Carbon black and application thereof

Abstract

Provided is carbon black having excellent dispersibility. The carbon black has a full width at half maximum (FWHM) of more than 0 and 0.3 [mu] m or less as measured by a centrifugal sedimentation method in which absolute ethyl alcohol is used as a solvent.

Description

Technical Field

[0001] The invention relates to carbon black, in particular to carbon black suitable for coatings. Background Art

[0002] Carbon black (or carbon black) is an amorphous carbon widely used as a colorant or filler in industry. When used as a colorant, it can provide black or dark effects to inks or coatings. When used as a filler, it can improve the mechanical strength of rubber products. Since carbon black can not only give products color, but also enhance the mechanical properties of products, it is widely used in various fields.

[0003] However, in actual application, the carbon black content in the product is usually not very high, because once it exceeds a certain limit, the mechanical strength of the product will decrease. Therefore, the industry generally hopes that the blackness of the carbon black is as high as possible, so that a smaller amount of carbon black can be used to make the product reach the desired blackness. Summary of the invention

[0004] In view of the above problems, the object of the present invention is to provide a carbon black which can be added to a product to give the product a high blackness.

[0005] In order to achieve the above object, the present invention provides a carbon black having a full width at half maximum (FWHM) greater than 0 and less than 0.3 microns measured by a centrifugal sedimentation method, wherein the centrifugal sedimentation method uses anhydrous ethanol as a solvent.

[0006] Further, the full width at half maximum is greater than 0 and less than 0.2 micrometers. Further, the full width at half maximum is greater than 0 and less than 0.17 micrometers.

[0007] Furthermore, the carbon black has a mode particle size greater than 0 and less than 0.4 micrometers measured by a centrifugal sedimentation method, wherein anhydrous ethanol is used as a solvent. Furthermore, the mode particle size is greater than 0 and less than 0.3 micrometers.

[0008] Furthermore, the primary particle size of the carbon black is 10 to 80 nanometers.

[0009] Furthermore, the particle size of the carbon black aggregate is 100 to 600 nanometers.

[0010] Furthermore, the carbon black has a volatile matter content of 2 to 10 wt %.

[0011] Furthermore, the carbon black has a tinting strength (Tint) of 90% to 128%.

[0012] The present invention also provides a use of the carbon black, which is used in coatings.

[0013] Furthermore, the coating is ink, metallic paint or color paste.

[0014] The carbon black of the invention has good dispersibility and can be added into products to give the products high blackness. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1A , Figure 1B and Figure 1C 3 and 4 are particle size distribution curves showing the carbon blacks of Production Example 1, Production Example 2, and Comparative Example 1, respectively. DETAILED DESCRIPTION

[0016] The “full width at half maximum (FWHM)” referred to in the present invention refers to the width of the particle size distribution curve at half peak height.

[0017] The "mode particle size (D mode )” refers to the diameter determined by the maximum peak of the particle size distribution curve.

[0018] The "particle size distribution curve" in the present invention is obtained by a centrifugal sedimentation method, wherein the centrifugal sedimentation method uses anhydrous ethanol as a solvent.

[0019] In the present invention, “between X and Y” is equivalent to “X to Y”, which includes the end values ​​X and Y.

[0020] Carbon black provided by the present invention has a full width at half maximum (FWHM) measured by centrifugal sedimentation method that is greater than 0 and is less than 0.3 microns. In certain embodiments, the full width at half maximum is between any two of the following values: 0.3, 0.27, 0.25, 0.23, 0.21, 0.2, 0.19, 0.17, 0.16, 0.13, 0.1, 0.07, 0.05, 0.03 and 0.01 microns. In certain embodiments, the full width at half maximum is greater than 0 and is less than 0.2 microns. In certain embodiments, the full width at half maximum is greater than 0 and is less than 0.17 microns.

[0021] The carbon black may have a mode particle size greater than 0 and less than 0.4 microns as measured by centrifugal sedimentation. In certain embodiments, the mode particle size is between any two of the following values: 0.4, 0.37, 0.35, 0.33, 0.31, 0.29, 0.28, 0.27, 0.26, 0.25, 0.24, 0.23, 0.22, 0.21, 0.17, 0.15, 0.13, 0.1, 0.08, 0.06, 0.049, 0.04, 0.288, 0.02 and 0.01 microns. In certain embodiments, the mode particle size is greater than 0 and less than 0.3 microns. In certain embodiments, the mode particle size is greater than 0 and less than 0.2 microns.

[0022] In certain embodiments, the primary particle size of the carbon black is 10 to 80 nanometers. In certain embodiments, the primary particle size of the carbon black is between any two of the following values: 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 and 75 nanometers. In certain embodiments, the particle size of the aggregate of the carbon black is 100 to 600 nanometers. In certain embodiments, the particle size of the aggregate of the carbon black is between any two of the following values: 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550 and 575 nanometers.

[0023] The carbon black may have a volatile content of 2 to 10 wt %. In certain embodiments, the volatile content is between any two of the following values: 2.2 wt %, 2.4 wt %, 2.6 wt %, 2.8 wt %, 3.5 wt %, 4.0 wt %, 4.5 wt %, 5 wt %, 5.5 wt %, 6 wt %, 6.5 wt %, 7 wt %, 7.5 wt %, 8 wt %, 8.5 wt %, 9 wt % and 9.5 wt %.

[0024] In the present invention, the carbon black may have a tinting strength (Tint) of 90% to 128%. In certain embodiments, the tinting strength is between any two of the following values: 91%, 95%, 97%, 100%, 102%, 107%, 110%, 112%, 115%, 117%, 120%, 123%, 125% and 127%.

[0025] The present invention also provides a use of the aforementioned carbon black, which is used in coatings. The coatings include but are not limited to: inks, metallic paints or color pastes. The color pastes can be PU (polyurethane) color pastes.

[0026] Production Example: Production of Carbon Black

[0027] The carbon blacks of Examples 1 and 2 were obtained by modifying JE4205 carbon black of International Rubber using the carbon material post-modification treatment system disclosed in Taiwan Patent No. 1796678B, and the manufacturing conditions are shown in Table 1. The contents of Taiwan Patent No. 1796678B are incorporated herein by reference in their entirety.

[0028] Table 1

[0029]

[0030] Table 2 shows the nitrogen adsorption specific surface area (NSA), carbon black oil absorption value (OAN), tinting strength (Tint) and volatile content (volatile) of the carbon black of Preparation Example 1, Preparation Example 2 and Comparative Example 1. The carbon black of Comparative Example 1 in Table 2 refers to unmodified JE4205 carbon black. The measurement items listed in Table 2 were carried out in the following manner:

[0031] [NSA]

[0032] The specific surface area of ​​carbon black is measured according to ASTM D6556. The gas pressure of carbon black adsorbed and desorbed on the surface and pore size at a constant temperature is measured, and the total surface area of ​​the external surface area and the internal surface area is measured according to the BET theoretical formula using the nitrogen surface area. The specific surface area is calculated using the gas molecular cross-sectional area, gas molecular volume, and sample weight.

[0033]

[0034] P is pressure, P 0 is the saturation pressure, V a is the total absorption volume, C is the BET constant, V m The volume of gas required to form a monolayer.

[0035] [OAN (oil absorption number)]

[0036] Measure carbon black OAN according to ASTM D2414. Weigh a certain amount of carbon black with a density of 1.042 to 1.047 g / cm 3 Titrate white mineral oil to the endpoint, calculate the absorption value based on the weight of the carbon black sample and the titration amount, and substitute it into the following formula to obtain the OAN value.

[0037]

[0038] D: White mineral oil (petroleum) absorption value of carbon smoke,

[0039] V: Volume of white mineral oil (petroleum) consumed,

[0040] M: Sample weight

[0041] [Tint Strength]

[0042] The carbon black tinting strength is measured according to ASTM D3265. A certain amount of carbon black, zinc oxide, and epoxidized soybean oil are weighed and ground and dispersed, and then a film-pulling device is used to pull out a 7 mm long and 4 mm wide ink film. The ink reflectivity is measured using a densitometer. The tinting strength is calculated according to the following formula. T in the following formula represents the tinting strength.

[0043]

[0044] [Volatile matter]

[0045] This is a measure of the organic compounds emitted by carbon black when baked at 950℃ for 7 minutes. All of them are residual oil, adhesives, and surface functional groups. The weight of the crucible before and after the carbon black is burned is measured and the percentage of loss is calculated.

[0046] Table 2

[0047] Production Example 1 Production Example 2 Comparative Example 1 <![CDATA[NSA(m 2 / g)]]> 125 125 125 OAN(mL / 100g) 65 72 60 Tinting strength (%) 120 101 130 Volatile matter (%) 2.5 5.0 Less than 1

[0048] Figure 1A , Figure 1B and Figure 1C The particle size distribution curves of carbon black of manufacturing example 1, manufacturing example 2 and comparative example 1 are shown respectively. The aggregate particle size distribution curve is measured by centrifugal sedimentation method using anhydrous ethanol as solvent without using any dispersant. The particle size distribution curve is measured using a Brookhaven BI-DCP disc centrifuge, with a red light diode, and the distribution curve of the aggregate of the dispersed solid is determined based on the absorption value measurement. The detailed measurement method is described as follows.

[0049] Place 2 grams of carbon black and 25 mL of anhydrous ethanol in a 50 mL beaker, place the beaker containing the carbon black slurry in an ultrasonic oscillation water tank, and oscillate it for 1 minute for pre-dispersion. Then, place a probe oscillator in the slurry, cool the beaker with ice, and disperse it under ultrasonic oscillation (70% pulse) for 5 minutes to obtain a carbon black dispersion.

[0050] Before starting the measurement, the centrifuge was operated at 8000 rpm for 10 minutes. Then, 1 mL of anhydrous ethanol and 15 mL of deionized water were injected as the rotating solution, and 200 μL of n-dodecane was used to cover the rotating solution of the centrifuge. Then, 0.2 mL of the dispersion was injected into the turntable containing the rotating solution, and the measurement program was started. Under astigmatism correction and automatic baseline correction, the raw data was calculated using the instrument's calculation process, and the obtained Figure 1A , Figure 1B , Figure 1C And the results in Table 3.

[0051] Table 3

[0052] Production Example 1 Production Example 2 Comparative Example 1 Mode particle size (micrometer) 0.288 0.049 0.494 FWHM(μm) 0.153 0.031 0.52

[0053] Example:

[0054] Manufacturing of metallic paint

[0055] The components listed in Table 4 were mixed in proportion, wherein the carbon black was the carbon black of Manufacturing Example 1, Manufacturing Example 2 or Comparative Example 1. After mixing, the mixture was uniformly mixed by a high-speed stirrer, and the resulting slurry was added to a horizontal bead mill for a predetermined grinding time of 50 minutes. After grinding, the fineness was determined by a fineness meter until the fineness was less than 10 microns. Then, a solvent was added to adjust the viscosity to the same range (i.e., the viscosity was FC#4 60±10 seconds), thereby obtaining the metallic paints of Example 1, Example 2 and Comparative Example 2.

[0056] Table 4

[0057] Metallic paint ingredients Weight A136-70 (solid content 70%) purchased from Dali Polymer Co., Ltd. 114 Melamine MR625 (solid content 76%) purchased from Changchun Chemical as a crosslinking agent 20 BYK-118 (solid content 80%) 1.5 Carbon Black 15 BYK057 (solid content 40%) 0.5 South Korea CKB POLYFLOW No.90 3 Thinner 45

[0058] <Note> In the above table, BCS / Xylene / #150=40 / 40 / 20 is used as the diluent, where #150 refers to paint solvent-150 (High-Flash Aromatic Naphtha-150); BYK-118, BYK057 and POLYFLOW No.90 are used as additives.

[0059] The metallic paints of Example 1, Example 2 and Comparative Example 2 were coated on tinplate with a wire rod and baked at 130°C for 30 minutes. Then, the gloss was measured with a gloss meter (Dr Lange REFO3), and the blackness and hue were measured with a colorimeter (X-rite Ci7600). When measuring the blackness and hue, the SCE* (specular light removal) mode was used to exclude the specular reflected light, so that the color seen by the human eye can be truly presented. The test results are shown in Table 5.

[0060] Table 5

[0061]

[0062] As shown in Table 5, the metallic paint added with the carbon black (modified) of the present invention exhibits excellent blackness (i.e., L* is significantly lower) and has a higher glossiness. It is worth noting that, as shown in Table 2, although the carbon blacks of Preparation Examples 1 and 2 have a certain degree of blackness, the blackness is significantly lower than that of the carbon black of Comparative Example 1. However, in the experimental results of Table 5, the metallic paints prepared using the carbon blacks of Preparation Examples 1 and 2 have a higher blackness than the metallic paint prepared using Comparative Example 1. This result proves that the carbon blacks of Preparation Examples 1 and 2 have extremely excellent dispersibility in the metallic paint, and therefore can well present the nature of carbon black in the metallic paint, thereby making the metallic paint have excellent blackness.

[0063] Manufacturing of PU color paste

[0064] The ingredients listed in Table 6 were mixed in proportion, wherein the carbon black was the carbon black of Manufacturing Example 1 and Manufacturing Example 2, respectively, to prepare the PU color paste precursors of Example 3 and Example 4.

[0065] Table 6

[0066] Items Weight(g) Polyester polyols 66 Carbon Black 33 Dispersant (BYK-9076) 1 Total weight 100

[0067] 18 g of #150 solvent was added to the PU color paste precursors of Examples 3 and 4 and stirred for 10 minutes. The viscosity (centipoises, cps) and torque % (Torque %) values ​​were measured using a BROOKFIELD instrument. The results are shown in Table 7.

[0068] Table 7

[0069]

[0070] From the results in Table 7, it can be seen that the PU color paste precursors of Examples 3 and 4 have good fluidity, which means that the carbon black of Preparation Examples 1 and 2 can be well dispersed in the PU color paste.

[0071] In summary, the carbon black of the present invention can not only give the coating a higher glossiness, but also give the coating an excellent blackness, and the carbon black of the present invention has good dispersibility and has good dispersibility in the coating.

[0072] The above are merely preferred embodiments of the present invention, and should not be used to limit the scope of implementation of the present invention. That is, simple equivalent changes and modifications made in accordance with the scope of the patent application and the content of the invention description of the present invention are still within the scope of the patent of the present invention.

Claims

1. A carbon black having a full width at half maximum (FWHM) greater than 0 and less than 0.3 μm as measured by a centrifugal sedimentation method, wherein the centrifugal sedimentation method uses anhydrous ethanol as a solvent.

2. The carbon black as claimed in claim 1, wherein the full width at half maximum is greater than 0 and is less than 0.2 micrometers.

3. The carbon black as claimed in claim 2, wherein the full width at half maximum is greater than 0 and is less than 0.17 micrometer.

4. Carbon black as claimed in claim 1, having a mode particle size (D mode ) is greater than 0 and less than 0.4 microns, wherein the centrifugal sedimentation method uses anhydrous ethanol as the solvent.

5. The carbon black as claimed in claim 4, wherein the mode particle size is greater than 0 and is less than 0.3 microns.

6. The carbon black according to claim 1, wherein the primary particle size is 10 to 80 nanometers.

7. The carbon black as claimed in claim 1, wherein the particle size of the aggregates is 100 to 600 nanometers.

8. The carbon black according to claim 1, which has a volatile matter of 2 to 10% by weight.

9. The carbon black according to claim 1, having a tinting strength of 90% to 128%.

10. Use of the carbon black as claimed in claim 1 for coatings.

11. The use according to claim 10, wherein the coating is ink, metallic paint or color paste.

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