CN112195534A - Colored polylactic acid tow and preparation method thereof - Google Patents
Colored polylactic acid tow and preparation method thereof Download PDFInfo
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- CN112195534A CN112195534A CN202010945701.8A CN202010945701A CN112195534A CN 112195534 A CN112195534 A CN 112195534A CN 202010945701 A CN202010945701 A CN 202010945701A CN 112195534 A CN112195534 A CN 112195534A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- General Chemical & Material Sciences (AREA)
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- Artificial Filaments (AREA)
- Biological Depolymerization Polymers (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention provides a colored polylactic acid tow, which comprises a material A, a material B and a proper amount of coloring agent; the material A comprises the following components in percentage by mass: 45 to 89 weight percent of crystalline polylactic acid and 0.02 to 0.2 weight percent of nucleating agent; the material B comprises the following components in percentage by mass: 7 to 45 weight percent of non-crystalline polylactic acid and 3.8 to 9.98 weight percent of color fixing material. The invention also provides a preparation method of the colored polylactic acid tow, and the colored polylactic acid tow has good heat resistance and excellent coloring performance and color retention.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to a colored polylactic acid tow and a preparation method of the colored polylactic acid tow.
Background
Polylactic acid (PLA) is a biodegradable novel material, and is prepared from renewable crop starch (such as starch of corn, cassava, sugarcane and the like) as a raw material, the PLA has good biodegradability, and finally, degradation products are carbon dioxide and water after the PLA is used and subjected to natural degradation processes such as composting and the like, so that the PLA does not pollute the environment, does not consume high energy, and does not additionally generate carbon dioxide.
At present, polylactic acid is widely applied in fiber textile industry, such as manufacturing non-woven fabrics, health care fabrics, carpets and the like. With the increasing requirements of people on product differentiation, functionalization and diversification, colored polylactic acid fiber tows are also under development, and the colored polylactic acid fiber tows are mainly realized by pigment blending and dye dyeing at present. In view of the material characteristics of polylactic acid, in order to balance the comprehensive performance of materials, the existing dye and dyeing method are not easy to color the polylactic acid fiber, and the polylactic acid fiber is easy to fade and fade even in the later period of coloring, so that the stability of the product is affected, and the psychological sense of insecurity of consumers in the using process can also be caused.
Disclosure of Invention
The first purpose of the invention is to provide a colored polylactic acid tow.
The second purpose of the invention is to provide a preparation method of the colored polylactic acid tow.
The first purpose of the invention is realized by the following technical scheme:
a colored polylactic acid tow comprises a material A, a material B and a proper amount of coloring agent;
the material A comprises the following components in percentage by mass: 45 to 89 weight percent of crystalline polylactic acid and 0.02 to 0.2 weight percent of nucleating agent;
the material B comprises the following components in percentage by mass: 7 to 45 weight percent of non-crystalline polylactic acid and 3.8 to 9.98 weight percent of color fixing material.
Further, the colored polylactic acid tow is of a skin-core structure, the material A serves as a core layer of the skin-core structure, and the material B serves as a skin layer of the skin-core structure. Through such setting, can realize that skin layer structure has the colour, and core layer structure does not have the colour to bring special outward appearance and visual perception for polylactic acid silk bundle.
Furthermore, the cross section shape of the core-skin structure tow comprises a cross-shaped, an X-shaped, an H-shaped or core-skin-like structure and the like.
Furthermore, the crystallinity of the crystalline polylactic acid is 25-55%, the melt index is 15-35 g/10min (210 ℃, 2.16kg), and the melting temperature is 180-220 ℃.
Furthermore, the crystallinity of the non-crystalline polylactic acid is 5-15%, the melt index is 15-35 g/10min (210 ℃, 2.16kg), and the melting temperature is 135-170 ℃.
The crystalline polylactic acid can be selected from one or more polylactic acids with crystallinity and/or melt index. Similarly, the non-crystalline polylactic acid may be selected from one or more of the polylactic acids having crystallinity and/or melt index. The invention has the advantages that the polylactic acid tows with the skin-core structure and the excellent heat resistance can be prepared by respectively selecting polylactic acid materials with different crystallinities and melt indexes for the skin-layer structure and the core-layer structure.
Further, the color fixing material comprises a methacrylate polymer.
Further, the methacrylate polymer comprises at least one of polymethyl methacrylate, methacrylic acid-methyl methacrylate copolymer, methyl methacrylate-acrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer, methyl methacrylate-styrene-maleic anhydride terpolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-butyl acrylate copolymer, methyl methacrylate-acrylic acid-2-hydroxyethyl ester copolymer or methyl methacrylate-hydroxypropyl acrylate copolymer. The color fixing material can increase the combination fastness of the coloring agent and the polylactic resin and has the function of adjusting the color brightness.
Further, the nucleating agent comprises at least one of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide, graphene oxide or carbon nano tubes. The nucleating agent can increase the crystallization speed and the crystallinity of the polylactic acid of the core layer and improve the heat resistance.
Furthermore, the single denier of the filament bundle is 1.0-15 dtex.
Further, the coloring agent is a high-temperature-resistant dye, and comprises one of monascus red natural pigment (red), gardenia blue natural pigment (blue), sodium copper chlorophyllin natural pigment (green), grape skin red natural pigment (purple), sorghum red natural pigment (brown), plant carbon black natural pigment (black) and turmeric natural pigment (yellow).
For polylactic acid tow for food grade use, the colorant is a food grade dye.
The second purpose of the invention is realized by the following technical scheme:
a preparation method of colored polylactic acid tows comprises the following steps:
s1) taking materials according to the raw material ratio, and preparing polylactic acid nascent tows;
s2) carrying out water bath drafting coloring on the primary tow obtained in S1) to obtain colored polylactic acid tow.
Further, the specific process for preparing the polylactic acid nascent tow comprises the following steps: mixing the material A and the material B according to a proportion, and placing the mixture in a screw extruder for extrusion; then oiling, winding and collecting the primary tows.
Further, the specific process for preparing polylactic acid nascent tow in S1 includes: mixing the material A serving as a core layer according to a set proportion, mixing the material B serving as a skin layer according to a set proportion, and respectively putting the mixed material A and the mixed material B into different screw extruders to extrude a semi-finished product with a skin-core structure; then oiling, winding and collecting the primary tows.
Further, the extrusion conditions of the screw extruder are set as follows: the screw temperature is set in a gradient way at 170-235 ℃, the filter temperature is 235-245 ℃, the spinneret plate is 230-250 ℃, the cooling temperature is 10-40 ℃, and the traction speed is 500-1200 m/min.
Further, the method also comprises the step of drying the material A and/or the material B.
Preferably, the drying process is that the material A is placed in a vacuum drum dryer at 80 ℃ to be rotated and dried for 12 hours, then is cooled to be below 45 ℃, and is placed in a screw extruder to be extruded; and (3) placing the material B in a vacuum drum dryer at 60 ℃ for rotating and drying for 24h, cooling to below 45 ℃, and then placing in a screw extruder for extrusion.
Further, the water bath drawing and coloring of the as-spun filament bundle in S2 is performed by using an aqueous solution containing 0.5 wt% to 5 wt% of a coloring agent.
Further, the water bath drafting and coloring process comprises bundling the nascent filament bundle, wherein the water bath drafting speed is 100-250 m/min, the heating medium is an aqueous solution containing a coloring agent, the temperature of the first water bath is 68-72 ℃, the temperature of the second water bath is 72-76 ℃, the total drafting multiple is 2.5-4 times, then the preformed shape is realized by water vapor, the water cooling and curling are carried out, and the colored polylactic acid filament bundle is obtained after the filament bundle is dried.
Preferably, the number of crimped tows is 23-30/25 mm.
Preferably, the tows are dried at the temperature of 58-70 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the colored polylactic acid tow has good heat resistance and excellent coloring performance and color retention, does not fade or fade after being soaked in hot water at 50-80 ℃ for 12-24 h, and has the fiber tow shrinkage rate of less than 0.6%.
(2) The polylactic acid tow can be widely applied to the industries of clothes, non-woven fabrics, tobacco and the like, and can effectively improve the differentiation, the functionalization and the diversification of products.
Drawings
FIG. 1 is a cross sheath-core structured tow of colored polylactic acid according to the present invention;
FIG. 2 is a cross sheath-core structured tow of colored polylactic acid according to the present invention;
FIG. 3 shows a colored H-shaped sheath-core tow of polylactic acid according to the present invention;
FIG. 4 shows a colored H-shaped sheath-core tow of polylactic acid according to the present invention;
the reference numbers in the figures are as follows: 1-skin layer structure and 2-core layer structure.
Detailed Description
The present invention is further described below in conjunction with specific examples to better understand and implement the technical solutions of the present invention for those skilled in the art.
Example 1
A preparation method of colored polylactic acid tows comprises the following steps:
1) preparing the primary raw silk: mixing 60 parts of polylactic acid (with the crystallinity of 40 percent and the melt index of 30g/10min) and 0.1 part of nano silicon dioxide in a core layer, placing the mixture in a vacuum drum dryer at the temperature of 80 ℃, drying the mixture for 12 hours in a rotating manner, cooling the mixture to the temperature below 45 ℃, and discharging the mixture into a hopper of a single-screw extruder; mixing 35 parts of polylactic acid (with crystallinity of 5 percent and melt index of 20g/10min) and 4.9 parts of polymethyl methacrylate in a vacuum drum dryer at 60 ℃ for drying for 24 hours, cooling to below 45 ℃, and discharging to a hopper of another single-screw extruder; the screw temperature is 185-.
2) Preparing post-spun drawn colored tows: the nascent tows are reasonably bundled according to the requirements, the water bath drafting speed is 150m/min, the heating medium is 0.5 wt% of a water solution of a scarlet natural pigment, the temperature of the first water bath is 70 ℃, the temperature of the second water bath is 74 ℃, the total drafting multiple is 3.2 times, the primary tows are pre-shaped by water vapor, water-cooled and curled, the number of curls is 26/25 mm, and the colored polylactic acid tows with the skin-core structure are obtained after drying at 65 ℃, as shown in figure 1, the colored polylactic acid tows with the skin-core structure comprise a skin layer structure 1 and a core layer structure 2.
Comparative example 1
A method of making a colored polylactic acid tow, this comparative example being different from example 1 in that:
the core layer comprises: 60 parts of polylactic acid (crystallinity 40%, melt index 30g/10 min);
the cortex layer comprises: 40 parts of polylactic acid (crystallinity is 5 percent, and melt index is 20g/10 min);
heating a medium: 0.5 wt% of a natural pigment aqueous solution of red yeast.
Example 2
The difference between the preparation method of the colored polylactic acid tow and the embodiment 1 is that:
the core layer comprises: 85 parts of polylactic acid (the crystallinity is 25 percent, and the melt index is 25g/10min), and 0.08 part of nano titanium dioxide;
the cortex layer comprises: 10 parts of polylactic acid (crystallinity 10%, melt index 30g/10min), 4.92 parts of methacrylic acid-methyl methacrylate copolymer;
heating a medium: 1.0 wt% aqueous solution of natural pigment of gardenia blue.
Comparative example 2
A method of making a colored polylactic acid tow, this comparative example being different from example 2 in that:
the core layer comprises: 85 parts of polylactic acid (the crystallinity is 25 percent, and the melt index is 25g/10 min);
the cortex layer comprises: 15 parts of polylactic acid (the crystallinity is 10 percent, and the melt index is 30g/10 min);
heating a medium: 1.0 wt% aqueous solution of natural pigment of gardenia blue.
Example 3
A preparation method of colored polylactic acid tows comprises the following steps:
1) preparing the primary raw silk: mixing 45 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 35g/10min) and 0.15 part of graphene, placing the mixture in a vacuum drum dryer at the temperature of 80 ℃, drying the mixture for 12 hours in a rotating manner, cooling the mixture to the temperature below 45 ℃, and discharging the mixture into a hopper of a single-screw extruder; mixing 45 parts of polylactic acid (with the crystallinity of 15 percent and the melt index of 25g/10min) and 9.85 parts of methyl methacrylate-acrylic acid copolymer, placing the mixture in a vacuum drum dryer at the temperature of 60 ℃, drying for 24 hours in a rotating manner, cooling to the temperature below 45 ℃, discharging the mixture into a hopper of another single-screw extruder; the screw temperature is 185-195-205-215-225 ℃, the filter temperature is 236 ℃, the spinneret plate is 231 ℃, the spinneret holes are cross spinneret holes, the cooling temperature is 15 ℃, the traction speed is 600m/min, and the nascent filament bundles are oiled, wound and dropped into a barrel to be collected.
2) Preparing post-spun drawn colored tows: the nascent filament bundle is reasonably bundled according to the requirement, the water bath drafting speed is 230m/min, the heating medium is a 1.5 wt% chlorophyll copper salt natural pigment aqueous solution, the first water bath temperature is 68 ℃, the second water bath temperature is 72 ℃, the total drafting multiple is 2.5 times, steam is preformed, water-cooling curling is carried out, the number of curls is 23/25 mm, and the colored polylactic acid filament bundle with the sheath-core structure is obtained after drying at 60 ℃, as shown in figure 2, the colored polylactic acid filament bundle comprises a sheath-core structure 1 and a core-layer structure 2.
Comparative example 3
A method of making a colored polylactic acid tow, this comparative example being different from example 3 in that:
the core layer comprises: 55 parts of polylactic acid (55 percent of crystallinity and 35g/10min of melt index);
the cortex layer comprises: 45 parts of polylactic acid (crystallinity 15%, melt index 25g/10 min);
heating a medium: 1.5 wt% aqueous solution of natural pigment of copper chlorophyllin salt.
Example 4
The embodiment of a preparation method of colored polylactic acid tows is different from that of example 3 in that:
the core layer comprises: 50 parts of polylactic acid (with the crystallinity of 30 percent and the melt index of 35g/10min) and 0.2 part of nano aluminum oxide;
the cortex layer comprises: 40 parts of polylactic acid (with the crystallinity of 12 percent and the melt index of 30g/10min), 9.8 parts of methyl methacrylate-maleic anhydride copolymer;
heating a medium: 2.0 wt% of grape skin red natural pigment aqueous solution.
Comparative example 4
A method of making a colored polylactic acid tow, this comparative example being different from example 4 in that:
the core layer comprises: 60 parts of polylactic acid (with the crystallinity of 30 percent and the melt index of 35g/10min) and 0.2 part of nano aluminum oxide;
the cortex layer comprises: 40 parts of polylactic acid (with the crystallinity of 12 percent and the melt index of 30g/10min), 9.8 parts of methyl methacrylate-maleic anhydride copolymer;
heating a medium: 2.0 wt% of grape skin red natural pigment aqueous solution.
Example 5
A preparation method of colored polylactic acid tows comprises the following steps:
1) preparing the primary raw silk: mixing 50 parts of polylactic acid (with the crystallinity of 30 percent and the melt index of 35g/10min), 20 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 30g/10min) and 0.15 part of carbon nano tube in a vacuum drum dryer at the temperature of 80 ℃, drying for 12 hours in a rotating manner, cooling to the temperature below 45 ℃, discharging into a hopper of a single-screw extruder; mixing 25 parts of polylactic acid (with the crystallinity of 12 percent and the melt index of 30g/10min) and 4.85 parts of methyl methacrylate-styrene-maleic anhydride terpolymer, placing the mixture in a vacuum drum dryer at the temperature of 60 ℃, drying the mixture for 24 hours in a rotating manner, cooling the mixture to the temperature below 45 ℃, and discharging the mixture into a hopper of another single-screw extruder; the screw temperature is 185-195-205-215-225 ℃, the filter temperature is 244 ℃, the spinneret plate is 248 ℃, the spinneret holes are H-shaped spinneret holes, the cooling temperature is 35 ℃, the traction speed is 1000m/min, and the nascent filament bundles are oiled, wound and dropped into a barrel to be collected.
2) Preparing post-spun drawn colored tows: the nascent tows are reasonably bundled according to the requirements, the water bath drafting speed is 200m/min, the heating medium is 3.0 wt% of sorghum red natural pigment aqueous solution, the first water bath temperature is 72 ℃, the second water bath temperature is 76 ℃, the total drafting multiple is 4 times, the primary tows are preformed by water vapor and are crimped by water cooling, the number of crimps is 30/25 mm, and the colored polylactic acid tows with the skin-core structure are obtained after drying at 68 ℃, as shown in figure 3, the colored polylactic acid tows with the skin-core structure comprise a skin layer structure 1 and a core layer structure 2.
Comparative example 5
A method of making a colored polylactic acid tow, this comparative example being different from example 5 in that:
the core layer comprises: 50 parts of polylactic acid (crystallinity is 30 percent, and melt index is 35g/10min) and 25 parts of polylactic acid (crystallinity is 55 percent, and melt index is 30g/10 min);
the cortex layer comprises: 25 parts of polylactic acid (crystallinity 12%, melt index 30g/10 min);
heating a medium: 3.0 wt% of natural sorghum red pigment aqueous solution.
Example 6
The difference between the preparation method of the colored polylactic acid tow and the embodiment 5 is that:
the core layer comprises: 40 parts of polylactic acid (with the crystallinity of 30 percent and the melt index of 15g/10min), 30 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 35g/10min) and 0.02 part of graphene oxide;
the cortex layer comprises: 20 parts of polylactic acid (crystallinity is 5 percent, and melt index is 35g/10min), 9.98 parts of methyl methacrylate-acrylic acid-2-hydroxyethyl ester copolymer;
heating a medium: 4.0 wt% of a plant carbon black natural pigment aqueous solution.
Comparative example 6
A method of making a colored polylactic acid tow, this comparative example being different from example 6 in that:
the core layer comprises: 40 parts of polylactic acid (with the crystallinity of 30 percent and the melt index of 15g/10min) and 30 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 35g/10 min);
the cortex layer comprises: 30 parts of polylactic acid (crystallinity is 5 percent, and melt index is 35g/10 min);
heating a medium: 4.0 wt% of a plant carbon black natural pigment aqueous solution.
Example 7
A preparation method of colored polylactic acid tows comprises the following steps:
1) preparing the primary raw silk: mixing 20 parts of polylactic acid (with the crystallinity of 35 percent and the melt index of 15g/10min) and 50 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 30g/10min) and 0.05 part of carbon nano tube in a vacuum drum dryer at the temperature of 80 ℃, drying for 12 hours in a rotating manner, cooling to the temperature below 45 ℃, discharging into a hopper of a single-screw extruder; mixing 10 parts of polylactic acid (with the crystallinity of 5 percent and the melt index of 35g/10min),15 parts of polylactic acid (with the crystallinity of 10 percent and the melt index of 30g/10min) and 4.95 parts of methyl methacrylate-hydroxypropyl acrylate copolymer, placing the mixture in a vacuum drum dryer at the temperature of 60 ℃, drying the mixture for 24 hours in a rotating manner, cooling the mixture to the temperature below 45 ℃, and discharging the mixture into a hopper of another single-screw extruder; the screw temperature is 185-195-205-215-225 ℃, the filter temperature is 239 ℃, the spinneret plate is 245 ℃, the spinneret holes are H-shaped spinneret holes, the cooling temperature is 33 ℃, the traction speed is 900m/min, and the nascent filament bundles are oiled, wound and dropped into a barrel to be collected.
2) Preparing post-spun drawn colored tows: the nascent filament bundle is reasonably bundled according to the requirement, the water bath drafting speed is 230m/min, the heating medium is a 5.0 wt% turmeric natural pigment aqueous solution, the first water bath temperature is 70 ℃, the second water bath temperature is 73 ℃, the total drafting multiple is 3.5 times, the water vapor pre-shaping is carried out, the water-cooling curling is carried out, the curling number is 28/25 mm, and the colored polylactic acid filament bundle with the sheath-core structure is obtained after drying at 64 ℃, as shown in figure 4, the colored polylactic acid filament bundle comprises a sheath-core structure 1 and a core-layer structure 2.
Comparative example 7
A method of making a colored polylactic acid tow, this comparative example being different from example 7 in that:
the core layer comprises: 20 parts of polylactic acid (the crystallinity is 35 percent, and the melt index is 15g/10min) and 50 parts of polylactic acid (the crystallinity is 55 percent, and the melt index is 30g/10 min);
the cortex layer comprises: 15 parts of polylactic acid (crystallinity is 5 percent, and melt index is 35g/10min),15 parts of polylactic acid (crystallinity is 10 percent, and melt index is 30g/10 min);
heating a medium: 5.0 wt% aqueous solution of natural curcumin.
Example 8
The difference between the embodiment and the embodiment 1 is that:
the core layer comprises: 45 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 30g/10min) and 0.1 part of nano silicon dioxide;
the cortex layer comprises: 10 parts of polylactic acid (crystallinity 5%, melt index 15g/10min),35 parts of polylactic acid (crystallinity 10%, melt index 35g/10min), 9.9 parts of methyl methacrylate-ethyl acrylate copolymer;
heating a medium: 3.5 wt% aqueous solution of natural pigment of red yeast.
Comparative example 8
A method of making a colored polylactic acid tow, this comparative example being different from example 8 in that:
the core layer comprises: 55 parts of polylactic acid (55 percent of crystallinity and 30g/10min of melt index);
the cortex layer comprises: 10 parts of polylactic acid (crystallinity is 5 percent, and melt index is 15g/10min),35 parts of polylactic acid (crystallinity is 10 percent, and melt index is 35g/10 min);
heating a medium: 3.5 wt% aqueous solution of natural pigment of red yeast.
Example 9
The difference between the preparation method of the colored polylactic acid tow and the embodiment 1 is that:
the core layer comprises: 45 parts of polylactic acid (with the crystallinity of 55 percent and the melt index of 30g/10min) and 0.1 part of nano silicon dioxide;
the cortex layer comprises: 10 parts of polylactic acid (crystallinity is 5 percent, and melt index is 15g/10min),35 parts of polylactic acid (crystallinity is 10 percent, and melt index is 35g/10min), and 9.9 parts of methyl methacrylate-butyl acrylate copolymer;
heating a medium: 2.5 wt% of gardenia blue natural pigment aqueous solution.
Comparative example 9
A method of making a colored polylactic acid tow, this comparative example being different from example 9 in that:
the core layer comprises: 55 parts of polylactic acid (55 percent of crystallinity and 30g/10min of melt index);
the cortex layer comprises: 10 parts of polylactic acid (crystallinity is 5 percent, and melt index is 15g/10min),35 parts of polylactic acid (crystallinity is 10 percent, and melt index is 35g/10 min);
heating a medium: 2.5 wt% of gardenia blue natural pigment aqueous solution.
Performance testing
And (3) testing heat resistance: cutting a certain length L1 sample after completely opening the tow sample, measuring the length L2 again after placing the tow sample in an environment at 65 ℃ for 30min, and calculating the shrinkage L as follows:
the smaller the shrinkage L, the higher the heat resistance.
Color fastness test: after selecting a part of tow samples to be completely loosened, placing the tow samples in hot water at 50 ℃ and 80 ℃ for soaking for 24 hours, taking out the tows to observe the color change of the aqueous solution, wherein the color of the aqueous solution indicates poor color fastness, and the color of the aqueous solution does not indicate excellent color fastness.
The shrinkage and color fastness of the polylactic acid tows prepared in the examples 1-9 and the comparative examples 1-9 by different processes were measured, and the results are shown in table 1.
TABLE 1 shrinkage and color fastness test conditions of polylactic acid tows prepared by different processes
The above embodiments illustrate various embodiments of the present invention in detail, but the embodiments of the present invention are not limited thereto, and those skilled in the art can achieve the objectives of the present invention based on the disclosure of the present invention, and any modifications and variations based on the concept of the present invention fall within the scope of the present invention, which is defined by the claims.
Claims (10)
1. The colored polylactic acid tow is characterized by comprising a material A, a material B and a proper amount of coloring agent;
the material A comprises the following components in percentage by mass: 45 to 89 weight percent of crystalline polylactic acid and 0.02 to 0.2 weight percent of nucleating agent;
the material B comprises the following components in percentage by mass: 7 to 45 weight percent of non-crystalline polylactic acid and 3.8 to 9.98 weight percent of color fixing material.
2. The colored polylactic acid tow according to claim 1, wherein the colored polylactic acid tow is of a sheath-core structure, the material A is used as a core layer of the sheath-core structure, and the material B is used as a skin layer of the sheath-core structure.
3. The colored polylactic acid tow according to claim 2, wherein the cross-sectional shape of the tow with the sheath-core structure comprises a cross shape, an X shape, an H shape, a sheath-core-like structure or the like.
4. The colored polylactic acid tow according to claim 1 or 2, wherein the crystallinity of the crystalline polylactic acid is 25-55%, the melt index is 15-35 g/10min, and the melting temperature is 180-220 ℃.
5. The colored polylactic acid tow according to claim 1 or 2, wherein the crystallinity of the amorphous polylactic acid is 5-15%, the melt index is 15-35 g/10min, and the melting temperature is 135-170 ℃.
6. The colored polylactic acid tow according to claim 1 or 2, wherein the color fixing material comprises a methacrylate polymer.
7. The colored polylactic acid tow according to claim 6, wherein the methacrylate-based polymer comprises at least one of polymethyl methacrylate, methacrylic acid-methyl methacrylate copolymer, methyl methacrylate-acrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer, methyl methacrylate-styrene-maleic anhydride terpolymer, methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-butyl acrylate copolymer, methyl methacrylate-2-hydroxyethyl acrylate copolymer, or methyl methacrylate-hydroxypropyl acrylate copolymer.
8. The colored polylactic acid tow according to claim 1 or 2, wherein the nucleating agent comprises at least one of nano-silica, nano-titania, nano-alumina, graphene oxide, or carbon nanotubes.
9. The colored polylactic acid tow according to claim 1 or 2, wherein the coloring agent is a high-temperature-resistant dye, and comprises one of monascus red natural pigment, gardenia blue natural pigment, sodium copper chlorophyllin natural pigment, grape skin red natural pigment, sorghum red natural pigment, plant carbon black natural pigment and turmeric natural pigment.
10. The preparation method of the colored polylactic acid tow according to claims 1 to 9, which is characterized by comprising the following steps:
s1) taking materials according to the raw material ratio, and preparing polylactic acid nascent tows;
s2) carrying out water bath drafting coloring on the primary tow obtained in S1) to obtain colored polylactic acid tow;
the water bath drafting coloring is carried out on the nascent filament bundle in S2, and the water bath drafting coloring is carried out by adopting an aqueous solution with the coloring agent content of 0.5-5 wt%.
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