Metal highlight color master batch and production process thereof

Abstract

The invention provides a metal highlight color master batch and a production process thereof, belongs to the technical field of color master batch production, and solves the technical problems that the existing color master batch does not have stable and lasting metal luster, is poor in compatibility with an EVA (Ethylene-Vinyl Acetate) substrate and the like. The production process comprises the following steps: step 1, material selection and pretreatment; 2, material picking and preparing; step 3, banburying; step 4, three-roller grinding; step 5, granulating; and step 6, detecting and packaging. The metal highlight color master batch comprises a golden color master batch, a silver color master batch and a colored color master batch. According to the production technology, through the technological processes of pretreatment, material preparation, temperature-controlled internal mixing, three-roller grinding, multi-stage detection and circulating cooling granulation, it is guaranteed that the produced metal highlight color master batch is consistent in color batch, finished product particles are uniform in refining, and the quality is stable and controllable. The metal highlight color master batch has the advantages of long-term stability in appearance, high migration resistance grade, lasting and uniform color, excellent aging resistance, stable performance, metal luster and texture, and good compatibility with an EVA substrate.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of color master batch production, and relates to a metal high-light color master batch, in particular to a production process of the metal high-light color master batch. BACKGROUND

[0002] As a core component of sports running shoes, the MD midsole is a key carrier for brands to show product performance and technological content, and its forming process mainly includes chemical foaming and physical foaming, and the main base materials are high molecular materials such as EVA, POE and TPU. In order to meet the needs of consumers for the appearance of products in terms of 'technological aesthetics', the MD midsole often needs to present a metal high-light effect, and the traditional implementation method is a spraying process, but this process has obvious defects: VOC emission does not meet environmental protection standards, production efficiency is low, the coating has poor adhesion to the base material, is easy to fall off and crack after long-term use, and has poor color and luster durability.

[0003] Although the existing metal color master batch can replace part of the spraying process, the poor dispersibility of the metal pigment leads to uneven luster, the compatibility of the carrier resin with the EVA base material is poor, affecting the physical properties of the product, the heat resistance is insufficient, the pigment is easy to decompose in the foaming process, and the color development effect is poor, and the anti-yellowing, anti-migration and anti-aging properties are difficult to meet the long-term use requirements of sports equipment.

[0004] Therefore, the present application provides a metal high-light color master batch and a production process thereof. SUMMARY

[0005] The present application aims to solve the above problems of the prior art, and provides a metal high-light color master batch and a production process thereof, which solves the technical problem of how to prepare a metal high-light color master batch with long-term stable appearance, persistent and uniform color, stable mechanical properties, good compatibility with the EVA base material, and metal luster and texture through the process flow of pretreatment, material preparation, temperature control compounding, three-roll grinding, multi-stage detection and cyclic cooling granulation.

[0006] The object of the present application can be achieved by the following technical solutions: A production process of a metal high-light color master batch, comprising the following steps: Step 1: material selection and pretreatment: mix the metal pigment with the surfactant, stir at 60±1 DEG C for 30±1 min for surface modification, the modified metal pigment can be better compatible with the carrier resin, after modification, take a sample for observation, the modified metal pigment has no lumps, and feels smooth and has no particle sensation, and is ready for use, test the high-performance pigment by preparing a sheet on a small two-roll mixing machine according to 0.5% and 0.05% addition amount, make a foaming test piece by using an 80T oil pressure forming machine, compare the color by using a colorimeter, and then perform physical property testing, and confirm that the test piece is correct and ready for use after no error is found; Step two, material and preparation: according to the formula, weigh each raw material, the raw material composition is as follows: carrier resin, high performance pigment, fixing agent, modified metal pigment, dispersing agent and stabilizer, use electronic scale to weigh, the weighing precision of each component is ±0.01g, after weighing, classify and label, put in clean hopper, keep the same batch of modified metal pigment and high performance pigment for subsequent color matching and material supplement; Step three, internal mixing: clean the internal mixer before production, wipe the steel wire ball and calcium powder clean to avoid cross contamination of materials, stage feeding, first stage, add carrier resin into the internal mixer for pre-plasticization; second stage, add high performance pigment and fixing agent into the internal mixer, continue stirring to ensure the preliminary mixing of high performance pigment and carrier resin, after melting, continue to add modified metal pigment, dispersing agent and stabilizer, heat to 115±5℃, after strong pressure, shear and mixing, make it uniformly dispersed, plasticized and agglomerated into semi-finished product, clean the material during mixing for 3 times to ensure no local material accumulation, the material is uniformly plasticized into dense block, after forming semi-finished product, test for the first time and test for midsole shoe sample to confirm whether the color is qualified, if the test result is unqualified, return to continue internal mixing, then test again; if the test result is qualified, deliver the semi-finished product to three roll grinding process; Step four, three roll grinding: add qualified semi-finished product into hydraulic three roll grinder, grind under the condition of 80-90℃ and 0.3-0.5MPa to further refine and uniform the pigment particles in the semi-finished product, then test for the second time and test for midsole shoe sample to confirm whether the color is qualified, if the test result is unqualified, continue grinding and recheck, if the test result is qualified, deliver to granulation process; Step five, granulation: after the qualified material after grinding is added into the internal mixer for re-agglomeration, pour into single screw granulator set, which includes constant temperature machine, cold water machine, vacuum pump, screw extruder, circulating water cutting machine and centrifugal dryer, the constant temperature machine maintains the internal melting temperature of the screw extruder consistent through closed loop temperature control to ensure the stable extrusion of the metal pigment dispersion, after the material is plasticized and extruded by the screw extruder, it enters the circulating water cutting machine for underwater cutting and granulation, the particle size is controlled within 2-3mm, the cooling water of the circulating water cutting machine rapidly cools the color master batch generated during granulation, at the same time avoids the surface oxidation of the color master batch caused by high temperature, and the water containing color master batch is delivered into the centrifugal dryer, the water separated by the centrifugal dryer is delivered into the cold water machine, the cold water machine is provided with filtering structure to filter the particles, impurities in the circulating cooling water, and cool the filtered cooling water, the cooled cooling water flows back to the circulating water cutting machine to form cooling water circulation, remove the moisture on the surface of the color master batch, and output the finished color master batch after drying; Step six, detection and packaging: after granulation, sample pressure secondary shoe sample, after the quality group confirms qualified, carries on the resistance to yellowing test, the resistance to migration test and the specific gravity test, the production quantity > 200kg needs to stir first again package, before the electronic scale is calibrated with the weight, adopts the special aluminum foil bag package, every bag 25kg, the net weight error of finished product is ± 0.2kg, the qualified product covers the qualified chapter and is stored, accompanied by MSDS, TDS technical parameter data.

[0007] The metal high light color master batch includes gold color master batch, silver color master batch and color master batch, all of which have metal high light luster and are suitable for injection molding and foaming processing technology of EVA shoe material.

[0008] The gold color master batch is composed of the following components by mass percentage: carrier resin 35-37%, crystal gold powder 44-46%, crystal white gold powder 9-11%, high-performance pigment 1-3%, dispersant 3-5%, stabilizer 0.4-0.6%, color fixing agent 1-3% and surfactant 0.4-0.6%, and the sum of the mass percentages of the components is 100%.

[0009] The silver color master batch is composed of the following components by mass percentage: carrier resin 37-39%, aluminum silver powder 35-45%, crystal white gold powder 14-16%, dispersant 3-5%, stabilizer 0.4-0.6%, color fixing agent 1-3% and surfactant 0.4-0.6%, and the sum of the mass percentages of the components is 100%.

[0010] The color master batch is composed of the following components by mass percentage: carrier resin 35-40%, aluminum silver powder 10-20%, crystal gold powder 10-20%, crystal white gold powder 30-45%, color gold powder 5-15%, dispersant 3-5%, stabilizer 0.4-0.6%, color fixing agent 1-3% and surfactant 0.4-0.6%, and the sum of the mass percentages of the components is 100%.

[0011] The aluminum silver powder is composed of 93-97% Al, 1-3% isopropyl alcohol and 2-4% silicon dioxide; The crystal gold powder is composed of 42-46% synthetic fluorphlogopite, 44-48% titanium dioxide, 0-1% tin dioxide and 6-10% diiron trioxide; The crystal white gold powder is composed of 52-56% synthetic fluorphlogopite and 44-48% titanium dioxide; The color gold powder is composed of 52-56% synthetic fluorphlogopite, 40-45% titanium dioxide, 0-1% tin dioxide and 5-8% high-performance pigment.

[0012] The carrier resin is a blend of EVA7350M and EVA7470M in a mass ratio of 3:7, wherein EVA7350M provides good processing fluidity, and EVA7470M improves the compatibility with EVA shoe materials.

[0013] The dispersant is a compound of Honeywell 400A and BASF hindered phenolic antioxidant in a mass ratio of 2:1, which inhibits the agglomeration of high-performance pigments and reduces the thermal degradation of materials during processing; the surfactant is Lutensol XP 70.

[0014] The stabilizer is zinc stearate, which plays a heat stabilizing role, and the color fixing agent is 9160 color powder temperature resistant agent, which enhances the binding force of high-performance pigments and carrier resin, and cooperates to improve the heat resistance temperature of high-performance pigments.

[0015] The high-performance pigment is one of heat-resistant peach red PR122, heat-resistant red PR254, heat-resistant pink PV19, phthalocyanine blue PB15:3, phthalocyanine blue PB15:0, heat-resistant yellow brown PY42, heat-resistant red brown PBP101, ultramarine blue PB29, titanium cyanine green G7, carbon black PBK6, carbon black PBK7, heat-resistant yellow PY83, heat-resistant lemon yellow PY81 and ultramarine purple PV15, or a mixture of any combination of the above components, and the heat resistance temperature of the high-performance pigment is ≥280℃, and the color fastness is grade 7-8.

[0016] Compared with the prior art, the metal high-light color master batch and its production process have the following advantages: The production process of the metal high-light color master batch ensures the consistency of the color of the produced metal high-light color master batch, ensures the refinement and uniformity of the finished particle, and the quality is stable and controllable, through pretreatment, multi-stage detection, three-roll grinding, closed-loop temperature control and circulating cooling granulation.

[0017] The metal high-light color master batch has outstanding yellowing resistance, long-term stable appearance, high migration resistance grade, persistent and uniform color, excellent aging resistance, stable mechanical properties, metal luster and texture, and good compatibility with EVA base material. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is the production process flow chart of the present application.

[0019] Figure 2 is the specific gravity test result table in the present application.

[0020] Figure 3 is the yellowing resistance test result table in the present application.

[0021] Figure 4 is the migration resistance test result table in the present application.

[0022] Figure 5is the table of aging test results in the present application.

[0023] Figure 6 is the table of physical property test results of navy blue metal high-gloss color master batch in the present application.

[0024] Figure 7 is the first page of test report of white gold, black gold and raw wood color metal high-gloss color master batch in the present application.

[0025] Figure 8 is the second page of test report of white gold, black gold and raw wood color metal high-gloss color master batch in the present application.

[0026] Figure 9 is the third page of test report of white gold, black gold and raw wood color metal high-gloss color master batch in the present application. DETAILED DESCRIPTION

[0027] The following is a specific embodiment of the present application and further describes the technical solutions of the present application in combination with the drawings, but the present application is not limited to these embodiments.

[0028] As shown in Figure 1 , a production process of metal high-gloss color master batch, the specific steps are as follows: Step one, material selection and pretreatment: mix metal pigment and surfactant, stir at 60±1℃ for 30±1min for surface modification, the modified metal pigment can be better compatible with carrier resin, after modification, take sample observation, the modified metal pigment has no lump, the hand touch is fine and has no particle feeling, standby, test the test piece of high-performance pigment, prepare the sheet according to 0.5% and 0.05% addition amount with special base material on a small two-roll mixing machine, make foaming test piece through 80T oil pressure forming machine, compare the color with colorimeter, and then do physical property test, confirm no error, standby, special base material as base material, the single-pot amount of special base material is 100kg EVA7470M, 0.8kg stearic acid, 0.8kg zinc stearate, 1kg zinc oxide, 0.34kg odorless crosslinking agent and 3kg foaming agent AC600H; Step two, material taking and preparation: weigh each raw material according to the formula, the raw material composition is as follows: carrier resin, high-performance pigment, fixing agent, modified metal pigment, dispersant and stabilizer, use electronic scale to weigh, the weighing precision of each component is ±0.01g, after weighing, classify and label, place in clean hopper, keep the modified metal pigment and high-performance pigment of the same batch for subsequent color matching and material supplementing; Step 3, Internal Mixing: Before production, clean the internal mixer, wiping it clean with steel wool and calcium powder to avoid cross-contamination of materials. Feed materials in stages. In the first stage, add the carrier resin to the internal mixer for pre-plasticization. In the second stage, add the high-performance pigment and fixing agent to the internal mixer and continue stirring to ensure the high-performance pigment and carrier resin are initially mixed. After melting, add modified metallic pigment, dispersant, and stabilizer. Heat to 115±5℃, and after strong pressure, shearing, and mixing, ensure uniform dispersion, plasticization, and agglomeration into a semi-finished product. During mixing, turn and clean the material three times to ensure no localized material accumulation. The material is uniformly plasticized into a dense block. After forming the semi-finished product, conduct the first test piece test and midsole shoe sample test to confirm color compliance. If the test results are unqualified, return to continue internal mixing and then test again. If the test results are qualified, the semi-finished product is conveyed to the three-roll milling process. Step 4, Three-roll grinding: Add the qualified semi-finished product into a hydraulic three-roll grinding mill and grind it at 80-90℃ and 0.3-0.5MPa to further refine and homogenize the pigment particles in the semi-finished product. Then, conduct a second test piece test and a midsole shoe sample test to confirm whether the color is qualified. If the test result is unqualified, continue grinding and re-inspect. If the test result is qualified, it is sent to the granulation process. Step 5, Granulation: After the qualified ground material is added to the internal mixer and agglomerated, it is poured into a single-screw granulator unit. The single-screw granulator unit includes a temperature control unit, a chiller, a vacuum pump, a screw extruder, a circulating underwater cutter, and a centrifugal dryer. The temperature control unit maintains a consistent melting temperature inside the screw extruder through closed-loop temperature control, ensuring stable extrusion of the melt after the metal pigment is dispersed. After the material is plasticized and extruded by the screw extruder, it enters the circulating underwater cutter for underwater cutting and granulation, with the particle size controlled at 2-3mm. The machine's cooling water rapidly cools the masterbatch produced during granulation, preventing oxidation of the masterbatch surface due to high temperatures. The water containing the masterbatch is then fed into a centrifugal dryer, from which the water separated is fed into a chiller. The chiller has a built-in filter structure that filters out particulate debris and impurities from the circulating cooling water and cools the filtered water. The cooled water is then returned to the underwater cutting machine to form a cooling water circulation, removing moisture from the surface of the masterbatch. After drying, the finished masterbatch product is output. Step Six, Testing and Packaging: After granulation, samples are taken and pressed into secondary shoe samples. After the quality team confirms that they are qualified, yellowing resistance test, migration resistance test, and specific gravity test are conducted. When the production quantity is >200kg, the mixture must be stirred before packaging. Before packaging, the electronic scale is calibrated with weights. Special aluminum foil bags are used for packaging, each bag weighing 25kg. The net weight error of the finished product is ±0.2kg. Qualified products are stamped with a qualified stamp and put into storage. MSDS and TDS technical parameter data are attached.

[0029] Metallic high-gloss masterbatches include gold masterbatches, silver masterbatches, and colored masterbatches. All three have a metallic high-gloss luster and are suitable for injection molding and foaming processes of EVA shoe materials.

[0030] The gold masterbatch is composed of the following components by weight percentage: 35-37% carrier resin, 44-46% crystal gold powder, 9-11% crystal platinum powder, 1-3% high-performance pigment, 3-5% dispersant, 0.4-0.6% stabilizer, 1-3% fixing agent, and 0.4-0.6% surfactant, with the total weight percentage of each component being 100%.

[0031] The silver masterbatch is composed of the following components by mass percentage: 37-39% carrier resin, 35-45% aluminum silver powder, 14-16% crystal platinum powder, 3-5% dispersant, 0.4-0.6% stabilizer, 1-3% fixing agent, and 0.4-0.6% surfactant, with the total mass percentage of each component being 100%.

[0032] The colored masterbatch is composed of the following components by weight percentage: 35-40% carrier resin, 10-20% aluminum silver powder, 10-20% crystal gold powder, 30-45% crystal platinum powder, 5-15% colored gold powder, 3-5% dispersant, 0.4-0.6% stabilizer, 1-3% fixing agent, and 0.4-0.6% surfactant, with the total weight percentage of each component being 100%.

[0033] Aluminum silver powder is composed of 93-97% Al, 1-3% isopropanol and 2-4% silicon dioxide; The crystal gold powder is composed of 42-46% synthetic fluorophlogopite, 44-48% titanium dioxide, 0-1% tin dioxide and 6-10% ferric oxide; Crystal platinum powder is composed of 52-56% synthetic fluorophlogopite and 44-48% titanium dioxide; The colored gold powder consists of 52-56% synthetic fluorophlogopite, 40-45% titanium dioxide, 0-1% tin dioxide and 5-8% high-performance pigments.

[0034] The carrier resin is a blend of EVA7350M and EVA7470M in a mass ratio of 3:7. EVA7350M provides good processing fluidity, while EVA7470M improves compatibility with EVA footwear materials.

[0035] The dispersant is a compound of Honeywell 400A and BASF hindered phenolic antioxidant in a mass ratio of 2:1, which inhibits the agglomeration of high-performance pigments and reduces the thermal degradation of materials during processing. The surfactant is Lutensol XP 70.

[0036] The stabilizer is zinc stearate, which plays a role in heat stabilization. The fixing agent is 9160 color powder heat resistance agent, which enhances the bonding force between high-performance pigments and carrier resin, and together they improve the heat resistance temperature of high-performance pigments. The high-performance pigment is one of the following: heat-resistant pink PR122, heat-resistant red PR254, heat-resistant pink PV19, phthalocyanine blue PB15:3, phthalocyanine blue PB15:0, heat-resistant yellow-brown PY42, heat-resistant red-brown PBP101, ultramarine blue PB29, titanium green G7, carbon black PBK6, carbon black PBK7, heat-resistant yellow PY83, heat-resistant lemon yellow PY81, and ultramarine violet PV15, or a mixture of any combination of the above components. The high-performance pigment has a heat resistance temperature ≥280℃ and a color fastness of 7-8. Example

[0037] Gold masterbatch: 11.4% EVA7350M, 26.6% EVA7470M, 44% crystal gold powder, 10% crystal platinum powder, 1% heat-resistant yellow PY83, 2.7% Honeywell 400A, 1.3% BASF hindered phenolic antioxidant, 0.4% zinc stearate, 2% 9160 color powder heat-resistant agent and 0.6% Lutensol XP 70, and midsole shoe samples and test pieces were prepared using the gold masterbatch.

[0038] Step 1, Material Selection and Pretreatment: Mix the metallic pigment with the surfactant and stir at 60℃ for 30 minutes for surface modification. The modified metallic pigment can better compatibility with the carrier resin. After modification, take samples for observation. The modified crystal gold powder has no lumps and is smooth to the touch without any grainy feel. Set aside for later use. Test pieces of high-performance pigment are tested. Thin sheets are prepared on a small two-roll mill with special natural colorant at an addition amount of 0.5% and 0.05%. The sheets are made into foamed test pieces by an 80T hydraulic molding machine. After the color is qualified by colorimeter comparison, physical property tests are performed. After confirming that there are no errors, they are set aside for later use. The special natural colorant is used as the base material. The single batch dosage of the special natural colorant is 100kg EVA7470M, 0.8kg stearic acid, 0.8kg zinc stearate, 1kg zinc oxide, 0.34kg odorless crosslinking agent and 3kg foaming agent AC600H. Step 2, Material Requisition and Preparation: Weigh each raw material according to the formula. The raw material composition is as follows: carrier resin, high-performance pigment, fixing agent, modified crystal gold powder, modified crystal platinum powder, dispersant and stabilizer. Weigh using a 0.01g electronic scale, with a weighing accuracy of ±0.01g for each component. After weighing, classify and label them, and place them in a clean hopper. Reserve 0.5kg each of the modified crystal gold powder and high-performance pigment from the same batch for subsequent color matching and replenishment. Step 3, Internal Mixing: Before production, clean the internal mixer, wiping it clean with steel wool and calcium powder to avoid cross-contamination of materials. Feed materials in stages. In the first stage, add the carrier resin to the internal mixer, heat to 80℃, and stir for 5 minutes for pre-plasticization. In the second stage, add the high-performance pigment and fixing agent to the internal mixer, continue stirring for 3 minutes to ensure initial mixing of the high-performance pigment and carrier resin. After melting, add modified crystal gold powder, dispersant, and stabilizer, heat to 115℃, and after strong pressure, shearing, and mixing, ensure uniform dispersion, plasticization, and agglomeration into a semi-finished product. During mixing, turn and clean the material three times to ensure no localized material accumulation. The material is uniformly plasticized into a dense block. After forming the semi-finished product, conduct the first test piece test and midsole shoe sample test to confirm color compliance. If the test results are unqualified, return to continue internal mixing and then test again. If the test results are qualified, the semi-finished product is conveyed to the three-roll milling process. Step 4, Three-roll grinding: Add the qualified semi-finished product into the hydraulic three-roll grinding mill, set the front roller to 20r / min, the middle roller to 30r / min, the rear roller to 40r / min, the temperature to 85℃, and the pressure to 0.4MPa, so that the pigment particles in the semi-finished product are further refined and uniform. Then, a second test piece test and a midsole shoe sample test are carried out to confirm whether the color is qualified. If the test result is not qualified, grinding is continued and re-inspection is carried out. If the test result is qualified, it is sent to the granulation process. Step 5, Granulation: After the qualified ground material is added to the internal mixer and agglomerated, it is poured into a single-screw granulator unit. The single-screw granulator unit includes a temperature control unit, a chiller, a vacuum pump, a screw extruder, a circulating underwater cutter, and a centrifugal dryer. The temperature control unit maintains a consistent melting temperature inside the screw extruder through closed-loop temperature control, ensuring stable extrusion of the melt after the metal pigment is dispersed. After the material is plasticized and extruded by the screw extruder, it enters the circulating underwater cutter for underwater cutting and granulation, with the particle size controlled at 2-3mm. The machine's cooling water rapidly cools the masterbatch produced during granulation, preventing oxidation of the masterbatch surface due to high temperatures. The water containing the masterbatch is then fed into a centrifugal dryer, from which the water separated is fed into a chiller. The chiller has a built-in filter structure that filters out particulate debris and impurities from the circulating cooling water and cools the filtered water. The cooled water is then returned to the underwater cutting machine to form a cooling water circulation, removing moisture from the surface of the masterbatch. After drying, the finished masterbatch product is output. Step Six, Testing and Packaging: After granulation, samples are taken and pressed into secondary shoe samples. After the quality team confirms that they are qualified, yellowing resistance test, migration resistance test, and specific gravity test are conducted. When the production quantity is >200kg, the mixture must be stirred before packaging. Before packaging, the electronic scale is calibrated with weights. Special aluminum foil bags are used for packaging, each bag weighing 25kg. The net weight error of the finished product is ±0.2kg. Qualified products are stamped with a qualified stamp and put into storage. MSDS and TDS technical parameter data are attached. Example

[0039] Silver masterbatch: 11.1% EVA7350M, 25.9% EVA7470M, 39% aluminum silver powder, 16% crystal platinum powder, 2.6% Honeywell 400A, 1.4% BASF hindered phenolic antioxidant, 0.5% zinc stearate, 3% 9160 color powder heat resistant agent and 0.5% Lutensol XP 70. Midsole shoe samples and test pieces were prepared using the silver masterbatch, and the production process was the same as in Example 1. Example

[0040] Blue-gold metallic high-gloss masterbatch: 11.0% EVA7350M, 30.0% EVA7470M, 13% crystal gold powder, 30% crystal platinum powder, 6% phthalocyanine blue PB15:3, 4% heat-resistant reddish brown PBP101, 2.8% Honeywell 400A, 1.2% BASF hindered phenolic antioxidant, 0.4% zinc stearate, 2% 9160 color powder heat-resistant agent, and 0.6% Lutensol XP 70. Midsole shoe samples and test pieces were prepared using the colored masterbatch, and the production process was the same as in Example 1. Example

[0041] Ink Blue Metallic High-Gloss Masterbatch: 9.7% EVA7350M, 30% EVA7470M, 30% Crystal Platinum Powder, 10% Colored Gold Powder, 8% Phthalocyanine Blue PB15:0, 0.3% Heat-Resistant Pink PR122, 6% Carbon Black PBK7, 1.8% Honeywell 400A, 1.2% BASF Hindered Phenolic Antioxidant, 2% 9160 Color Powder Heat Resistance Agent, 0.5% Lutensol XP 70, and 0.5% Zinc Stearate. Midsole shoe samples and test pieces were prepared using the colored masterbatch, with the production process the same as in Example 1. Example

[0042] Black and gold metallic high-gloss masterbatch: 12% EVA7350M, 35% EVA7470M, 1% Honeywell 400A, 0.3% BASF hindered phenolic antioxidant, 10% colored gold powder, 10% crystal white gold powder, 30% carbon black PBK7, 0.7% phthalocyanine blue PB15:3, 0.5% Lutensol XP 70 and 0.5% zinc stearate. Midsole shoe samples and test pieces were prepared using the colored masterbatch, and the production process was the same as in Example 1. Example

[0043] Raw wood-colored metallic high-gloss masterbatch: 10% EVA7350M, 38.46% EVA7470M, 1.5% Honeywell 400A, 1.5% BASF hindered phenolic antioxidant, 45% crystal platinum powder, 0.12% carbon black PBK6, 0.15% heat-resistant pink PR122, 0.27% heat-resistant yellow PY83, 2% 9160 color powder heat-resistant agent, 0.5% Lutensol XP 70 and 0.5% zinc stearate. Midsole shoe samples and test pieces were prepared using the colored masterbatch, and the production process was the same as in Example 1. Example

[0044] White gold metallic high-gloss masterbatch: 25% EVA7350M, 20% EVA7470M, 1.4% Honeywell 400A, 1.6% BASF hindered phenolic antioxidant, 51% crystal platinum powder, 0.05% ultramarine blue PB29, 0.5% Lutensol XP 70 and 0.45% zinc stearate. Midsole shoe samples and test pieces were prepared using the colored masterbatch, and the production process was the same as in Example 1.

[0045] EVA midsole samples and test pieces were prepared by spraying EVA midsole with traditional metallic paint, with a coating thickness of 0.1 mm and a drying temperature of 80℃ for 30 min.

[0046] The formulation is the same as in Example 1, except that only 4% Honeywell 400A is used as the dispersant, and no BASF hindered phenolic antioxidant is added. Midsole shoe samples and test pieces are prepared, and the production process remains unchanged.

[0047] The formulation is the same as in Example 1, except that only 38% EVA7470M is used as the carrier resin, and midsole shoe samples and test pieces are prepared. The production process remains unchanged.

[0048] To better illustrate the present invention, performance tests were conducted on the color masterbatch and midsole shoe samples obtained from each embodiment. The tests were performed using industry standard testing methods, and comparisons were made with each comparative example.

[0049] Test plan: Sample pretreatment: Randomly take about 5g of the finished color masterbatch from each example / comparative example, put it in an oven at 105℃ for 2 hours to dry, remove surface moisture, and cool to room temperature for later use. Instrument calibration: Calibrate the electronic densitometer and electronic analytical balance using standard weights to ensure test accuracy; Air mass weighing: Place the dried sample on an electronic analytical balance and weigh its mass in air. Repeat 3 times and take the average value. Immersion mass weighing: Immerse the sample completely in the sample cell of the densitometer containing anhydrous ethanol (ethanol temperature 20℃), weigh its mass in ethanol, repeat 3 times, and take the average value. Density calculation: Calculate the specific gravity according to the formula.

[0050] Test plan: Sample preparation: The color masterbatch of each example / comparative example was blended with EVA substrate at a ratio of 1:20 and pressed into standard sample pieces of 50mm×50mm×2mm. Three pieces of each sample were prepared. Initial color difference test: Use a colorimeter to test the initial value of the sample and calculate the initial color difference ΔE0; Accelerated aging test: Method A: Place the sample in a yellowing resistance test chamber, set the temperature to 50℃, and expose it to ultraviolet light continuously for 4 hours; Method C: Set the temperature to 63℃ and irradiate continuously for 6 hours; Post-aging test: Remove the sample and cool it to room temperature, then test it again. Calculate the color difference ΔE1 after aging and determine the yellowing resistance level (level 1 is the worst, level 5 is the best).

[0051] Test plan: 1. Sample preparation Test sample: The color masterbatch and EVA substrate were blended at a ratio of 1:20 and pressed into a sample sheet; Blank sample: A sample of the same size pressed from pure EVA substrate; Sample assembly: Place the stained side of the test sample against the clean side of the blank sample, sandwich a layer of qualitative filter paper in between, and place it in a pressure block to ensure tight contact; Accelerated migration test: Place the combined sample in a constant temperature oven, set the temperature to 70℃, and keep it at that temperature for 72 hours; Migration determination: Remove the sample and cool it to room temperature. Observe whether there is color migration on the blank sample and filter paper. Use a colorimeter to test the color difference ΔE2 after the blank sample comes into contact with the filter paper. Determine the migration resistance level (level 1 is the worst, level 5 is the best).

[0052] Test plan: Dry aging test 1.1 Sample preparation: The color masterbatch and EVA substrate were blended at a ratio of 1:20 and pressed into 100mm×50mm×2mm sample pieces (for color difference testing) and dumbbell-shaped strips (for tensile strength testing). One sample was reserved as the initial sample. 1.2 Accelerated aging: Place the sample in a hot air aging chamber, set the temperature to 70℃, and keep it at that temperature for 72 hours; 1.3 After removing and cooling to room temperature, test the color difference ΔE3 of the sample (compared with the initial sample), test the tensile strength of the dumbbell-shaped sample, and calculate the tensile strength retention rate (strength after aging / initial strength × 100%).

[0053] Wet aging test 2.1 Preparation of simulated sweat: Prepared with 0.5% NaCl, 0.2% urea, and 0.1% lactic acid, and adjusted to pH 6.5; 2.2 Sample soaking: The color masterbatch-EVA sample was completely immersed in simulated sweat and placed in a constant temperature water bath. The temperature was set at 40℃ and the sample was soaked for 96 hours. 2.3 Remove the sample and dry it, then test the color difference ΔE4 (compared with the initial sample).

[0054] Specific gravity test results as follows Figure 2 As shown, although the specific gravity of Comparative Examples 2 and 3 is similar, the batch-to-batch fluctuation is greater than that of Examples 1, 2, 3 and 4. The local density of Comparative Examples 2 and 3 is higher. The color masterbatch or its products of Examples 1, 2, 3 and 4 are more uniformly distributed and have better specific gravity consistency. Yellowing resistance test results are as follows Figure 3 and Figure 6 As shown, the yellowing resistance grades of methods A and C in Examples 1, 2, 3 and 4 are better than those of Comparative Examples 1, 2 and 3, and the color difference ΔE1 after aging is also better than that of Comparative Examples 1, 2 and 3. Under light and high temperature environments, the masterbatches or their products in Examples 1, 2, 3 and 4 can effectively inhibit the oxidation of high-performance pigments and the degradation of carrier resin, improve color stability and have better yellowing resistance.

[0055] Migration resistance test results are as follows Figure 4 and Figure 6 As shown, Examples 1, 2, 3 and 4 all achieved a migration resistance level of 5, and the migration color difference ΔE2 of the blank sample was ≤0.3. However, Comparative Example 1 only reached level 3 and showed obvious migration. Comparative Examples 2 and 3 also showed migration phenomena. This indicates that the fixing agent and surfactant used in Examples 1, 2, 3 and 4 worked synergistically to enhance the bonding force between high-performance pigments and resins, inhibit the diffusion of high-performance pigment molecules, and make the material more stable.

[0056] Aging test results as follows Figure 5 and Figure 6 As shown, after dry and wet aging, Examples 1, 2, 3 and 4 showed small color differences and minimal mechanical property degradation, while Comparative Examples 2 and 3 showed increased color differences and greater mechanical property degradation. The dispersant and stabilizer worked synergistically to improve the material's tolerance to complex environments.

[0057] like Figures 7-9 As shown, the midsole shoe samples and test pieces prepared in Examples 5, 6, and 7 were tested, and the prepared metallic high-gloss masterbatch showed stable quality and good performance. The production process of this high-gloss metallic masterbatch involves pretreatment, multi-stage testing, three-roll milling, intensive mixing, closed-loop temperature control, and circulating cooling granulation. This ensures that the produced high-gloss metallic masterbatch has a consistent color, and that the finished product has fine and uniform particles with stable and controllable quality.

[0058] This metallic high-gloss masterbatch exhibits outstanding resistance to yellowing, long-term stable appearance, high migration resistance, durable and uniform color, excellent aging resistance, stable mechanical properties, metallic luster and texture, and good compatibility with EVA substrates.

[0059] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A production process of metal high light color master batch, the specific steps are as follows: Step one, material selection and pretreatment: mix metal pigment with surfactant, stir at 60±1℃ for 30±1min for surface modification, the modified metal pigment can be better compatible with carrier resin, after modification, take sample observation, the modified metal pigment has no lump, the hand touch is fine and has no particle feeling, standby, test the test piece of high performance pigment, prepare flake on small two roll mixing machine according to 0.5% and 0.05% addition amount with special base color, make foaming test piece through 80T oil pressure forming machine, compare the color with colorimeter, and then do physical property test, confirm no error and standby; Step two, material and preparation: weigh each raw material according to the formula, the raw material composition is as follows: carrier resin, high performance pigment, fixing agent, modified metal pigment, dispersing agent and stabilizer, use electronic scale to weigh, the weighing precision of each component is ±0.01g, after weighing, classify and label, place in clean hopper, reserve modified metal pigment and high performance pigment of the same batch for subsequent color matching and material supplement; Step three, internal mixer: clean the internal mixer before production, wipe the steel wire ball and calcium powder clean to avoid material cross contamination, stage feeding, add the carrier resin into the internal mixer in the first stage and pre-plasticize; The second stage adds high performance pigment and fixing agent into the internal mixer, continues to stir, ensures the preliminary mixing of high performance pigment and carrier resin, after melting, continues to add modified metal pigment, dispersing agent and stabilizer, heats to 115±5℃, after strong pressure, shearing and mixing, makes it uniformly dispersed, plasticized, lumped into semi-finished product, turns over and sweeps 3 times during mixing to ensure no local material accumulation, the material is uniformly plasticized into dense block, after forming semi-finished product, do first test piece test and midsole shoe sample test, confirm whether the color is qualified, if the test result is unqualified, return to continue mixing, then detect again; if the test result is qualified, deliver the semi-finished product to three roll grinding process; Step four, three roll grinding: add qualified semi-finished product into hydraulic three roll grinding machine, grind at 80-90℃, 0.3-0.5MPa, further refine and uniform the pigment particles in semi-finished product, then do second test piece test and midsole shoe sample test, confirm whether the color is qualified, if the test result is unqualified, continue to grind and recheck, if the test result is qualified, deliver to granulation process; Step five, granulation: after the qualified material after grinding is added into the internal mixer and re-agglomerated, it is poured into a single screw granulator set, which includes a constant temperature machine, a cold water machine, a vacuum pump, a screw extruder, a circulating water cutting machine and a centrifugal dryer. The constant temperature machine maintains the internal melting temperature of the screw extruder consistent through closed-loop temperature control, ensuring the stable extrusion of the melt after the dispersion of the metal pigment. After the material is plasticized and extruded by the screw extruder, it is cut and granulated underwater by the circulating water cutting machine, with the particle size controlled at 2-3 mm. The cooling water of the circulating water cutting machine rapidly cools the color master batch generated during the granulation, while avoiding the surface oxidation of the color master batch caused by high temperature. The water containing the color master batch is transported into the centrifugal dryer, and the separated water is transported into the cold water machine. The cold water machine has a built-in filtering structure to filter the particles, debris and impurities in the circulating cooling water, and to cool the filtered cooling water. The cooled cooling water is returned to the circulating water cutting machine to form a cooling water circulation, and the water on the surface of the color master batch is removed. After drying, the finished color master batch is output. Step six, detection and packaging: after granulation, the sample is pressed into a second shoe sample, and after the quality group confirms that it is qualified, the resistance to yellowing test, the resistance to migration test and the specific gravity test are carried out. When the production quantity is >200 kg, the color master batch needs to be stirred before packaging. The electronic scale is calibrated with weights before packaging, and the color master batch is packaged in special aluminum foil bags, with each bag containing 25 kg. The net weight error of the finished product is ±0.5 kg, and the qualified products are stored in the warehouse.

2. The metal high light color masterbatch produced by the production process of claim 1, characterized by, The metal high-gloss color master batch includes gold color master batch, silver color master batch and colored color master batch, all of which have metal high-gloss luster and are suitable for EVA shoe material injection molding and foaming processing technology.

3. The metal high light color masterbatch according to claim 2, characterized in that, The gold color master batch is composed of the following components by mass percentage: carrier resin 35-40%, crystal gold powder 44-46%, crystal white gold powder 9-11%, high-performance pigment 1-3%, dispersant 3-5%, stabilizer 0.4-0.6%, color fixing agent 1-3% and surfactant 0.4-0.6%, and the total mass percentage of each component is 100%.

4. The metal high light color masterbatch according to claim 3, characterized in that, The silver color master batch is composed of the following components by mass percentage: carrier resin 37-45%, aluminum silver powder 35-45%, crystal white gold powder 14-16%, dispersant 3-5%, stabilizer 0.4-0.6%, color fixing agent 1-3% and surfactant 0.4-0.6%, and the total mass percentage of each component is 100%.

5. The metal high light color masterbatch according to claim 4, characterized in that, The colored color master batch is composed of the following components by mass percentage: carrier resin 35-50%, aluminum silver powder 0-20%, crystal gold powder 0-20%, crystal white gold powder 30-55%, colored gold powder 0-15%, dispersant 3-5%, stabilizer 0.4-0.6%, color fixing agent 1-3% and surfactant 0.4-0.6%, and the total mass percentage of each component is 100%.

6. The metal high light color masterbatch according to claim 5, characterized in that, The aluminum silver powder is composed of 93-97% Al, 1-3% isopropyl alcohol and 2-4% silicon dioxide; The crystal gold powder is composed of 42-46% synthetic fluoro phlogopite, 44-48% titanium dioxide, 0-1% tin dioxide and 6-10% ferric oxide; The crystal white gold powder is composed of 42-46% synthetic fluoro phlogopite, 44-48% titanium dioxide, 0-1% tin dioxide and 6-10% ferric oxide; The crystal white gold powder is composed of 52-56% synthetic fluorphlogopite and 44-48% titanium dioxide; The color gold powder is composed of 52-56% synthetic fluorphlogopite, 40-45% titanium dioxide, 0-1% tin dioxide and 5-8% high-performance pigments.

7. The metal high light color masterbatch according to claim 6, characterized in that, The carrier resin is a blend of EVA7350M and EVA7470M at a mass ratio of 3:7, wherein EVA7350M provides good processing fluidity and EVA7470M improves the compatibility with EVA shoe materials.

8. The metal high light color masterbatch according to claim 7, characterized in that, The dispersant is a compound of Honeywell 400A and BASF hindered phenolic antioxidant at a mass ratio of 2:1, which inhibits the agglomeration of high-performance pigments and reduces the thermal degradation of materials during processing. The surfactant is Lutensol XP 70.

9. The metal high light color masterbatch according to claim 8, characterized in that, The stabilizer is zinc stearate, which plays a heat stabilizing role, and the fixing agent is 9160 color powder temperature-resistant agent, which enhances the binding force of high-performance pigments and carrier resin, and together improves the heat-resistant temperature of high-performance pigments.

10. The metal high light color masterbatch according to claim 9, characterized in that, The high-performance pigments are one of heat-resistant peach red PR122, heat-resistant red PR254, heat-resistant pink PV19, phthalocyanine blue PB15:3, phthalocyanine blue PB15:0, heat-resistant yellow brown PY42, heat-resistant red brown PBP101, ultramarine blue PB29, titanium cyanine green G7, carbon black PBK6, carbon black PBK7, heat-resistant yellow PY83, heat-resistant lemon yellow PY81 and ultramarine purple PV15, or a mixture of any combination of the above components, and the heat-resistant temperature of high-performance pigments is ≥280℃, and the color fastness is grade 7-8.

Images