 60 - 90 min; the centrifugation time is 10 - 20 min, and the rotation speed is 3000 - 5000 r / min.

[0019] Carbon black is a nanoscale functional material composed of amorphous carbon elements. Its physical form is a light and fluffy black ultrafine powder, with an extremely high specific surface area (10–3000 m 2 / g). This material is mainly prepared by incomplete combustion or pyrolysis of hydrocarbon compounds under anoxic conditions. The aqueous carbon black paste made from it has the advantages of safety and environmental friendliness and is widely used in PU and PVC plastics. It can be used in aspects such as artificial leather, automobile interiors, automobile topcoats, and floors. With the wide application of artificial leather and automobile topcoats, the demand for hydrophobic self-cleaning in this industry is increasing day by day. In this study, a hydrophobic color paste was obtained by hydrophobically modifying carbon black with a copolymer [p(GMA-CO-MMA)] of hydrophobic glycidyl methacrylate (GMA) and methyl methacrylate (MMA).

[0020] The advantages of the present invention compared with the prior art are as follows:

[0021] The present invention hydrophobicizes carbon black through a copolymer of hydrophobic GMA and MMA [p(GMA-CO-MMA)] to obtain a hydrophobic aqueous carbon black paste for artificial leather, enabling the artificial leather to have better anti-fouling, waterproof, and self-cleaning properties in daily life. Detailed implementation manners

[0022] In the description of the present invention, unless otherwise specified, the meaning of "a plurality" is two or more. In addition, the term "comprising" and any of its variations are intended to cover non-exclusive inclusion.

[0023] The following further elaborates on the present invention in conjunction with the implementation manners.

[0024] When implementing the embodiments of the present invention:

[0025] Embodiment 1

[0026] A composite material for artificial leather, and the raw material ratio of the composite material is as follows: 3000 g of carbon black, 5 g of initiator, 600 g of GMA, 100 g of MMA, 5 g of inhibitor, 100 g of dispersant, 10 g of defoamer, 10 g of preservative, 30 g of wetting agent, 30 g of lubricant.

[0027] Sodium polyacrylate is used as the dispersant, polydimethylsiloxane is used as the defoamer, benzisothiazolinone is used as the preservative, polyether-modified trisiloxane is used as the wetting agent, and sodium stearate is used as the lubricant.

[0028] The preparation method of the hydrophobic carbon black paste of the composite material for artificial leather includes the following steps:

[0029] Step 1: Weigh carbon black of 2000 mesh and add it to DMF solvent, and ultrasonically treat for 40 min to obtain a carbon black suspension with a mass fraction of 20%;

[0030] Step 2: First add the initiator azobisisobutyronitrile to the carbon black suspension and add it in a molar ratio of GMA:MMA of 4:1, react at 60 °C and a rotation speed of 200 r / min for 6 hours, stop heating, and after cooling to 40 °C, add the inhibitor, add deionized water, filter and collect the precipitate to obtain hydrophobic modified carbon black;

[0031] Step 3: Mix the dispersant, defoamer, preservative, wetting agent, lubricant, DMF, deionized water and hydrophobic modified carbon black, and mechanically oscillate and ball mill at a frequency of 3 Hz. This step is repeated 2 times, each time for 30 min. Subsequently, centrifuge and defoam at a rate of 2000 r / min for 20 min. Filter out the zirconium beads with a 100-mesh screen to obtain the hydrophobic aqueous carbon black paste.

[0032] The present invention and its embodiments have been described above, and such description is not restrictive. If those of ordinary skill in the art are inspired by it and, without departing from the gist of the present invention, creatively design similar embodiments to this technical solution, they shall fall within the protection scope of the present invention.

[0033] Example 2

[0034] A composite material for artificial leather, and the raw material ratio of the composite material is as follows: 5000 g of carbon black, 8 g of initiator, 1000 g of GMA, 200 g of MMA, 8 g of inhibitor, 200 g of dispersant, 20 g of defoamer, 20 g of preservative, 50 g of wetting agent, 50 g of lubricant.

[0035] Use polymaleic anhydride as the dispersant, ethylene glycol siloxane as the defoamer, octyl isothiazolinone as the preservative, 2,4,7,9 - tetramethyl - 5 - decyne - 4,7 - diol ethoxylate as the wetting agent, and calcium stearate as the lubricant.

[0036] The preparation method of the hydrophobic carbon black slurry of the composite material for artificial leather described above includes the following steps:

[0037] Step 1: Weigh carbon black with a mesh size of 2000 and add it to DMF solvent, and perform ultrasonic treatment for 60 min to obtain a carbon black suspension with a mass fraction of 20%;

[0038] Step 2: First add the initiator azobisisobutyronitrile to the carbon black suspension and add it in a molar ratio of GMA:MMA of 4:1, react at 60 °C and a rotation speed of 400 r / min for 12 hours. After stopping heating and waiting for it to cool to 40 °C, add the inhibitor, add deionized water, filter and collect the precipitate, which is the hydrophobic modified carbon black;

[0039] Step 3: Mix the dispersant, defoamer, preservative, wetting agent, lubricant, DMF, deionized water and the hydrophobic modified carbon black, and perform mechanical vibration ball milling at a frequency of 3 Hz. This step is repeated 2 times, each time for 30 min. Then centrifuge and defoam at a rate of 3000 r / min for 20 min. Filter out the zirconium beads with a 100 - mesh screen to obtain the hydrophobic aqueous carbon black slurry.

[0040] Example 3

[0041] A composite material for artificial leather, and the raw material ratio of the composite material is as follows: 2000 g of carbon black, 3 g of initiator, 400 g of GMA, 80 g of MMA, 3 g of inhibitor, 80 g of dispersant, 8 g of defoamer, 8 g of preservative, 10 g of wetting agent, 10 g of lubricant.

[0042] Using ammonium acrylate-polyethylene copolymer as a dispersant, polydimethylsiloxane as an antifoaming agent, benzisothiazolinone and octylisothiazolinone as preservatives simultaneously, tetramethyl decynediol ethoxylate as a wetting agent, and pentaerythritol stearate as a lubricant.

[0043] The preparation method of the hydrophobic carbon black paste for the composite material used in artificial leather includes the following steps:

[0044] Step 1: Weigh carbon black with 2000 mesh and add it to DMF solvent, and perform ultrasonic treatment for 60 min to obtain a carbon black suspension with a mass fraction of 20%.

[0045] Step 2: First add initiator azobisisobutyronitrile to the carbon black suspension and add it in a molar ratio of GMA:MMA of 4:1, react at 60 °C and a rotation speed of 400 r / min for 12 hours. After stopping heating, wait until the temperature drops to 40 °C and then add an inhibitor, add deionized water, filter and collect the precipitate to obtain hydrophobically modified carbon black.

[0046] Step 3: Mix the dispersant, antifoaming agent, preservative, wetting agent, lubricant, DMF, deionized water and hydrophobically modified carbon black, and perform mechanical vibration ball milling at a frequency of 5 Hz. This step is repeated 2 times, 30 min each time. Then centrifuge and defoam at a rate of 3000 r / min for 20 min. Filter out the zirconium beads with a 100-mesh screen to obtain a hydrophobic aqueous carbon black paste.

[0047] Performance detection method:

[0048] Stability test: Take 100 ml of the hydrophobically modified carbon black paste prepared in Examples 1, 2 and 3 respectively, put them into graduated cylinders, and let them stand for 1 day, 7 days, 14 days, 21 days and 30 days respectively. By comparing the ratio of the upper-layer paste to the total paste, the sedimentation ratio is obtained. The larger the sedimentation ratio value, the better the stability of the paste. The specific test results are shown in Table 1.

[0049] Hydrophobicity test: Coat the hydrophobically modified carbon black paste prepared in Examples 1, 2 and 3 on artificial leather PU, and use a contact angle measuring instrument to evaluate its hydrophobicity. The specific results are shown in Table 2.

[0050] Table 1 Stability of hydrophobically modified carbon black paste

[0051]

[0052] Table 2 Contact angle of water on artificial leather PU coated with hydrophobically modified carbon black paste

[0053] Performance Contact Angle Example 1 109.5° Example 2 105.3° Example 3 98.9° Unmodified Carbon Black 43°

[0054] From the comparison of Examples 1, 2 and 3, it is known that the carbon black modified by GMA-MMA copolymer has good stability and hydrophobicity. This shows that the GMA-MMA copolymer has good performance improvement on the dispersibility and stability of carbon black. In addition, it also obtains good hydrophobic effect. At the same time, the comparison between Example 1 and Examples 2 and 3 shows that adding too much or too little carbon black modification material will not improve the performance, but will reduce the performance to a certain extent.

[0055] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

[0056] The above description of the present invention and its embodiments is not restrictive, and the actual structure is not limited thereto. Generally speaking, if those of ordinary skill in the art are inspired by it and design similar structural modes and embodiments without creative work without departing from the purpose of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. Composite material for artificial leather, characterized in that, The composite material comprises the following components in parts by weight: 20-50 parts of hydrophobically modified carbon black, 5-10 parts of dispersant, 0.1-0.5 parts of defoamer, 0.1-0.2 parts of preservative, 0.1-0.5 parts of wetting agent, 0.3-0.5 parts of lubricant, 3-5 parts of DMF, 10-15 parts of deionized water, and 20-50 parts of zirconium beads.

2. The composite material for artificial leather according to claim 1, characterized in that: The dispersant is one of sodium polyacrylate, poly maleic anhydride, or ammonium acrylate-polyethylene copolymer.

3. The composite material for artificial leather according to claim 1, characterized in that: The defoamer is one of polydimethylsiloxane, ethylene glycol siloxane, or polydimethylsiloxane.

4. The composite material for artificial leather according to claim 1, characterized in that: The preservative is one or more of isothiazolinone and isothiazolinone.

5. The composite material for artificial leather according to claim 1, characterized in that: The wetting agent is one of polyether-modified trisiloxane or ethoxylated tetramethyl decynediol.

6. The composite material for artificial leather according to claim 1, wherein: The lubricant is one of sodium stearate, calcium stearate, or pentaerythritol stearate.

7. A method for preparing a hydrophobic carbon black paste for a composite material for artificial leather according to any one of claims 1-6, characterized in that, It includes the following steps: Step 1: Weigh a certain mass of carbon black and dissolve it in N,N-dimethylformamide. After ultrasonic treatment, a carbon black suspension is obtained. Step 2: Add GMA and MMA to the carbon black suspension in a certain ratio, heat and stir while dropping the initiator. After the heating and stirring are completed, add the inhibitor to obtain the polymerization product. Subsequently, add water for precipitation and filtration to obtain hydrophobically polymer-modified carbon black. Step 3: Mix the dispersant, defoamer, preservative, wetting agent, lubricant, DMF, deionized water, and hydrophobically modified carbon black. Add zirconium beads to the mixture for ball milling. Centrifuge the ball-milled product to defoam and filter out the zirconium beads to obtain a hydrophobic aqueous carbon black paste.

8. The preparation method of the hydrophobic carbon black paste for the composite material for artificial leather according to claim 7, characterized in that: In Step 1, the particle size of the carbon black is 2000-2500 mesh, the DMF is of analytical grade, and the ultrasonic time is 40-60 min.

9. The preparation method of the hydrophobic carbon black paste for the composite material for artificial leather according to claim 7, characterized in that: In Step 2, the molar ratio of GMA to MMA is 4-4.5:1; it needs to be heated to 60-80 °C and stirred at a speed of 200-400 r / min for 6-12 h; the initiator is azobisisobutyronitrile, and the inhibitor is hydroquinone.

10. The preparation method of the hydrophobic carbon black paste for the composite material for artificial leather according to claim 7, characterized in that: In Step 3, the particle size of the zirconium beads is 50-70 mesh, the ball milling time is 60-90 min; the centrifugation time is 10-20 min, and the speed is 3000-5000 r / min.

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