WO2023115257A1

WO2023115257A1 - Polymer color master batch containing natural herbal dye, and preparation method therefor

Info

Publication number: WO2023115257A1
Application number: PCT/CN2021/139637
Authority: WO
Inventors: 王军; 张瑞木; 王方方; 林怡然; 王佳; 朱恩斌; 时文艺; 匡贞成
Original assignee: 福建赛隆科技有限公司
Priority date: 2021-12-20
Filing date: 2021-12-20
Publication date: 2023-06-29
Also published as: CN117043237A

Abstract

The present invention belongs to the technical field of color master batches, and more specifically relates to an environmentally friendly polymer color master batch containing a natural herbal dye, and a preparation method therefor. Provided is a polymer color master batch containing a natural herbal dye, the polymer color master batch comprising, in parts by weight: 50-98 parts of a polymer, 1-10 parts of a dispersing agent, 0.5-1 part of an antioxidant and 0.1-30 parts of a herbal dye, wherein the average particle size of the herbal dye is 0.1-2 µm. The environmentally friendly polymer color master batch containing a natural herbal dye provided in the present invention can avoid the negative influences of synthetic dyes and pigments on body health and the ecological environment, also can solve the problems caused by post-finishing and dyeing, and environmental problems and low color fastness problem caused by herbal plant dyes during the later dyeing process, and furthermore, by means of studying the coloring properties of the melt blending of the herbal dye on the polymer, can fill the gap and provide a reference for technical studies in the field.

Description

Polymer color masterbatch containing natural herbal dye and preparation method thereof

technical field

The invention belongs to the technical field of color masterbatches, and more specifically relates to an environment-friendly polymer color masterbatch containing natural herbal dyes and a preparation method thereof.

Background technique

The conventional dyeing method of polyester fiber is to dye the fiber and textile through post-finishing dyeing (i.e. carrier dyeing) or high temperature and high pressure dyeing. This method will produce a large amount of printing and dyeing wastewater to pollute the environment, and will also generate more energy consumption. The new coloring treatment method is to use the pre-spinning dope coloring, and add the special PET color masterbatch to the PET raw material in proportion to make fibers before spinning, such as the preparation method of a dope-colored elastic polyester fiber published in patent application CN109082726A. Another example is the patent application CN107964223A, which discloses a high-concentration color masterbatch for dyeing bright red fiber and its preparation method. Although it solves the problem of spinnability of coloring before spinning, reduces floating yarns and broken ends, and prolongs the service life of spinning components, However, whether it is the dyes used in the post-dyeing or the masterbatch method, they are all synthetic dyes or pigments. However, the use of synthetic dyes/pigments will cause serious environmental pollution, irreversible consumption of energy and resources, and some will cause skin diseases and even carcinogenic. From 2002 to 2005, Donghua University undertook the national high-tech research and development project, and carried out research on the preparation of natural dyes and its technical application in the development of ecological textiles and the clean production of wool. Currently, the research on the use of plant dyes is concentrated in the finishing Dyeing application, the study found that dyeing with herbal plant dyes has disadvantages such as low light fastness, low washing fastness, dyes that require mordants, and possible metal pollution. Patent No. EP2020172742 discloses cellulose fibers containing indigo pigments in oxidized form. This method is to add indigo pigments to the spinning solution, and then extrude them into the coagulation bath to prepare fibers according to the Modal spinning process. The cellulose fibers prepared by this method contain The fiber color fastness and migration resistance of the oxidized form of indigo dye are stronger than that of vat dye through post-dyeing, but the dispersibility of indigo dye in the masterbatch in the melt spinning process cannot be guaranteed.

PepsiCo Materials (Qingdao) Co., Ltd. has applied for several articles at home and abroad in 2020 for the functional modification of polyester by plant extracts and the preparation of plant functional polyester masterbatches, most of which have antibacterial properties. For example, WO2021088307A1 corresponds to the Chinese patent application CN110863252A, the invention name is "a kind of plant functional polyester filament and its preparation method", the functional plant extracts are peppermint extract, valerian extract, lavender extract, wormwood extract and seaweed extract, the fiber Antibacterial and deodorizing, good wear resistance, high elasticity, comfortable hand feeling, not easy to pilling, not easy to stain, etc.; Chinese patent application CN112011847A, the invention name is "a lotus leaf, isatidis or aloe modified polyester fiber and its Preparation method", the polyester fiber provided by it has good antibacterial durability; the antibacterial rate of Staphylococcus aureus, Escherichia coli, Candida albicans and other bacteria is 97.1-98.8%; Chinese patent application CN112030261A is a kind of polyester fiber containing dandelion and Its preparation method, Chinese patent application CN111118652A a kind of seaweed polyester fiber and its preparation method, Chinese patent application CN112251838A a kind of polyester fiber containing lavender and its preparation method, and Chinese patent application CN112281245 a kind of olive green polyester fiber and its preparation method, etc. Other common herbal plants with antibacterial or antibacterial effects, such as tea and Chinese herbal medicines, have been applied for patents for antibacterial functions. The extracts of these plants mainly use these plants to have antibacterial, antibacterial and anti-inflammatory effects. However, the above-mentioned prior art does not conduct corresponding research on the influence of these extracts on the color change of polyester fibers.

Contents of the invention

In view of the above-mentioned technical problems in the background technology, it is necessary to provide a polymer masterbatch containing natural herbal dyes and a preparation method thereof to overcome the environmental pollution caused by a large amount of printing and dyeing wastewater and high energy consumption caused by herbal dyes in post-dyeing. Consumption problems, while avoiding the unsafe factors and environmental pollution caused by synthetic dyes or pigments, and the research on the coloring effect of polymers prepared by directly blending herbal dyes and polymers to prepare polymer masterbatches containing natural herbal dyes.

In order to achieve the above object, in the first aspect of the present invention, the inventor provides the polymer masterbatch containing natural herbal dyes, in parts by weight, including:

50-98 parts of polymer;

1 to 10 parts of dispersant;

0.5 to 1 part of antioxidant; and

0.1-30 parts of herbal dyes, wherein,

In terms of mesh, the average particle size of the herbal dye is 0.1-2um.

There are many types of polymers that can be used, but some colors may affect the color of some dyes due to volatilization, melting or even decomposition at higher processing temperatures such as polyimide processing temperatures of about 350 ° C, or raw material phases Poor meltability leads to poor color fastness such as dye migration during use. The polymer to be adopted in the present invention is suitable for the field of chemical fiber, considering the interaction between dispersant and dyestuff and the performance of polymer raw materials, in order to obtain a color masterbatch with better dispersibility, as a preferred embodiment of the present invention, the following Said polymer is selected from one of polyester, polyamide or polypropylene.

As a preferred embodiment of the present invention, the herbal dye is one or more composite dyes of watermelon red, bright yellow, indigo, olive green and black dyes extracted from herbal plants. Specifically, for example, but not limited to, it can be watermelon red prepared by extracting madder, bright yellow prepared by extracting gardenia fruit, indigo prepared by extracting bluegrass, olive green prepared by extracting fruit of Myrobalan fruit, black prepared by extracting fruit of Myrobalan and Galla fruit, etc. , and other pure herbal plant dyes of other colors obtained from the above extracts through scientific and reasonable proportioning. In this way, the damage to human health and the impact on the ecological environment of synthetic dyes and pigments in the application process of products can be completely avoided.

As a preferred embodiment of the present invention, the content of the herbal dye is 0.1-30% by weight percentage. According to the needs of different shades and color matching during spinning preparation, polymer masterbatches containing different contents of herbal dyes are selected. For example, when the concentration of herbal dyes in silk fabrics is 0.005%, 0.025%, or less than 0.01%, it is better to choose a polymer masterbatch with a concentration of 0.1%. If a certain color is used less in color matching or in order to ensure that the color error is as small as possible in small batch production, a lower concentration of polymer masterbatch can be used. On the contrary, when color matching requires darker colors, more dyes need to be added to prepare darker corresponding colors. At this time, a higher concentration of polymer masterbatches should be selected, such as 20% or 30% of such high-concentration color masterbatches. Masterbatch is more suitable for mass production. In particular, when the substrate of the polymer masterbatch is inconsistent with the material to be processed, the polymer masterbatch with different contents of herbal dyes can minimize the impact of the polymer masterbatch on the physical properties of the product. Within this range, herbal dyes can achieve better dispersion stability and color uniformity in polymer masterbatches.

Different from the prior art, the above technical solution has at least the following beneficial effects:

Using herbal plant dyes and polymers as the main raw materials to obtain masterbatches can not only avoid the negative impact of synthetic dyes and pigments on human health and the ecological environment, but also solve the problems caused by post-dyeing and herbal plant dyes in the later stage. The environmental problems caused by dyeing and the problems of low light fastness and washing fastness.

In the second aspect of the present invention, the inventor provides the preparation method of the polymer masterbatch containing natural herbal dyes described in the first aspect of the present invention, comprising the following steps:

Vacuum-dry the herbal dye for 4-12 hours, crush the polymer slices into a powder with a mesh number of 20-50 mesh, and vacuum-dry at 120°C-220°C for 4-12 hours before use;

Weighing the dried herbal dye, the dried polymer raw material, the dispersant and the antioxidant respectively according to parts by weight;

adding the weighed dried herbal dyes, dried polymer raw materials, dispersant and antioxidant raw materials into a high-speed mixer, and mixing evenly at a mixing temperature of 30-80°C to obtain a mixture containing natural herbal dyes;

Add the mixture containing natural herbal dyes to a twin-screw extruder for mixing, extrude and granulate to make a polymer masterbatch containing natural herbal dyes, wherein the twin-screw extruder adopts 11 zone temperature settings , the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, the cooling temperature is 15-30°C, twin-screw extrusion The screw speed of the machine is set at 300-500r/min.

As a preferred embodiment of the present invention, the drying temperature in the step of vacuum drying the herbal dye is 60-80°C. In this way, the herbal dyes can be avoided from pyrolysis during drying. If the drying temperature is too low, the drying time will be too long and the drying effect will be poor.

As a preferred embodiment of the present invention, the stirring speed of the high-speed mixer is 100-150 r/min, and the stirring time is 15-30 min. The above-mentioned stirring speed can ensure that the material will not melt and agglomerate during the stirring process, and will not cause waste due to splashing of the material due to excessive stirring speed.

As a preferred embodiment of the present invention, when adding the weighed dried herbal dye and the dried polymer raw material into the high-speed mixer, the raw materials are accurately and continuously added through an online meter, and the dried polymer slices are mixed at a high speed. The main feeding port of the mixer is added, and the dried herbal dye is added through the side feeding port of the high-speed mixer. In this way, the separate continuous feeding of polymer slices and herbal dyes can be realized, so that the process of producing the polymer masterbatch containing natural herbal dyes according to the present invention can be continuously carried out, ensuring the consistency of product quality of the polymer masterbatches containing natural herbal dyes sex and stability.

As a preferred embodiment of the present invention, the herbal dye is a modified herbal dye granule, and the preparation method of the modified herbal dye granule is as follows:

Grind the herbal dyes in a ball mill until the particle size is 0.1-2um, use deionized water as a solvent to form a thick liquid of herbal dyes with a mass concentration of 40-80%, and then granulate them through a wet granulator. The granulation temperature is 60-80°C, and a dispersant is added before granulation to obtain modified herbal dye granules.

As a preferred embodiment of the present invention, the dispersant is one or both of ester dispersant and EBS (N,N'-ethylenebisstearamide) with a concentration of 60-90% by mass.

First, the herbal plant dyes and polymers are melt-blended to prepare the masterbatch, and then the masterbatch is directly added during spinning to make the fibers and textiles have color, which can avoid the negative impact of synthetic dyes and pigments on human safety and the ecological environment. It can also solve the problems caused by post-dyeing, and can also avoid the environmental problems and low color fastness of herbal plants in the post-dyeing. It is also possible to study the coloring performance of herbal dyes on polymers by melt blending. Technical research in this field fills in gaps and provides reference.

Description of drawings

Fig. 1 is the flow chart of the preparation method of the polymer masterbatch containing natural herbal dyes described in the specific embodiment.

Detailed ways

In order to explain in detail the technical content, structural features, achieved goals and effects of the technical solution, the following will be described in detail in conjunction with specific embodiments and accompanying drawings. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application.

The raw materials of natural herbal dyes used in the present invention are all purchased from Guizhou Lixian Buyi Garment Technology Research Institute Co., Ltd.

Example 1

A polymer color masterbatch containing natural herbal dyes, consisting of the following raw materials in parts by weight:

64 parts of PET (polyethylene terephthalate), 5 parts of ester dispersant polyethylene wax for preparing modified herbal dye particles, 1 part of antioxidant, 30 parts of herbal dyes. Therefore, the concentration of herbal dyes in the polymer masterbatch containing natural herbal dyes provided in this embodiment is 30%.

The antioxidant used in this example is a combination of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

The herbal plant dye used in this example is watermelon red prepared by extracting madder, which is ground to an average particle size of 2 μm.

The preparation steps of the polymer masterbatch containing natural herbal dyes include:

Step 1: Vacuum-dry the herbal dye at 50°C for 4 hours, and vacuum-dry the PET slices at 180°C for 4 hours before use;

Step 2, crushing the dried PET chips into powder with a mesh size of 50 mesh, and drying again under vacuum conditions at 120°C for 4 hours;

Step 3, weighing the dried herbal dye, dried PET powder, dispersant and antioxidant according to parts by weight;

Step 4: Add the weighed dried herbal dyes, dried polymer raw materials, dispersant and antioxidant raw materials into a high-speed mixer, and stir for 20 minutes at a stirring rate of 100r/min to mix evenly, and the mixing temperature is 80°C , to obtain a mixture containing natural herbal dyes;

Step 5, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer color masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, The cooling temperature was 15°C. The screw speed of the twin-screw extruder was set at 500r/min.

Add the polymer color masterbatch that contains natural herbal dyestuff provided by this embodiment with conventional chemical fiber polymer and carry out melt spinning, make textile, wherein, the concentration that this textile contains herbal dyestuff (pure watermelon red herbal dyestuff) is 1% , labeled as sample A.

Example 2

An environment-friendly polymer masterbatch containing natural herbal dyes, consisting of the following raw materials in parts by weight:

93.9 parts of PET (polyethylene terephthalate), 5 parts of dispersant EBS (N,N'-ethylenebisstearamide), 1 part of antioxidant, and 0.1 part of herbal dye.

The antioxidant used in this example is a composition composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

The herbal plant dye used in this example is watermelon red extracted from madder, which is ground to an average particle size of 1um, that is, the dye concentration in the polymer masterbatch containing natural herbal dye is 0.1%.

The preparation steps of the polymer color masterbatch that this embodiment contains natural herbal dyestuff comprises:

Step 2, crushing the dried PET chips into powder with a mesh size of 50 mesh, and drying at 120° C. under vacuum for 4 hours;

Step 3, weighing the dried herbal dye, dried PET powder, dispersant and antioxidant according to the above parts by weight;

Step 5, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer color masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, The cooling temperature was 30°C. The screw speed of the twin-screw extruder was set at 500r/min.

Use conventional chemical fiber polymers plus the polymer masterbatch containing natural herbal dyes prepared in this example to carry out melt spinning to make textiles, so that the concentration of herbal dyes in the textiles is 0.05%, which is recorded as sample B.

Example 3

74 parts of PET, 5 parts of EBS (N,N'-ethylene bis stearamide), 1 part of antioxidant, 20 parts of herbal dye.

The antioxidant used in this embodiment is the composition of antioxidant 1010 and antioxidant 168 according to 1:1.

The herbal plant dye used in this example is indigo prepared by extracting bluegrass, which is ground to an average particle size of 0.1 μm, that is, the dye concentration in the polymer masterbatch containing natural herbal dye is 20%.

Step 3, take by weight the herbal dye after drying, the PET powder after drying, dispersant and antioxidant;

Step 5, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer color masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, The cooling temperature was 20°C. The screw speed of the twin-screw extruder was set at 500r/min.

Conventional chemical fiber polymers plus the polymer masterbatch containing natural herbal dyes prepared in this example are used for melt spinning to make textiles, so that the concentration of herbal dyes in the textiles is 1%, which is designated as sample C.

Example 4

78 parts of PET, 1 part of dispersant formed by any combination of polyethylene wax + EBS (N,N'-ethylene bis stearamide), 1 part of antioxidant, 20 parts of herbal dye.

Step 1: Vacuum-dry the herbal dye at 50°C for 12 hours, and vacuum-dry the PET slices at 180°C for 4 hours before use;

Step 5, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer color masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, The cooling temperature was 25°C. The screw speed of the twin-screw extruder was set at 500r/min.

Conventional chemical fiber polymers plus the polymer masterbatch containing natural herbal dyes prepared in this example are melt-spun to make textiles, so that the concentration of herbal dyes in the textiles is 0.1%, which is designated as sample D.

Example 5

64 parts of PET (polyethylene terephthalate), 10 parts of EBS (N,N'-ethylenebisstearamide), 1 part of antioxidant, 25 parts of herbal dye.

The antioxidant used in this example is a composition of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

The herbal plant dye used in this example is black prepared by extracting Galla chinensis, which is ground to an average particle size of 0.5um, that is, the dye concentration in the polymer masterbatch containing natural herbal dye is 25%.

Step 2, weighing the dried herbal dye, the dried PET chip raw material, the dispersant and the antioxidant according to parts by weight;

Step 3: add the weighed dried herbal dyes and dried polymer raw materials accurately and continuously through the online meter, add the dried PET slices through the main feeding port, and extrude the dried herbal dyes The side feeding port of the machine is added, and the polymer masterbatch containing natural herbal dyes is prepared by melt extrusion and granulation. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 180°C-250°C-260°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, The cooling temperature was 30°C. The screw speed of the twin-screw extruder was set at 300r/min.

Conventional chemical fiber polymers plus the polymer masterbatch containing natural herbal dyes prepared in this example were melt-spun to make textiles, so that the concentration of herbal dyes in the textiles was 1%, which was designated as sample E.

Example 6

70 parts of PET (polyethylene terephthalate), 5 parts of EBS (N,N'-ethylenebisstearamide), 0.5 parts of antioxidant, and 24.5 parts of herbal dyes.

The herbal plant dye used in this example is olive green extracted from chebula fruit, which is ground to an average particle size of 2um, that is, the dye concentration in the polymer masterbatch containing natural herbal dye is 24.5%.

Step 1, the olive green herbal dye is ground in a ball mill to an average particle size of 2um, dissolved in deionized water to form a dye solution with a mass concentration of 40%, and then granulated by a wet granulator at a temperature of 60 ℃, spray dispersant EBS (N,N'-ethylenebisstearamide) powder evenly into it before granulation to obtain modified herbal dye granules;

Step 2, vacuum-dry the modified herbal dye particles at 50°C for 10 hours, and vacuum-dry the PET slices at 180°C for 10 hours for later use;

Step 3, crushing the dried PET chips into powder with a mesh size of 50 mesh, and drying at 120° C. under vacuum for 4 hours;

Step 4, weighing the dried herbal dye, dried PET powder and antioxidant according to parts by weight;

Step 5, adding the weighed dried herbal dye, dried polymer raw material and antioxidant raw material into a high-speed mixer, stirring at a stirring rate of 100r/min for 20min to mix evenly, and the mixing temperature is 50°C to obtain A blend of natural herbal dyes;

Step 6, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, The cooling temperature was 20°C. The screw speed of the twin-screw extruder was set at 300r/min.

Conventional chemical fiber polymers plus the polymer masterbatch containing natural herbal dyes prepared in this example are used for melt spinning to make textiles, so that the concentration of herbal dyes in the textiles is 1%, which is designated as sample F.

Example 7

84 parts of PET chips (polyethylene terephthalate), 5 parts of EBS (N,N'-ethylenebisstearamide), 1 part of antioxidant, and 10 parts of herbal dyes.

The herbal plant dye used in this example is a bright yellow dye prepared by extracting gardenia fruit, which is ground to an average particle size of 1 μm, that is, the dye concentration in the polymer masterbatch containing natural herbal dye is 10%.

Step 1, the bright yellow herbal dye is ground in a ball mill to an average particle size of 1um, dissolved in deionized water to form a dye solution with a mass concentration of 50%, and then granulated by a wet granulator at a temperature of 80 ℃, uniformly add dispersant EBS (N,N'-ethylenebisstearamide) powder to it before granulation to obtain modified herbal dye granules.

Step 2: Vacuum-dry the modified herbal dye at 50°C for 4 hours, and vacuum-dry the PET slices at 180°C for 4 hours before use;

Step 3, crushing the dried PET chips into powder with a mesh size of 30 mesh, and drying at 120° C. under vacuum for 4 hours;

Step 5, add the dried herbal dye, the dried polymer raw material and the antioxidant raw material into a high-speed mixer, stir for 20 minutes at a stirring rate of 100r/min and mix evenly, and the mixing temperature is 50°C to obtain a natural herbal dye. mixture;

Step 6, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer masterbatches containing natural herbal dyes. The twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C. The cooling temperature is 15-30°C. The screw speed of the twin-screw extruder was set at 500r/min.

Conventional chemical fiber polymers plus the polymer masterbatch containing natural herbal dyes prepared in this example are used for melt spinning to make textiles, so that the concentration of herbal dyes is 1%, which is designated as sample G.

Example 8

78 parts of polypropylene (PP), 1 part of polyethylene wax + EBS (N,N'-ethylenebisstearamide), 1 part of antioxidant, 20 parts of herbal dye.

The antioxidant used in this embodiment is the composition of antioxidant 1010 and antioxidant 168 according to the mass ratio of 1:1.

The herbal plant dye used in this example is indigo prepared by extracting indigo, with an average particle size of 0.1 um, that is, the dye concentration in the polymer masterbatch containing natural herbal dye is 20%.

Step 1: vacuum-dry the herbal dye at 50°C for 12 hours, and dry the polypropylene (PP) slices at 120°C for 4 hours for use;

Step 2, crushing the dried PP chips into powder with a mesh size of 50 mesh, and drying at 120°C for 4 hours;

Step 3, weighing the dried herbal dye, dried PP powder, dispersant and antioxidant according to parts by weight;

Step 5, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer color masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 50°C-120°C-160°C-200°C-220°C-240°C-220°C-220°C-220°C-220°C-240°C, The cooling temperature was 25°C. The screw speed of the twin-screw extruder was set at 500r/min.

Use conventional chemical fiber polymers to add the polymer masterbatch containing natural herbal dyes prepared in this example for melt spinning to make textiles, so that the concentration of herbal dyes is 1%, which is recorded as sample H.

Example 9

78 parts of polyamide (nylon-6), 1 part of polyethylene wax + EBS (N, N'-ethylene bisstearamide), 1 part of antioxidant, 20 parts of herbal dye.

Step 1, vacuum-dry the herbal dye at 50°C for 12 hours, and dry the nylon-66 slices at 80°C for 4 hours before use;

Step 2, crushing the dried nylon 66 slices into 50-mesh powder, and drying under vacuum at 80°C for 4 hours;

Step 3, weighing the dried herbal dye, dried nylon-66 powder, dispersant and antioxidant according to parts by weight;

Step 4: Add the weighed dried herbal dyes, dried polymer raw materials, dispersant and antioxidant raw materials into a high-speed mixer, and stir for 20 minutes at a stirring rate of 100r/min to mix evenly, and the mixing temperature is 60°C , to obtain a mixture containing natural herbal dyes;

Step 5, adding the above-mentioned mixture containing natural herbal dyes into a twin-screw extruder for mixing, extruding and granulating to prepare polymer color masterbatches containing natural herbal dyes. Among them, the twin-screw extruder adopts 11 temperature settings, and the setting temperature is 160°C-240°C-260°C-270°C-270°C-240°C-240°C-230°C-230°C-230°C-260°C, The cooling temperature was 25°C. The screw speed of the twin-screw extruder was set at 500r/min.

The conventional chemical fiber polymer plus the polymer masterbatch containing natural herbal dyes prepared in this embodiment is melt-spun to make textiles, and the concentration of the herbal dyes is 1%, which is recorded as sample I.

Comparative example 1

The watermelon red dye extracted from madder was used to dye the PET textile through post-dyeing and the sample was recorded as A'.

Comparative example 2

The indigo dye prepared from bluegrass was used to dye PET textiles through post-dyeing to prepare samples, which were recorded as D'.

Comparative example 3

The black dye prepared from Galla chinensis was used to dye PET textiles through post-dyeing to prepare samples, denoted as E'.

Comparative example 4

The olive green extracted from Myrobalan was used to dye PET textiles through post-dyeing to prepare samples, which were recorded as F'.

Comparative example 5

The bright yellow color extracted from gardenia fruit was used to dye PET textiles through post-dyeing to prepare samples, which were denoted as G'.

Dyeing process:

Dye solution formula, vegetable dye 0.5% owf, acetic acid 0.5g/L, penetrant 1g/L, liquor ratio 1:30.

Add pre-treated PET fabric at 40°C, heat up to 130°C at 2°C/min, keep warm at 130°C for 30 minutes, and then cool down to 40°C at 2°C/min for dyeing. The dyed cloth is taken out to be washed and then dried.

For black dyeing, iron media is required, iron media prescription, 1g/L ferrous sulfate and 1g/Ld acetic acid, the bath ratio is 1:20. After washing the dyed cloth, soak the wet cloth in the above solution at 40°C for 30 minutes, Then wash and dry. Repeat the staining and ferric treatment one more time.

The textiles made of the polymer color masterbatch containing natural herbal dyes provided by the embodiments of the present invention 1-7 have carried out washing fastness, perspiration fastness (alkaline) and rubbing fastness, test standard, rating standard and used The equipment is shown in Table 1, and the test results are shown in Table 2.

Table 1 Color Fastness Test Standards, Rating Standards and Instruments Used

Table 2 Examples 1-9 and Comparative Examples 1-5 provide the grades of color fastness of the textile samples

As can be seen from Table 2, the color fastness (washing fastness, perspiration fastness, and rubbing fastness) of the samples obtained by directly spinning the color masterbatch is higher than that of the samples obtained by direct dyeing and finishing of herbal dyes. )high.

There are three methods for the determination of the dispersion of herbal dyes in polymers, namely the two-roll machine method, the filter pressure rise method and the thin film method. The dispersibility of the polymer color masterbatch containing natural herbal dye provided by the present invention in the polymer is tested by the filter pressure difference method. Test principle: The increase in the internal melt pressure of the extruder caused by the blockage of the filter screen when the pigment sample passes through the filter screen of the extruder is a measure of the dispersibility of the pigment.

Filtration Pressure Value (FPV) Definition: The pressure value increased per gram of pigment during extrusion. Examples 1-9 See Table 3 for the filtration performance test results of the herbal dye masterbatch.

Table 3 embodiment 1-9 herbal dye masterbatch filtration performance test result

It can be found from the test results of the filtration performance of herbal dye masterbatches in Examples 1-9 in Table 3 that the filter pressure difference is within 0.06MPa, indicating that these herbal dyes are evenly dispersed in the polymer matrix and do not affect the processing and application of the masterbatch .

It should be noted that although the foregoing embodiments have been described herein, the scope of protection of the present invention is not limited thereby. Therefore, based on the innovative concept of the present invention, the changes and modifications made to the embodiments described herein, or the equivalent structure or equivalent process transformation made by using the description of the present invention and the contents of the accompanying drawings, directly or indirectly apply the above technical solutions In other related technical fields, all are included in the patent protection scope of the present invention.

Claims

The polymer color masterbatch containing natural herbal dyes is characterized in that, in parts by weight, it comprises:

50-98 parts of polymer;

1 to 10 parts of dispersant;

0.5 to 1 part of antioxidant; and

0.1-30 parts of herbal dyes, wherein,

The average particle size of the herbal dye is 0.1-2um.
The polymer color masterbatch containing natural herbal dyes according to claim 1, wherein said polymer is selected from one of polyester, polyamide or polypropylene.
The polymer masterbatch containing natural herbal dyes according to claim 1, wherein said herbal dyes are one or more of watermelon red, bright yellow, indigo, olive green and black dyes extracted from herbal plants Compound dyes.
The polymer masterbatch containing natural herbal dyes according to claim 1, characterized in that, the content of said herbal dyes is 0.1-30% by weight.
According to the preparation method of the polymer masterbatch containing natural herbal dyes according to any one of claims 1 to 4, it is characterized in that, comprising the following steps:

Vacuum-dry the herbal dye for 4-12 hours, crush the polymer slices into a powder with a mesh number of 20-50 mesh, and vacuum-dry at 120°C-220°C for 4-12 hours before use;

Weighing the dried herbal dye, the dried polymer raw material, the dispersant and the antioxidant respectively according to parts by weight;

adding the weighed dried herbal dyes, dried polymer raw materials, dispersant and antioxidant raw materials into a high-speed mixer, and mixing evenly at a mixing temperature of 30-80°C to obtain a mixture containing natural herbal dyes;

Add the mixture containing natural herbal dyes to a twin-screw extruder for mixing, extrude and granulate to make a polymer masterbatch containing natural herbal dyes, wherein the twin-screw extruder adopts 11 zone temperature settings , the setting temperature is 160°C-240°C-250°C-260°C-260°C-230°C-230°C-230°C-230°C-230°C-250°C, the cooling temperature is 15-30°C, twin-screw extrusion The screw speed of the machine is set at 300-500r/min.
The method for preparing a polymer masterbatch containing natural herbal dyes according to claim 5, wherein the drying temperature in the step of vacuum drying the herbal dyes is 60-80°C.
The preparation method of the polymer masterbatch containing natural herbal dyes according to claim 5, characterized in that the stirring speed of the high-speed mixer is 100-150 r/min, and the stirring time is 15-30 min.
According to the preparation method of the polymer masterbatch containing natural herbal dyes according to claim 5, it is characterized in that, when the said dried herbal dyes and dried polymer raw materials are added to the high-speed mixer, by online metering The machine adds raw materials accurately and continuously, the dried polymer slices are added through the main feeding port of the high-speed mixer, and the dried herbal dyes are added through the side feeding port of the high-speed mixer.
According to the preparation method of the polymer masterbatch containing natural herbal dyes according to claim 5, it is characterized in that, the herbal dyes are modified herbal dye particles, and the preparation method of the modified herbal dye particles is:

Grind the herbal plant dyes in a ball mill until the particle size is 0.1-2um, and then granulate them through a wet granulator at a temperature of 60-80°C. Add a dispersant before granulation to obtain a modified herb Dye particles.
According to the preparation method of the polymer color masterbatch containing natural herbal dyes according to claim 9, it is characterized in that the dispersant is one or both of an ester dispersant and EBS with a mass percent concentration of 60-90%. .