High-color-fastness TPEE monofilament fluorescent color master batch and preparation method thereof

Abstract

The invention mainly relates to the technical field of coloring of plastic products, in particular to a high-color-fastness TPEE monofilament fluorescent color master batch and a preparation method thereof. The fluorescent color master batch comprises the following components in parts by mass: 5-20 parts of a fluorescent pigment, 1-5 parts of an organic pigment, 1-5 parts of a hyperdispersant, 1-5 parts of an anti-yellowing agent, 1-5 parts of a weather-proof agent, 50-70 parts of a thermoplastic polyester elastomer and the like. According to the high-color-fastness TPEE monofilament fluorescent color master batch and the preparation method thereof provided by the invention, the color brightness and color fastness of TPEE color yarns are remarkably improved, the comprehensive color fastness of the TPEE color yarns drawn by using the color master batch is greater than or equal to grade 4 and far exceeds the general grade 2-3 in the industry, and meanwhile, the method simplifies the production process, reduces the cost, reduces the environmental pollution, and is suitable for industrial production. The selected environment-friendly materials further improve the market competitiveness of the product, and the product has a wide application prospect.

Description

Technical Field

[0001] The invention mainly relates to the technical field of plastic product coloring, and more specifically to a high color fastness TPEE monofilament fluorescent masterbatch and a preparation method thereof. Background Art

[0002] In the field of shoe upper fabric manufacturing, TPEE (thermoplastic polyester elastomer) monofilament has become the preferred material for many footwear products due to its excellent elasticity, wear resistance and weather resistance. However, as consumers' requirements for product aesthetics and durability continue to increase, the color performance of TPEE fabrics is also facing more stringent standards; Traditional printing and dyeing technology is complex, costly, and causes serious environmental pollution. It is difficult to meet the needs of modern manufacturing. Therefore, the industry has begun to adopt the method of coloring before drawing, that is, directly adding masterbatch during the process of melt extrusion drawing to produce colored yarn of the required color. This method not only simplifies the production process and reduces costs, but also significantly reduces pollution to the environment. Nevertheless, the selection and use of pigments in the TPEE coloring process still face many challenges. At present, TPEE coloring mainly relies on two types of pigments: organic pigments and fluorescent pigments. Although organic pigments have high color fastness and can maintain color stability under various environmental conditions, their color brightness is relatively low and it is difficult to meet the market demand for bright colors. In contrast, fluorescent pigments are bright in color and can significantly improve the visual effect of fabrics, but their color fastness is often low and may contain high formaldehyde content, which poses certain risks to human health and the environment. It is worth noting that the comprehensive color fastness level of the existing industry is generally at level 2-3, which is far from meeting the strict color fastness requirements of the high-end upper fabric market. Insufficient color fastness will cause the fabric to fade, discolor and migrate during processing, use and storage, seriously affecting the overall appearance and quality of the product. In particular, during the processing and storage of TPEE plastics, due to the particularity of its material structure, yellowing is more likely to occur, further increasing the difficulty of coloring; In response to these problems, although some improvement plans have been proposed, such as the patent with application number CN202110894875.0 and patent name "A high-solidity masterbatch and its preparation method", which aims to improve the color vividness and color fastness of the carrier resin (a mixture of polyethylene terephthalate, polyethylene, and polystyrene) by optimizing the formula and preparation process of the masterbatch, the patent still has some defects. First, the carrier resin has different properties from TPEE (thermoplastic polyester elastomer), and it contains a more complex combination and proportion of ingredients, such as a specific proportion of multiple pigments, dispersants, antioxidants and fillers, which makes it impossible for the selected pigments and additives to take into account the requirements of fluorescent effect and color fastness. At the same time, there may still be problems such as uneven pigment dispersion, migration and discoloration during the preparation process, resulting in unstable fabric color; In summary, although the existing technology has proposed some improvement plans, how to further improve the TPEE coloring technology and develop a new formula that can not only improve the color brightness and color fastness of the fabric (especially reach or exceed the existing industry's level 3 color fastness level) but also reduce environmental pollution and production costs is still a technical problem that needs to be solved urgently in the current upper fabric manufacturing field. In particular, it is necessary to explore a formula that effectively combines organic pigments and fluorescent pigments to overcome the shortcomings of the existing technology and meet the market demand for high-quality upper fabrics. Summary of the invention

[0003] The purpose of the present invention is to solve the technical problems faced in the existing TPEE monofilament coloring process, such as difficulty in pigment selection, insufficient color fastness, substandard color brightness, environmental pollution and high production costs. The present invention provides a high color fastness TPEE monofilament fluorescent masterbatch and a preparation method thereof. The masterbatch is intended to improve the performance of fabrics composed of monofilaments in terms of color brightness and color fastness, and the preparation method thereof also achieves an environmentally friendly effect.

[0004] In order to achieve the above-mentioned purpose, the present invention specifically adopts the following technical solutions: The present invention provides a TPEE monofilament fluorescent masterbatch with high color fastness, comprising the following components in parts by mass: 5-20 parts of fluorescent pigment, 1-5 parts of organic pigment, 1-5 parts of hyperdispersant, 1-5 parts of anti-yellowing agent, 1-5 parts of weathering agent and 50-70 parts of thermoplastic polyester elastomer.

[0005] As a preferred technical solution of the present invention, the fluorescent pigment is a Z series fluorescent pigment produced by DayGlo Corporation of the United States, and the specific model is one of EZ11, EZ15, EZ17, EZ18 or EZ21.

[0006] As a preferred technical solution of the present invention, the hyperdispersant is a high molecular polymer containing a polyester chain.

[0007] As a preferred technical solution of the present invention, the hyperdispersant is a high molecular polymer containing a polyester chain.

[0008] As a preferred technical solution of the present invention, the weathering agent is an ultraviolet absorber containing azinone substances.

[0009] The present invention also provides a method for preparing a high color fastness TPEE monofilament fluorescent masterbatch, for preparing any of the above-mentioned high color fastness TPEE monofilament fluorescent masterbatch, the preparation method comprising the following steps: first, accurately weighing a thermoplastic polyester elastomer, a fluorescent pigment, an organic pigment, a hyperdispersant, an anti-yellowing agent and a weathering agent according to the mass ratio; then, adding these raw materials into a mixer in turn, and mixing them for 5-10 minutes to ensure that the components are evenly dispersed; finally, unloading the mixed materials and putting them into a twin-screw extruder for granulation, thereby obtaining the high color fastness TPEE monofilament fluorescent masterbatch.

[0010] As a preferred technical solution of the present invention, the fluorescent masterbatch is mixed with 96% of thermoplastic polyester elastomer at a ratio of 4% and drawn to obtain TPEE monofilament with high color fastness.

[0011] As a preferred technical solution of the present invention, during the mixing process, the thermoplastic polyester elastomer is first poured into the mixer, and then the diffusion oil is added and mixed for 3 minutes in a ratio of 6-7:1 between the thermoplastic polyester elastomer and the diffusion oil.

[0012] As a preferred technical solution of the present invention, when a twin-screw extruder is used for granulation, the temperature of the extruder is controlled within the range of 185-225°C.

[0013] The beneficial effects of the present invention are as follows: the high color fastness TPEE monofilament fluorescent masterbatch and the preparation method thereof provided by the present invention significantly improve the color vividness and color fastness of TPEE colored yarn. When the masterbatch is used for wire drawing, the comprehensive color fastness of TPEE colored yarn is ≥ level 4, far exceeding the general level of 2-3 levels in the industry. At the same time, the method simplifies the production process, reduces costs, and reduces environmental pollution. The selected environmentally friendly materials further enhance the market competitiveness of the product and have broad application prospects. DETAILED DESCRIPTION

[0014] The present invention provides a TPEE monofilament fluorescent masterbatch with high color fastness, comprising the following components in parts by mass: 5-20 parts of fluorescent pigment, 1-5 parts of organic pigment, 1-5 parts of hyperdispersant, 1-5 parts of anti-yellowing agent, 1-5 parts of weathering agent and 50-70 parts of thermoplastic polyester elastomer.

[0015] The fluorescent pigment is a Z series fluorescent pigment produced by DayGlo Corporation of the United States, and the specific model is one of EZ11, EZ15, EZ17, EZ18 or EZ21.

[0016] Wherein, the hyperdispersant is a high molecular polymer containing a polyester chain.

[0017] Wherein, the hyperdispersant is a high molecular polymer containing a polyester chain.

[0018] Wherein, the weathering agent is an ultraviolet absorber containing azinone substances.

[0019] The present invention also provides a method for preparing a high color fastness TPEE monofilament fluorescent masterbatch, for preparing any of the above-mentioned high color fastness TPEE monofilament fluorescent masterbatch, the preparation method comprising the following steps: first, accurately weighing a thermoplastic polyester elastomer, a fluorescent pigment, an organic pigment, a hyperdispersant, an anti-yellowing agent and a weathering agent according to the mass ratio; then, adding these raw materials into a mixer in turn, and mixing them for 5-10 minutes to ensure that the components are evenly dispersed; finally, unloading the mixed materials and putting them into a twin-screw extruder for granulation, thereby obtaining the high color fastness TPEE monofilament fluorescent masterbatch.

[0020] Among them, the fluorescent masterbatch is mixed with 96% of thermoplastic polyester elastomer at a ratio of 4% and drawn to obtain TPEE monofilament with high color fastness.

[0021] In the mixing process, the thermoplastic polyester elastomer is first poured into the mixer, and then the diffusion oil is added, and mixed for 3 minutes according to the ratio of thermoplastic polyester elastomer to diffusion oil of 6-7:1.

[0022] Wherein, when the twin-screw extruder is used for granulation, the temperature of the extruder is controlled within the range of 185-225°C.

[0023] Analysis of the advantages of high color fastness TPEE monofilament fluorescent masterbatch and its preparation method The high color fastness TPEE monofilament fluorescent masterbatch and its preparation method provided by the present invention have shown unique advantages in the field of upper fabric manufacturing and even in the entire plastic product coloring technology. The following is a detailed analysis of its advantages: 1. Advantages of coexistence of organic pigments and fluorescent pigments Traditionally, organic pigments and fluorescent pigments have their own advantages and disadvantages in coloring technology. Organic pigments have high color fastness, but relatively low color brightness; while fluorescent pigments have bright colors, but often low color fastness. The present invention achieves the coexistence of organic pigments and fluorescent pigments through careful screening and proportioning, and gives full play to the advantages of both: 1. Improved color vividness: The Z series fluorescent pigments (such as EZ11, EZ15, EZ17, EZ18 or EZ21) produced by DayGlo Company of the United States have excellent color vividness, which can significantly improve the visual effect of the fabric and meet the market demand for bright colors; 2. Enhanced color fastness: By adding an appropriate amount of organic pigments and combining them with additives such as hyperdispersants, anti-yellowing agents and weathering agents, the present invention effectively improves the color fastness of masterbatch. These additives can stabilize the pigment molecules to prevent them from migrating, fading or changing color during use, thereby ensuring that the fabric maintains stable color performance during processing, use and storage.

[0024] 2. Advantages of transforming defects in background technology In view of the many challenges faced in the selection and use of pigments in the TPEE coloring process mentioned in the background technology, as well as the problems of insufficient color fastness, uneven pigment dispersion, migration and discoloration in the prior art, the present invention converts these defects into advantages in the following ways: 1. Optimize the formula and preparation process: The present invention achieves uniform dispersion and stable coloring of the pigment by optimizing the formula and preparation process of the masterbatch, which effectively solves the problem of uneven pigment dispersion in the prior art and improves the color uniformity and stability of the fabric; 2. Improve color fastness and weather resistance: The selected fluorescent pigments have excellent light resistance, heat resistance, weather resistance and migration resistance (all above level 4), which is far higher than the general level of the industry. The improvement of these properties enables the fabric to maintain stable color performance in extreme environments, extending the service life of the product; 3. Environmental protection, energy saving and cost reduction: The preparation method of the present invention simplifies the production process, reduces the complex procedures and high costs of traditional printing and dyeing technology. At the same time, the selected raw materials are all environmentally friendly materials that meet the requirements of environmental protection and energy saving, which not only reduces environmental pollution, but also reduces production costs and improves the competitiveness of enterprises.

[0025] 3. Advantages of each material 1. Fluorescent pigments: The Z series fluorescent pigments produced by DayGlo in the United States have excellent color brightness and weather resistance. Their light resistance, heat resistance, weather resistance and migration resistance all reach level 4 or above, ensuring that the fabric can maintain bright colors and stable performance after long-term use and exposure to harsh environments; 2. Organic pigments: As auxiliary pigments, organic pigments play an important role in improving color fastness. They can effectively stabilize pigment molecules and prevent them from migrating or fading during use, thereby ensuring the color stability of the fabric; 3. Hyperdispersant: High molecular weight polymer hyperdispersant containing polyester chains can significantly improve the dispersibility and tinting power of pigments. It can evenly disperse pigment particles in the resin to form a stable pigment dispersion system, thereby improving the color uniformity and brightness of the fabric; 4. Anti-yellowing agents and weathering agents: These additives can effectively resist the damage of ultraviolet rays and oxidation to pigments, preventing the fabric from yellowing or fading during use. They further improve the weather resistance and service life of the fabric.

[0026] In summary, the high color fastness TPEE monofilament fluorescent masterbatch and its preparation method provided by the present invention have shown unique advantages in terms of color brightness, color fastness, environmental protection and energy saving, cost reduction and meeting market demand. These advantages make the present invention have broad application prospects and market competitiveness in the field of shoe upper fabric manufacturing and even in the entire plastic product coloring technology.

[0027] Examples and Comparative Examples Example 1

[0028] formula: Fluorescent pigment (Z series EZ17 from DayGlo, USA): 10 parts Organic pigment: 3 parts Hyperdispersant (polymer containing polyester chains): 3 parts Anti-yellowing agent: 2 parts Weathering agent (UV absorber containing oxazine): 2 parts Thermoplastic polyester elastomer: 70 parts Preparation method: Accurately weigh each component according to the above formula; Pour the thermoplastic polyester elastomer into a mixer, then add the diffusion oil (at a ratio of 6:1 between the thermoplastic polyester elastomer and the diffusion oil), and mix for 3 minutes; Add fluorescent pigment, organic pigment, super dispersant, anti-yellowing agent and weathering agent in sequence, and continue mixing for 5-10 minutes to ensure that all components are evenly dispersed; The mixed material is unloaded and put into a twin-screw extruder, and the extruder temperature is controlled at 200°C for granulation; The obtained fluorescent masterbatch was mixed with 96% of thermoplastic polyester elastomer at a ratio of 4% and drawn to obtain TPEE monofilament with high color fastness; Experimental results: Color vividness: Very high, meeting the market demand for bright colors; Color fastness (sunlight resistance, anti-yellowing performance): both reach level 4 or above. Example 2

[0029] formula: Fluorescent pigment (Z series EZ18 from DayGlo, USA): 15 parts Organic pigment: 2 parts Hyperdispersant (polymer containing polyester chain): 4 parts Anti-yellowing agent: 3 parts Weathering agent (UV absorber containing oxazine): 3 parts Thermoplastic polyester elastomer: 60 parts Preparation method (same as Example 1); Experimental results: Color vividness: Very high, excellent visual effect; Color fastness (sunlight resistance, anti-yellowing performance): both reach above level 4, and excellent weather resistance. Example 3

[0030] formula: Fluorescent pigment (Z series EZ21 from DayGlo, USA): 5 parts Organic pigment: 5 parts Hyperdispersant (polymer containing polyester chain): 1 part Anti-yellowing agent: 1 part Weathering agent (ultraviolet absorber containing oxazine): 1 part Thermoplastic polyester elastomer: 85 parts Preparation method (same as Example 1); Experimental results: Color vividness: moderate, but still higher than traditional organic pigment coloring; Color fastness (sunlight resistance, anti-yellowing performance): both reach level 4 or above, meeting the requirements of high-end upper fabrics.

[0031] Comparative Example 1 (Containing only fluorescent pigment) formula: Fluorescent pigment (Z series EZ17 from DayGlo, USA): 20 parts Thermoplastic polyester elastomer: 80 parts Preparation method (omitting the step of adding diffusion oil, and the rest is the same as in Example 1); Experimental results: Color vividness: very high, but color fastness is insufficient, and light fastness and anti-yellowing performance are both below level 3, which is consistent with the defects mentioned in the background technology.

[0032] Comparative Example 2 (containing only organic pigments) formula: Organic pigment: 10 parts Thermoplastic polyester elastomer: 90 parts Preparation method (same as comparative example 1); Experimental results: Color vividness: relatively low, does not meet the market demand for bright colors; Color fastness (sunlight fastness, anti-yellowing performance): both are around level 3, which is consistent with the general level of color fastness mentioned in the background technology.

[0033] Comparison table

[0034] In summary, through the comparison between the embodiments and the comparative examples, it can be seen that the high color fastness TPEE monofilament fluorescent masterbatch and the preparation method thereof provided by the present invention perform well in terms of color vividness and color fastness, far exceeding the comparative examples containing only fluorescent pigments or only organic pigments. These advantages enable the present invention to have broad application prospects and market competitiveness in the field of upper fabric manufacturing and even in the entire plastic product coloring technology.

[0035] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A high color fastness TPEE monofilament fluorescent masterbatch, characterized by: The fluorescent masterbatch comprises the following components in parts by mass: 5-20 parts of fluorescent pigment, 1-5 parts of organic pigment, 1-5 parts of hyperdispersant, 1-5 parts of anti-yellowing agent, 1-5 parts of weathering agent, and 50-70 parts of thermoplastic polyester elastomer.

2. The high color fastness TPEE monofilament fluorescent masterbatch according to claim 1, characterized in that: The fluorescent pigment is a Z series fluorescent pigment produced by DayGlo Corporation of the United States, and the specific model is one of EZ11, EZ15, EZ17, EZ18 or EZ21.

3. The high color fastness TPEE monofilament fluorescent masterbatch according to claim 1, characterized in that: The hyperdispersant is a high molecular polymer containing a polyester chain.

4. The high color fastness TPEE monofilament fluorescent masterbatch according to claim 1, characterized in that: The anti-yellowing agent includes one or more of a hindered amine light stabilizer, a benzotriazole ultraviolet absorber, and a salicylate ultraviolet absorber.

5. The high color fastness TPEE monofilament fluorescent masterbatch according to claim 1, characterized in that: The weathering agent is an ultraviolet absorber containing azinone substances.

6. A method for preparing a high color fastness TPEE monofilament fluorescent masterbatch according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: first, accurately weighing a thermoplastic polyester elastomer, a fluorescent pigment, an organic pigment, a superdispersant, an anti-yellowing agent and a weathering agent according to a mass ratio; then, adding the raw materials into a mixer in sequence, and mixing them thoroughly for 5-10 minutes to ensure that the components are evenly dispersed; finally, discharging the mixed materials and putting them into a twin-screw extruder for granulation, thereby obtaining the TPEE monofilament fluorescent masterbatch with high color fastness.

7. The method for preparing a high color fastness TPEE monofilament fluorescent masterbatch according to claim 6, characterized in that: The fluorescent masterbatch was mixed with 96% of thermoplastic polyester elastomer at a ratio of 4% and drawn to obtain TPEE monofilament with high color fastness.

8. The method for preparing a high color fastness TPEE monofilament fluorescent masterbatch according to claim 6, characterized in that: During the mixing process, first pour the thermoplastic polyester elastomer into the mixer, then add the diffusion oil, and mix for 3 minutes according to the ratio of thermoplastic polyester elastomer to diffusion oil of 6-7:

1.

9. The method for preparing a high color fastness TPEE monofilament fluorescent masterbatch according to claim 6, characterized in that: When the twin-screw extruder is used for granulation, the temperature of the extruder is controlled within the range of 185-225°C.

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