Metal leather and inflatable ball manufacturing method using same

Abstract

The invention discloses metal leather and a manufacturing method of an inflatable ball applying the metal leather in the field of leather. The metal leather is prepared from the following materials in parts by mass: 45-70 parts of hydroxyl-terminated polyurethane, 0-25 parts of vinyl liquid silica gel, 8-12 parts of nano-silver particles and 0-6 parts of nano-copper-zinc alloy. 2-4 parts of graphene oxide, 1-3 parts of a functional auxiliary agent and 30-50 parts of a solvent. According to the invention, a bimetallic-graphene synergistic network is adopted: nano-silver (conductive) and copper-zinc alloy (corrosion-resistant) form a flexible conductive path on a graphene skeleton, and low resistance is still maintained when the elongation at break is greater than 550%; a silane coupling agent is adopted to realize covalent bond combination of a metal particle-polymer interface, so that the problem of dispersion of a water-based system is solved; a multi-scale enhanced design is adopted, liquid silica gel provides low-temperature elasticity, polyurethane ensures high-temperature strength, and a light stabilizer inhibits photo-oxidative aging.

Description

Technical Field

[0001] The present invention relates to the field of leather, and specifically to a metal leather and a method for manufacturing a balloon filled with gas using the metal leather. Background Art

[0002] When traditional non-metallic leather materials are used, they cannot meet the antistatic requirements for electronic device packaging and flammable and explosive environments (the surface resistivity is required to be <10 6 Ω / square); they have poor weather resistance, and there is a contradiction between elasticity and strength. Although TPU has a high elongation rate, its tensile strength is <18 MPa, and it is difficult to withstand the stress of repeated inflation of the balloon filled with gas. When metal leather is used, it has poor corrosion resistance, mostly using the vacuum evaporation aluminum layer process, with poor bending resistance, and it is not environmentally friendly. Moreover, the existing balloon filled with gas has a low elongation at break, and traditional solvent-based metal leather uses carcinogenic solvents such as DMF and toluene, while it is difficult to stably disperse metal particles in the aqueous system, and agglomeration is likely to occur. Therefore, the technical personnel in this field provide a metal leather and a method for manufacturing a balloon filled with gas using the metal leather to solve the problems raised in the above background art. Summary of the Invention

[0003] The purpose of the present invention is to provide a metal leather and a method for manufacturing a balloon filled with gas using the metal leather to solve the problems raised in the above background art.

[0004] To achieve the above purpose, the present invention provides the following technical solutions:

[0005] A metal leather and a method for manufacturing a balloon filled with gas using the metal leather are made of the following materials in parts by mass: 45-70 parts of hydroxyl-terminated polyurethane, 0-25 parts of vinyl liquid silicone, 8-12 parts of nano silver particles, 0-6 parts of nano copper-zinc alloy; 2-4 parts of graphene oxide, 1-3 parts of functional additives, and 30-50 parts of solvent.

[0006] As a further scheme of the present invention: the functional additives include a silane coupling agent, a graphene dispersion liquid, and a crosslinking agent, and the ratio of the silane coupling agent, the graphene dispersion liquid, and the crosslinking agent is 4:2:1. The solvent is composed of a mixed solution of deionized water and ethanol, and the ratio of deionized water to ethanol is 5:1.

[0007] As a further scheme of the present invention: the molecular weight of the hydroxyl-terminated polyurethane is 50,000-100,000, and the vinyl content of the vinyl liquid silicone is 0.1-0.3 mmol / g.

[0008] As a further solution of the present invention: the particle size of the nano silver particles is 20-30 nm, the mass ratio of Cu to Zn in the nano copper-zinc alloy is 6:4 to 8:2, the number of layers of the graphene oxide is 1-3 layers, and the content of surface oxygen-containing groups (-OH, -COOH) is 5-8%.

[0009] A method for making metal leather includes the following steps:

[0010] Step (1): Ultrasonically disperse the nano silver particles, nano copper-zinc alloy and silane coupling agent in a solvent;

[0011] Step (2): Add polyurethane, liquid silicone, graphene oxide and light stabilizer, and mix them at high speed;

[0012] Step (3): Coat the mixture on the base cloth and hot press and cure it at 110-130 °C to form metal leather.

[0013] As a further solution of the present invention: the ultrasonic power in step (1) is 400-600 W, the frequency is 30-50 kHz, and the dispersion time is ≥45 min.

[0014] As a further solution of the present invention: the base cloth in step (3) is a corona-treated polyester woven cloth, and the surface tension is ≥42 mN / m.

[0015] A method for preparing an inflatable ball includes the following steps:

[0016] Step (1): Ball sheet design: Adopt 8-16 water droplet-shaped structures, the hot press welding temperature is 180-200 °C, and the welding time is 6-10 s;

[0017] Step (2): Air tightness test: Fill with dry air to 0.1-0.3 MPa, immerse in water to detect no bubbles, and the pressure drop after standing for 72 h is <2%

[0018] As a further solution of the present invention: in step (1), a double weld structure is provided at the edge of the ball sheet, the weld width is 5-8 mm, and in step (2), the gas filled inside during the air tightness test is helium or dry air.

[0019] As a further solution of the present invention: it includes an aerostat and an emergency rescue ball.

[0020] Compared with the prior art, the beneficial effects of the present invention are:

[0021] 1. The present invention has a breakthrough in conductivity: the surface resistivity <1.5×10 3 Ω / □, meeting the requirements of ESD protection level 3;

[0022] Balanced elasticity and strength: Elongation at break > 550%, tensile strength > 25 MPa, more than 50% better than traditional materials;

[0023] Environmentally friendly process: VOC content in the solvent system < 50 ppm, meeting the RoHS2.0 standard;

[0024] Long service life: Performance retention rate > 90% after 1000 h of xenon lamp aging.

[0025] 2. The present invention adopts a bimetal-graphene synergistic network: Nano silver (conductive) and copper-zinc alloy (corrosion-resistant) form a flexible conductive path on the graphene framework, and still maintain a low resistance when the elongation at break > 550%; Adopt an aqueous crosslinking process: Use a silane coupling agent to achieve covalent bond binding at the metal particle-polymer interface, solving the dispersion problem in the aqueous system; Adopt a multi-scale reinforcement design: Liquid silicone provides low-temperature elasticity, polyurethane ensures high-temperature strength, and light stabilizers inhibit photo-oxidative aging. Specific embodiments

[0026] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0027] In the embodiments of the present invention, a method for making a metal leather and a balloon filled with the metal leather includes the following materials in parts by mass: 45-70 parts of hydroxyl-terminated polyurethane, 0-25 parts of vinyl liquid silicone, 8-12 parts of nano silver particles, 0-6 parts of nano copper-zinc alloy; 2-4 parts of graphene oxide, functional additives: 1-3 parts, 30-50 parts of solvent.

[0028] Among them, the functional additives include a silane coupling agent, a graphene dispersion liquid and a crosslinking agent, and the ratio of the silane coupling agent, the graphene dispersion liquid and the crosslinking agent is 4:2:1. The solvent is composed of a mixed solution of deionized water and ethanol, and the ratio of deionized water to ethanol is 5:1.

[0029] Among them, the molecular weight of the hydroxyl-terminated polyurethane is 50000-100000, and the vinyl content of the vinyl liquid silicone is 0.1-0.3 mmol / g.

[0030] Among them, the particle size of the nano silver particles is 20-30 nm, the mass ratio of Cu to Zn in the nano copper-zinc alloy is 6:4 to 8:2, the number of layers of the graphene oxide is 1-3 layers, and the content of surface oxygen-containing groups (-OH, -COOH) is 5-8%.

[0031] A manufacturing method of metal leather, comprising the following steps:

[0032] Step (1): Ultrasonically disperse silver nanoparticles, nano copper-zinc alloy and silane coupling agent in a solvent;

[0033] Step (2): Add polyurethane, liquid silicone, graphene oxide and light stabilizer, and blend at high speed;

[0034] Step (3): Coating the mixture on the base fabric, and hot pressing and curing at 110-130 °C to form metal leather.

[0035] Among them, the ultrasonic power in step (1) is 400-600W, the frequency is 30-50kHz, and the dispersion time is ≥45min.

[0036] Among them, the base fabric in step (3) is a corona-treated polyester woven fabric with a surface tension of ≥42mN / m.

[0037] An inflatable ball, the preparation process includes the following steps:

[0038] Step (1): Ball piece design: Adopt 8-16 water droplet-shaped structures, the hot pressing and welding temperature is 180-200 °C, and the welding time is 6-10s;

[0039] Step (2): Airtightness test: Fill with dry air to 0.1-0.3MPa, immerse in water to detect no bubbles, and the pressure drops <2% after standing for 72h

[0040] Among them, in step (1), the edge of the ball piece is provided with a double weld structure, the weld width is 5-8mm, and in step (2), the gas filled inside during the airtightness test is helium or dry air.

[0041] Formulas of Examples 1-3 and Comparative Examples (unit: parts by mass)

[0042]

[0043] Detection methods and detection results:

[0044] 1. Material performance detection

[0045]

[0046] 2. Weather resistance detection (xenon lamp aging for 1000h)

[0047] Project Example 1 Example 2 Example 3 Commercially available PVC Color difference ΔE 1.2 1.5 1.0 4.5 Retention rate of tensile strength 93％ 91％ 95％ 60％ Change rate of surface resistivity +8％ +12％ +5％ +200％

[0048] 3. Inflatable ball performance

[0049] Test item Example 1 ball Commercially available basketball Air tightness (pressure drop in 24h) 0.9％ 3.2％ Antistatic time (s) 0.3 ＞10 Puncture strength (N) 85 60 Low temperature flexure (-30°C) No crack Cracking

[0050] Through the analysis of the above test results, it can be seen that the present invention has the following advantages:

[0051] Conductivity breakthrough: surface resistivity <1.5×10 3 Ω / □, meeting the ESD protection level 3 requirements;

[0052] Both elasticity and strength are taken into consideration: elongation at break>550%, tensile strength>25MPa, which is more than 50% better than traditional materials;

[0053] Environmentally friendly process: VOC content of solvent system is less than 50ppm, in compliance with RoHS2.0 standards;

[0054] Long life: The performance retention rate of xenon lamp after aging for 1000h is greater than 90%.

[0055] The bimetallic-graphene collaborative network of the present invention: nano silver (conductive) and copper-zinc alloy (corrosion resistant) form a flexible conductive path on the graphene skeleton, and the low resistance is maintained when the elongation at break is greater than 550%; an aqueous cross-linking process is adopted: a silane coupling agent is used to achieve covalent bonding of the metal particles and the polymer interface, solving the dispersion problem of the aqueous system; a multi-scale enhanced design is adopted: liquid silicone provides low-temperature elasticity, polyurethane ensures high-temperature strength, and a light stabilizer inhibits light-oxidation aging.

[0056] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A metal leather, characterized in that: The invention is made of the following materials in parts by weight: 45-70 parts of hydroxyl-terminated polyurethane, 0-25 parts of vinyl liquid silicone, 8-12 parts of nano silver particles, 0-6 parts of nano copper-zinc alloy, 2-4 parts of graphene oxide, 1-3 parts of functional additives and 30-50 parts of solvent.

2. The metal leather according to claim 1, characterized in that: The functional additive comprises a silane coupling agent, a graphene dispersion and a crosslinking agent, and the ratio of the silane coupling agent, the graphene dispersion and the crosslinking agent is 4:2:

1. The solvent is a mixture of deionized water and ethanol, and the ratio of the deionized water to the ethanol is 5:

1.

3. The metal leather according to claim 1, characterized in that: The molecular weight of the hydroxyl-terminated polyurethane is 50,000-100,000, and the vinyl content of the vinyl liquid silicone is 0.1-0.3 mmol / g.

4. The metal leather according to claim 1, characterized in that: The particle size of the nano silver particles is 20-30 nm, the mass ratio of Cu to Zn in the nano copper-zinc alloy is 6:4 to 8:2, the number of layers of the graphene oxide is 1-3, and the content of surface oxygen-containing groups (-OH, -COOH) is 5-8%.

5. A method for manufacturing metal leather, applied to a metal leather according to any one of claims 1 to 4, characterized in that: The steps include: Step (1) ultrasonically dispersing nano silver particles, nano copper-zinc alloy and silane coupling agent in a solvent; Step (2) adding polyurethane, liquid silicone, graphene oxide and light stabilizer, and blending at high speed; Step (3) coating the mixture on a base fabric, and hot pressing and curing at 110-130° C. to form metal leather.

6. The method for making metal leather according to claim 5, characterized in that: The ultrasonic power of step (1) is 400-600W, the frequency is 30-50kHz, and the dispersion time is ≥45min.

7. The method for making metal leather according to claim 5, characterized in that: The base fabric in step (3) is corona-treated polyester woven fabric with a surface tension of ≥42 mN / m.

8. An inflatable ball, characterized in that: The preparation method of the metal leather according to any one of claims 1 to 4 comprises the following steps: Step (1): Spherical piece design: adopt 8-16 pieces of water drop-shaped structure, hot pressing welding temperature 180-200℃, welding time 6-10s; Step (2): Air tightness test: Fill with dry air to 0.1-0.3MPa, immerse in water to detect no bubbles, and let stand for 72 hours with a pressure drop of <2%.

9. An inflatable ball according to claim 8, characterized in that: In the step (1), a double weld structure is provided at the edge of the ball piece, and the weld width is 5-8 mm. During the airtightness test in the step (2), the gas filled inside is helium or dry air.

10. Application of the inflatable ball according to claim 8 in the field of aerospace, including aerostats and emergency life-saving balls.

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