Colorless-phase black master batch, colorless-phase black fiber and preparation method thereof

Abstract

The invention discloses a colorless-phase black master batch, a colorless-phase black fiber and a preparation method of the colorless-phase black master batch, and belongs to the technical field of high polymer material coloring. Aiming at the defects of'dead black 'and'splicing black' technical color cast of the existing carbon black colored product, the master batch comprises a polyamide carrier, a coloring system (carbon black, phthalocyanine blue, permanent violet RL and dye blue 60) and a polymeric dispersant; master batches are prepared through twin-screw extrusion (nine-temperature-zone gradient heating), and the master batches and a carrier are further subjected to composite spinning to obtain colorless-phase black fibers. By means of spectrum complementary absorption of a coloring system, a value a and a value b of a product approach to zero (a is smaller than or equal to 0.1, and b is smaller than or equal to 0.1), an L value is 18-20, and neutral hue and high blackness are achieved; the dye blue 60 endows the transparent layering sense, the process is stable, the adaptability is high, and the method is suitable for the field of high-end products.

Description

Technical Field

[0001] This invention relates to the field of polymer material coloring technology, specifically to a colorless black masterbatch, fiber, and its preparation method. Background Technology

[0002] Black, as a classic and widely used color, holds an irreplaceable position in the automotive, home appliance, consumer electronics, high-end packaging, and building materials industries. Ideal pure black should possess extremely high blackness (low lightness L value) and visually devoid of any red, blue, or yellow hues (i.e., chromaticity a and b values ​​approaching zero), presenting a deep, pure, and substantial texture. As consumers' demands for the appearance and texture of high-end products continue to rise, the market's need for black masterbatches that combine high blackness, neutral hue, and visual transparency is becoming increasingly urgent.

[0003] Currently, the primary industrial technique for achieving black coloring in masterbatches is the use of carbon black. Carbon black is the preferred black colorant due to its extremely high tinting strength and low cost. Through its broad absorption and scattering of visible light, it achieves high hiding power and blackness. In addition, to achieve a black effect in certain specific applications (such as adjusting hue or for cost considerations), a "blending" technique exists that physically mixes different colored organic pigments. This method relies on the superposition of the absorption spectra of different colored pigments, theoretically covering a portion of the visible light spectrum.

[0004] Although carbon black and "black blending" techniques are widely used in color masterbatches, they both have significant technical limitations in applications pursuing ultimate aesthetics and high-quality appearance, making it difficult to achieve a truly "colorless deep black" effect. For example, patent CN112812359A aims to prepare carrier-free, colorless oil-black masterbatch by using a high proportion of carbon black, dye blends, and a special dispersant. However, this technical solution simply pursues physical covering performance; the use of a large amount of carbon black exacerbates light scattering within the system, resulting in a "dead black" appearance on the surface of the colored product, severely sacrificing the transparency and visual depth of the color. The resulting black lacks visual depth and dynamism, failing to meet the requirements of high-end consumer electronics products for a deep and vibrant black texture. Patent CN106433033A discloses a black masterbatch for improving the blackness of plastic products. Its technical solution focuses on adjusting the inherent yellow or brown hues of carbon black by blending it with a small amount of blue pigment, aiming to achieve a more visually "blue-black" effect. However, this method suffers from significant incomplete spectral compensation. This results in its colored products still showing a residual yellow-green tint under certain lighting conditions, making it impossible to achieve a true neutral black where both the a and b values ​​are close to zero. Summary of the Invention

[0005] The purpose of this invention is to provide a colorless black masterbatch, fiber, and preparation method thereof to solve the problem that existing spectral compensation is insufficient and cannot achieve neutral black.

[0006] The technical solution of the present invention to solve the above-mentioned technical problems is as follows: A colorless black masterbatch includes a carrier, a coloring system, and a dispersant; the coloring system is composed of carbon black, phthalocyanine blue, permanent violet RL, and dye blue 60; the carrier is a polyamide resin; and the dispersant is a polymeric dispersant.

[0007] In a further embodiment, the polyamide resin is glossy nylon 6 chips.

[0008] A further formulation, by weight, comprises the following components: 68-72 parts carrier, 18-20 parts carbon black, 2-6 parts phthalocyanine blue, 2-4 parts permanent violet RL, 1-3 parts dye blue 60, and 1-3 parts dispersant.

[0009] In a further embodiment, the dispersant is Tianshi NEW400, and the melting point of the dispersant is ≥118℃.

[0010] In a further embodiment, after the colorless black masterbatch is made into an article, the Lab color coordinates of the article satisfy the following: the lightness L value is 18-20, the absolute value of the chromaticity a value is ≤0.1, and the absolute value of the chromaticity b value is ≤0.1.

[0011] A method for preparing a colorless black masterbatch as described above includes the following steps: S1: Weigh carbon black, phthalocyanine blue, permanent violet RL, dye blue 60 and dispersant in the coloring system according to the proportion, and mix them evenly to obtain a premix; S2: Feed the carrier and the premix into an extrusion device respectively, and melt mix them to obtain a masterbatch melt; S3: Extrude the masterbatch melt, cool it and pelletize it to obtain a colorless black masterbatch.

[0012] In a further embodiment, the extrusion equipment is a twin-screw extruder; the twin-screw extruder has nine temperature zones, and the temperatures of each temperature zone along the material conveying direction are 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃ respectively, and the die head temperature of the twin-screw extruder is 230℃.

[0013] A colorless black fiber is made by mixing the above-mentioned colorless black masterbatch with a carrier; by weight, the amount of colorless black masterbatch added is 15-25 parts, and the amount of carrier added is 75-85 parts.

[0014] In a further embodiment, the colorless black fiber is FDY fiber with specifications of 24D / 24F-72D / 24F.

[0015] A method for preparing colorless black fiber includes the following steps: S21: Drying colorless black masterbatch and carrier separately, mixing them evenly, and feeding them into an extrusion device for melt composite compounding to obtain a composite melt; S22: Metering the composite melt and spinning it into fibers, followed by cooling, oiling, stretching and shaping, and winding to obtain colorless black fiber. The present invention has the following beneficial effects: This invention is the first to scientifically blend carbon black, phthalocyanine blue, permanent violet RL, and dye blue 60. This is not a simple physical mixture, but a design based on the precise optical absorption characteristics of each component (phthalocyanine blue absorbs orange-red light in the 620-680nm range, permanent violet RL absorbs yellow-green light in the 520-580nm range, and dye blue 60 assists in absorbing yellow-green light and increases transparency). This achieves perfect absorption and complementarity across the entire visible light spectrum, fundamentally solving the color shift problem of single carbon black and the incomplete spectral compensation problem of "black blending" technology.

[0016] This invention reveals a multi-layered optical mechanism that achieves a "transparent deep black" effect through "broad-spectrum absorption (carbon black) + selective absorption correction (pigment) + transparency adjustment (dye)". The introduction of dye blue 60 is key, as its transparency allows some light to penetrate to the pigment layer and be deeply absorbed, thus producing a sense of depth and layering that cannot be achieved by high-opacity pigments alone.

[0017] The black products prepared by the compound system have chromaticity coordinates a and b values ​​that can approach zero infinitely (e.g., |a|, |b|<0.1), exhibiting true "colorless black" while maintaining extremely low lightness L value. The visual blackness and purity significantly surpass traditional technical solutions. Attached Figure Description

[0018] Figure 1 Example 1 is a colorless nylon 6 black masterbatch.

[0019] Figure 2 Example 1: Colorless FDY Nylon 6 black fiber. Detailed Implementation

[0020] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0021] Example 1: This embodiment provides a method for preparing colorless nylon 6 black masterbatch, which consists of the following raw materials in parts by weight: 70 parts of bright nylon 6 chips, 18 parts of carbon black, 4 parts of phthalocyanine blue, 4 parts of permanent violet RL, 2 parts of dye blue 60, and 2 parts of dispersant.

[0022] In this embodiment, the carbon black is a black powder with a purity of 99.9%.

[0023] In this embodiment, the phthalocyanine blue pigment is a bright green-blue powder with a purity of 99.9%.

[0024] In this embodiment, the permanent violet RL pigment is a purple powder with a purity of 99.9%.

[0025] In this embodiment, the dye blue 60 pigment is a reddish-blue powder with a purity of 99.9%.

[0026] In this embodiment, the dispersant is Tianshi NEW400, which has a melting point as high as 118°C.

[0027] This embodiment provides a method for preparing colorless nylon 6 black masterbatch, including the following steps: S11: Weigh carbon black, phthalocyanine blue, permanent violet RL, dye blue 60 and dispersant according to the set ratio, premix and put into the buffer bin, then put into the hopper and stir with a spiral until the mixture is uniform to obtain the premixed material; S12: Feed bright nylon 6 chips from the main feed port and premix from the side feed port. Mix the bright nylon 6 chips and premix evenly and then melt-mix in a twin-screw extruder to obtain nylon 6 black masterbatch melt. S13: Nylon 6 black masterbatch melt strip is extruded from the outlet of the twin-screw extruder. After being cooled by a water cooling tank, the strip enters a pelletizer for pelletizing, vibration screening and blower drying to obtain the Nylon 6 black masterbatch.

[0028] This embodiment also provides a colorless nylon 6 black fiber, which is composed of the following raw materials in parts by weight: 20 parts nylon 6 black masterbatch and 80 parts bright nylon 6 chips.

[0029] This embodiment also provides a method for preparing colorless nylon 6 black fibers, including the following steps: S21: The black nylon 6 masterbatch and the bright nylon 6 chips are dried separately. The bright nylon 6 chips are fed into the main feed port. The black nylon 6 masterbatch is put into the buffer bin, then placed into the hopper and stirred evenly by a spiral. It is then fed into the side feed port. After being mixed evenly, it is compounded and melted in a twin-screw extruder to obtain a composite melt. S22: The composite melt obtained in step S21 is metered by a metering pump and then enters the spinning box. It is then spun into composite filaments through the components. After slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the channel, stretching and shaping, and winding, colorless FDY nylon 6 black fiber with a specification of 72D / 24F is obtained. In step S12 of this embodiment, the twin-screw extruder has nine temperature zones, with each temperature zone being 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃, and the die head temperature being 230℃.

[0030] Example 2: This embodiment provides a method for preparing colorless nylon 6 black masterbatch, which consists of the following raw materials in parts by weight: 68 parts of bright nylon 6 chips, 18 parts of carbon black, 6 parts of phthalocyanine blue, 4 parts of permanent violet RL, 2 parts of dye blue 60, and 2 parts of dispersant.

[0031] In this embodiment, the carbon black is a black powder with a purity of 99.9%.

[0032] In this embodiment, the phthalocyanine blue is a green powder with a purity of 99.9%.

[0033] In this embodiment, the permanent violet RL pigment is a purple powder with a purity of 99.9%.

[0034] In this embodiment, the dye blue 60 pigment is a reddish-blue powder with a purity of 99.9%.

[0035] In this embodiment, the dispersant is Tianshi NEW400, which has a melting point as high as 118°C.

[0036] This embodiment provides a method for preparing nylon 6 black masterbatch, including the following steps: S11: Weigh carbon black, phthalocyanine blue, permanent violet RL, dye blue 60 and dispersant according to the set ratio, premix and put into the buffer bin, then put into the hopper and stir with a spiral until the mixture is uniform to obtain the premixed material; S12: Feed bright nylon 6 chips from the main feed port and premix from the side feed port. Mix the bright nylon 6 chips and premix evenly and then melt-mix in a twin-screw extruder to obtain nylon 6 black masterbatch melt. S13: Nylon 6 black masterbatch melt strip is extruded from the outlet of the twin-screw extruder. After being cooled by a water cooling tank, the strip enters a pelletizer for pelletizing, vibration screening and blower drying to obtain the Nylon 6 black masterbatch.

[0037] This embodiment also provides a colorless nylon 6 black fiber, which is composed of the following raw materials in parts by weight: 20 parts nylon 6 black masterbatch and 80 parts bright nylon 6 chips.

[0038] This embodiment also provides a method for preparing colorless nylon 6 black fibers, including the following steps: S21: The black nylon 6 masterbatch and the bright nylon 6 chips are dried separately. The bright nylon 6 chips are fed into the main feed port. The black nylon 6 masterbatch is put into the buffer bin, then placed into the hopper and stirred evenly by a spiral. It is then fed into the side feed port. After being mixed evenly, it is compounded and melted in a twin-screw extruder to obtain a composite melt. S22: The composite melt obtained in step S21 is metered by a metering pump and then enters the spinning box. It is then spun into composite filaments through the components. After slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the channel, stretching and shaping, and winding, colorless FDY nylon 6 black fiber with specifications of 24D / 24F is obtained. In step S12 of this embodiment, the twin-screw extruder has nine temperature zones, with each temperature zone being 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃, and the die head temperature being 230℃.

[0039] Example 3: This embodiment provides a method for preparing colorless nylon 6 black masterbatch, which consists of the following raw materials in parts by weight: 70 parts of bright nylon 6 chips, 20 parts of carbon black, 4 parts of phthalocyanine blue, 2 parts of permanent violet RL, 2 parts of dye blue 60, and 2 parts of dispersant.

[0040] In this embodiment, the carbon black is a black powder with a purity of 99.9%.

[0041] In this embodiment, the phthalocyanine blue is a green powder with a purity of 99.9%.

[0042] In this embodiment, the permanent violet RL pigment is a purple powder with a purity of 99.9%.

[0043] In this embodiment, the dye blue 60 pigment is a reddish-blue powder with a purity of 99.9%.

[0044] In this embodiment, the dispersant is Tianshi NEW400, which has a melting point as high as 118°C.

[0045] This embodiment provides a method for preparing nylon 6 black masterbatch, including the following steps: S11: Weigh carbon black, phthalocyanine blue, permanent violet RL, dye blue 60 and dispersant according to the set ratio, premix and put into the buffer bin, then put into the hopper and stir with a spiral until the mixture is uniform to obtain the premixed material; S12: Feed bright nylon 6 chips from the main feed port and premix from the side feed port. Mix the bright nylon 6 chips and premix evenly and then melt-mix in a twin-screw extruder to obtain nylon 6 black masterbatch melt. S13: Nylon 6 black masterbatch melt strip is extruded from the outlet of the twin-screw extruder. After being cooled by a water cooling tank, the strip enters a pelletizer for pelletizing, vibration screening and blower drying to obtain the Nylon 6 black masterbatch.

[0046] This embodiment also provides a colorless nylon 6 black fiber, which is composed of the following raw materials in parts by weight: 20 parts nylon 6 black masterbatch and 80 parts bright nylon 6 chips.

[0047] This embodiment also provides a method for preparing colorless nylon 6 black fibers, including the following steps: S21: The black nylon 6 masterbatch and the bright nylon 6 chips are dried separately. The bright nylon 6 chips are fed into the main feed port. The black nylon 6 masterbatch is put into the buffer bin, then placed into the hopper and stirred evenly by a spiral. It is then fed into the side feed port. After being mixed evenly, it is compounded and melted in a twin-screw extruder to obtain a composite melt. S22: The composite melt obtained in step S21 is metered by a metering pump and then enters the spinning box. It is then spun into composite filaments through the components. After slow cooling, monomer suction, side blowing cooling, bundling and oiling, secondary cooling in the channel, stretching and shaping, and winding, colorless FDY nylon 6 black fiber with a specification of 48D / 24F is obtained. In step S12 of this embodiment, the twin-screw extruder has nine temperature zones, with each temperature zone being 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃, and the die head temperature being 230℃.

[0048] Comparative Example 1 (using glossy nylon 6 slices): Raw material: 100 parts of glossy nylon 6 chips. Preparation method is the same as in Example 1.

[0049] Comparative Example 2 (using glossy nylon 6 chips and reddish carbon black): Raw materials: 80 parts of glossy nylon 6 chips, 20 parts of reddish carbon black. Preparation method is the same as in Example 1.

[0050] Comparative Example 3 (using glossy nylon 6 chips and bluish carbon black): Raw materials: 80 parts of bright nylon 6 chips, 20 parts of bluish carbon black. Preparation method is the same as in Example 1.

[0051] Preferred Example 1: Nylon 6 Black Masterbatch Product Image (as shown) Figure 1 : The color of the yarns prepared in Examples 1-3 and the comparative examples was measured, and the measured Lab values ​​are shown in Table 1: Table 1. Colorimetric results of yarns in Examples 1-6 Through a horizontal comparison of the embodiments and comparative examples, the data clearly demonstrates the advantages of the present invention: Controllable blackness: The L value of the example is stable at 18-20, which is comparable to that of Comparative Examples 2-3 (single carbon black), both achieving high blackness, and is superior to Comparative Example 1 (no coloring). Hue neutrality: The absolute values ​​of a / b in the examples are ≤0.1 and ≤0.1 respectively, which are far superior to Comparative Examples 2-3 (a and b values ​​exceed 0.1, with obvious color deviation) and Comparative Example 1 (severe color deviation), truly achieving "hue-free black"; Process stability: The L / a / b values ​​of the five repeated tests in Example 1 showed very small fluctuations (as shown in Example 1, the L value was between 19.06 and 19.86, the a value was between -0.09 and -0.06, and the b value was between -0.09 and -0.07), indicating that the compound system is highly compatible with the twin-screw extrusion process and has high mass production stability.

[0052] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A colorless black masterbatch, characterized in that, It includes a carrier, a coloring system, and a dispersant; the coloring system is composed of carbon black, phthalocyanine blue, permanent violet RL, and dye blue 60; the carrier is a polyamide resin; and the dispersant is a polymeric dispersant.

2. The colorless black masterbatch according to claim 1, characterized in that, The polyamide resin is glossy nylon 6 chips.

3. The colorless black masterbatch according to claim 1, characterized in that, By weight, the contents of each component are as follows: 68-72 parts carrier, 18-20 parts carbon black, 2-6 parts phthalocyanine blue, 2-4 parts permanent violet RL, 1-3 parts dye blue 60, and 1-3 parts dispersant.

4. The colorless black masterbatch according to claim 1, characterized in that, The dispersant is Tianshi NEW400, and the melting point of the dispersant is ≥118℃.

5. The colorless black masterbatch according to claim 1, characterized in that, After the colorless black masterbatch is made into an article, the Lab color coordinates of the article satisfy the following: lightness L value is 18-20, absolute value of chromaticity a value is ≤0.1, and absolute value of chromaticity b value is ≤0.

1.

6. A method for preparing a colorless black masterbatch as described in any one of claims 1-5, characterized in that, Includes the following steps: S1: Weigh out carbon black, phthalocyanine blue, permanent violet RL, dye blue 60 and dispersant in the coloring system according to the proportion, and mix them evenly to obtain a premix; S2: The carrier and premix are fed into the extrusion equipment separately and melt-mixed to obtain masterbatch melt; S3: Extrude the masterbatch melt, cool it, and pelletize it to obtain a colorless black masterbatch.

7. The preparation method according to claim 6, characterized in that, The extrusion equipment is a twin-screw extruder; the twin-screw extruder has nine temperature zones, and the temperatures of each zone along the material conveying direction are 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃ respectively, and the die head temperature of the twin-screw extruder is 230℃.

8. A colorless black fiber, characterized in that, It is prepared by mixing the colorless black masterbatch as described in any one of claims 1-5 with a carrier; by weight, the amount of colorless black masterbatch added is 15-25 parts, and the amount of carrier added is 75-85 parts.

9. The colorless black fiber according to claim 8, characterized in that, The colorless black fiber is FDY fiber with specifications of 24D / 24F-72D / 24F.

10. A method for preparing colorless black fibers as described in claim 8 or 9, characterized in that, Includes the following steps: S21: After drying the colorless black masterbatch and the carrier separately, mix them evenly and feed them into an extrusion device for melt composite to obtain a composite melt; S22: After metering and spinning the composite melt, it is cooled, oiled, stretched and shaped, and wound to obtain colorless black fibers.

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