CN103966673B - Fine denier nylon raw material co-blended spinning master batch - Google Patents

Abstract

The invention discloses a fine-denier nylon raw material blended spinning masterbatch. The blended spinning masterbatch is prepared by pulverizing nylon and forming under pressure. Nylon is pulverized into powder and mixed with melt spinning additive powder to obtain the main material , The main material is press-molded, and dispersants, binders, disintegrants, co-solvents, lubricants, coating agents and other components are optionally added during the press-molding process. Using the masterbatch provided by the invention can significantly increase the effective concentration of melt spinning additives and auxiliary materials in the blended spinning masterbatch, and the various components of the blended spinning masterbatch are evenly dispersed, and the types and contents of the components are easier to control without high temperature Operation, production/processing/preparation process is safer.

Description

Fine denier nylon raw material blended spinning masterbatch

technical field

The invention relates to a textile technology, in particular to a raw material blended spinning masterbatch for producing fine-denier nylon (fiber).

Background technique

Generally speaking, the polymer materials that can be spun include natural fibers and chemical fibers. Among them, chemical fibers mainly include: polyamide (commonly known as "nylon" or "nylon"), polypropylene (commonly known as "polypropylene"), polyethylene terephthalate (commonly known as "polyester"), polyacrylonitrile (commonly known as "acrylic") ")Wait. These materials can be spun to form filaments for use in the textile industry. Melt spinning is a commonly used spinning technique, and fiber filaments suitable for textiles can be obtained through melt spinning.

Among them, nylon is the earliest synthetic fiber in the world. It is characterized by high strength and good wear resistance, and its strength and wear resistance rank first among all fibers. Nylon has the same disadvantages and deficiencies as other chemical fibers, such as poor softness, poor moisture absorption and permeability, etc.

With the improvement of people's living standards, the requirements for the performance of nylon fiber textiles are getting higher and higher, such as softness, hygroscopicity, dyeability, antistatic, flame resistance, anti-fouling, anti-pilling and other properties. Therefore, Scientists use chemical or physical methods to improve the properties of nylon fibers such as moisture absorption, dyeing, antistatic, flame resistance, stain resistance, and pilling resistance by changing the structure of the chemical fiber polymer monomer or changing the denier of the fiber.

Studies have shown that the softness, hygroscopicity, uniformity, strength and other properties of fibers are inversely proportional to the thickness of fibers, while the thickness of fibers is measured by "denier", that is, the quality of fiber per unit length, the unit is dtex, so high Performance and new varieties of fine-denier nylon fibers are often achieved by reducing the denier of nylon fibers, and reducing the denier of nylon is usually achieved by adding to nylon raw materials during the melt spinning process to modify, reduce defects, and improve performance. The addition of additives and auxiliary materials and the uniformity of the addition of additives and auxiliary materials play a key role in the modification of nylon.

The traditional methods of adding additives and auxiliary materials mainly include the following two methods: direct addition method and masterbatch addition method. The direct addition method refers to adding various additives and auxiliary materials directly to the nylon spinning raw materials in the melt spinning process to make a spinning melt for the preparation of nylon fibers; Various additives and auxiliary materials are mixed with a small amount of nylon spinning raw materials to prepare blended spinning masterbatches, and then the prepared blended spinning masterbatches are put into a large amount of nylon spinning raw materials in the melt spinning process to prepare nylon fibers .

Although the steps of the direct addition method are simple, it has the following disadvantages: the addition of additives/excipients is uneven and the aggregation is obvious, resulting in poor product uniformity; Stable; concentrated addition of chemically active additives may cause damage to production equipment.

In contrast, the masterbatch addition method has the advantages of constant proportion of various additives, easy control of the amount of spinning masterbatch, uniform dispersion, and no damage to production equipment, thus effectively ensuring the quality of spinning products. Stability, therefore, most high performance and new varieties of fibers are synthesized by masterbatch addition method.

At present, the spinning masterbatch used in the masterbatch addition method is basically prepared by hot melt blending, that is, before the melt spinning process, a small amount of nylon spinning raw material is melted to form a nylon spinning raw material melt, and the nylon spinning raw material The melt is fully stirred with various auxiliary materials, blended and sheared, and finally cooled to obtain spinning masterbatch. Using this method to prepare spinning masterbatches, the nylon spinning raw materials in the spinning masterbatches need to go through a high-temperature melting stage, which not only consumes a lot of energy, but also often causes problems such as thermal degradation of nylon. The fluidity of the molten spinning masterbatch raw material in the silk masterbatch process and the concentration of various auxiliary materials in the spinning masterbatch are limited, thus limiting the performance optimization of the spinning product.

Therefore, it is very important to develop a new generation of spinning masterbatches with low cost and low energy consumption.

Contents of the invention

In order to solve the above-mentioned problems, the present inventors have done a lot of research and experiments, and found that: the cold pressing method is used, that is, the mixed powder of nylon raw materials, melt spinning additives and auxiliary materials is directly blended without high temperature melting process, and then pressurized and formed by mechanical processing , to prepare the spinning masterbatch, the spinning masterbatch prepared by this method can effectively improve the effective concentration and uniformity of the melt spinning additives and auxiliary materials in the spinning masterbatch, and the preparation process does not go through the high temperature melting process, It can effectively avoid the thermal degradation of nylon raw materials, and can obtain more effective and higher-quality spinning masterbatch than the existing hot melt blending method.

The object of the present invention is to provide the following aspects:

In the first aspect, the present invention provides a fine-denier nylon raw material blended spinning masterbatch, which is characterized in that the blended spinning masterbatch includes:

(1) Masterbatch main material, including: nylon and melt spinning additives, wherein the weight ratio of nylon and melt spinning additives is 1:10～10:1;

The nylon includes nylon 6, nylon 66, nylon 10, nylon 12, nylon 1212, nylon 610;

The melt-spinning additive is selected from compounds or complexes formed by the following metal cations and the following anions,

The metal is selected from:

Magnesium, calcium, strontium, aluminum, gallium, indium, germanium, tin, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, molybdenum, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;

The anion is selected from: phosphate, carbonate, carboxylate, nitrate, sulfate, sulfonate, sulfite, halide anion, pseudohalide ion and other nitrogen-containing and/or oxygen-containing and/or sulfur-containing organic compounds Body or multiple ligands, and derivatives of the aforementioned groups;

(2) Excipients are selected from at least one of dispersants, binders, disintegrants, cosolvents, lubricants and coating agents;

in,

Described dispersing agent is selected from: hexenyl bis stearamide, monoglyceride stearate, glyceryl tristearate, hydrocarbon paraffin or mixture thereof; Barium stearate, zinc stearate, calcium stearate , cadmium stearate, magnesium stearate or copper stearate; ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer or polyethylene wax;

The binder is selected from: starch, protein, dextrin, animal glue, shellac, hide glue or rosin; asphalt; water glass; polyethylene, polypropylene, polystyrene, polyvinyl chloride, silicone rubber, fluorine rubber , polysulfide rubber, epichlorohydrin rubber, nitrile rubber, polyacrylate rubber, polyurethane rubber or butyl rubber; polyvinyl alcohol, carboxymethyl cellulose, polyurethane, polystyrene, polyacrylate, ethylene-vinyl acetate copolymer butyl rubber, vinyl resin, acrylic resin, chlorinated rubber, epoxy resin, silicone oil, dimethyl silicone oil used alone or in combination;

The disintegrant is selected from: dry starch, sodium carboxymethyl starch; low-substituted hydroxypropyl cellulose, effervescent disintegrant, cross-linked polyvinylpyrrolidone or cross-linked sodium carboxymethyl cellulose;

The co-solvent is selected from: sodium benzoate, sodium salicylate, p-aminobenzoic acid; urea, nicotinamide or acetamide; borax or potassium iodide;

The lubricant is selected from: machine oil, loom oil, spindle oil, rail oil, steel rolling oil, turbine oil, compressor oil, refrigeration oil, cylinder oil, marine oil, gear oil, machine pressure gear oil, axle Oil, instrument oil, vacuum pump oil; castor oil or tallow; silicone oil, fatty acid amides, oleic acid, polyester, synthetic fat or carboxylic acid; graphite, molybdenum disulfide, polytetrafluoroethylene, nylon, boron nitride or graphite fluoride ;

The coating agent is selected from: hydroxypropyl methylcellulose, hydroxypropyl cellulose, acrylic resin IV, polyvinylpyrrolidone, cellulose acetate phthalate, hydroxypropyl methylcellulose phthalate , polyvinyl phthalate, styrene-maleic acid copolymer, acrylic resin, ethyl cellulose, cellulose acetate, hydroxypropyl cellulose, hypromellose, microcrystalline cellulose, povidone , single use or mixed use of polyethylene glycol or polyvinyl alcohol;

Wherein, the weight ratio of main material and auxiliary material of masterbatch is 1:1～100:0.5.

In the second aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, which is characterized in that the weight ratio of the nylon powder to the melt spinning additive is 1:3-3:1.

In a third aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, which is characterized in that the weight ratio of the main material of the masterbatch to the auxiliary material is 10:1-100:2.

In the fourth aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, characterized in that the dispersant is glyceryl tristearate.

In the fifth aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, which is characterized in that the binder is acrylic resin.

In the sixth aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, characterized in that the disintegrant is dry starch.

In the seventh aspect, the present invention provides the above-mentioned blended spinning masterbatch of fine-denier nylon raw materials, characterized in that the co-solvent is selected from sodium benzoate or borax.

In the eighth aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, characterized in that the lubricant is selected from silicone oil or fluorinated graphite.

In the ninth aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, characterized in that the coating agent is selected from hydroxypropyl methylcellulose and hydroxypropyl cellulose and used alone or in combination.

In the tenth aspect, the present invention provides the above fine-denier nylon raw material blended spinning masterbatch, which is characterized in that the blended spinning masterbatch is prepared by the following steps:

A. Nylon pulverization: at a temperature of -200 to 100°C, pulverize nylon particles to obtain nylon powder with a diameter of less than 5 μm. ～10:1 mixing and stirring evenly to make the main material of masterbatch;

B. Pressure molding: under normal temperature and pressure, fully mix the masterbatch main material and auxiliary materials prepared in step A in a weight ratio of 1:1 to 100:0.5 to obtain the blended masterbatch raw material; Under the conditions of 0-200°C and a pressure of 0.1-10 MPa, pressurize the raw material of the blended masterbatch to obtain the blended spinning masterbatch.

In the method of the present invention, the term "melt spinning method" used refers to that the raw materials for spinning are heated and melted, and the molten body is extruded by a screw extruder and sent to the spinning machine, and the molten body is quantitatively pressed into the spinning machine through a metering pump. In the spinning part, the nylon melt is extruded in a fine filament state through the spinneret hole on the spinneret, cooled and formed after side blowing, and then the finished product is obtained by oiling and winding, or after oiling and clustering, it is hot-drawn Stretching to obtain fine denier nylon filaments.

In the method of the present invention, the term "press forming" refers to pressing nylon, melt spinning additives and other auxiliary materials into desired shapes by means of mechanical pressure.

In the method of the present invention, the term "melt spinning additive" used means that a small amount of addition to nylon raw materials in the melt spinning process can significantly improve fiber properties or give nylon spinning products some new, original nylon spinning properties. The product does not show the properties of the substance.

In the method of the present invention, the term "auxiliary material" used refers to an additive that is not used to improve the properties of fibers, but to increase the properties of the blended spinning masterbatch such as forming and disintegration.

The fine-denier nylon raw material blended spinning masterbatch provided according to the present invention has the following advantages:

(1) The effective concentration of melt spinning additives and auxiliary materials in the blended spinning masterbatch has been significantly increased;

(2) The types and contents of various additives and auxiliary materials in the blended spinning masterbatch are easier to control, and the components are evenly dispersed;

(3) The size of the blended spinning masterbatch is uniform, which is convenient for packaging, and can realize the accurate and quantitative addition of the blended spinning masterbatch in the subsequent melt spinning process;

(4) There is no high-temperature melting process in the preparation process of the blended spinning masterbatch, which effectively avoids the thermal degradation of nylon, thereby ensuring the quality of the nylon fiber obtained by spinning;

(5) The preparation process of blended spinning masterbatch does not require high-temperature operation, which reduces energy consumption, is environmentally friendly, reduces production costs, and makes the production, processing, and preparation processes safer and more reliable.

detailed description

The present invention is further described below through specific examples. The features and advantages of the present invention will become clearer along with these descriptions. However, these examples are merely exemplary for explaining the present invention, but do not limit the scope of the present invention in any way. Those skilled in the art should understand that without departing from the spirit and scope of the present invention, the present invention can be modified and/or changed and/or equivalently replaced in terms of details, and these modifications/modifications/replacements should all fall within the scope of the present invention within the scope of the claimed protection.

The invention provides a blended spinning masterbatch of fine denier nylon raw materials, which comprises the following components:

(1) The main material of the masterbatch, including: nylon and melt spinning additives with a weight ratio of 1:10 to 10:1, among which,

The nylon includes nylon 6, nylon 66, nylon 10, nylon 12, nylon 1212, nylon 610;

Melt spinning additives are the main substances that play a modifying role in the melt spinning process. In the subsequent spinning process, they use their own chemical properties to improve the process conditions and optimize the performance of the fibers produced. Strength, elongation at break, water absorption and softness, etc., wherein the metal is selected from magnesium, calcium, strontium, aluminum, gallium, indium, germanium, tin, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt , nickel, copper, zinc, yttrium, zirconium, molybdenum, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; the ligands of the anions or complexes are selected from : Phosphate, carbonate, carboxylate, nitrate, sulfate, sulfonate, sulfite, halide anion, pseudohalide ion and other nitrogen-containing and/or oxygen-containing and/or sulfur-containing organic ligands or multiple ligands , and derivatives of the aforementioned groups; a single component or a mixture of compounds composed of the above anions and cations can be used to improve the performance of nylon fibers.

(2) Excipients are selected from at least one of dispersants, binders, disintegrants, cosolvents, lubricants and coating agents;

In the spinning process, the more uniform the melt spinning additive is dispersed in the nylon raw material, the better its modification effect on nylon, so that the quality of the produced nylon fiber is better, so it is usually added to play a dispersing role Organic polymers or inorganic salts, dispersants can evenly disperse the main material of the masterbatch into the nylon raw material during the melt spinning process, so that the melt spinning additive and the nylon raw material can be fully mixed evenly, so the material that can be miscible with the nylon raw material is selected , or a material with good dispersion in nylon raw materials, the dispersant selected in the present invention is selected from: hexenyl bisstearamide (EBS), monoglyceride stearate (GMS), glyceryl tristearate (HTG ), hydrocarbon paraffin solids, etc. alone or in mixture; liquid paraffin or microcrystalline paraffin; barium stearate, zinc stearate, calcium stearate, cadmium stearate, magnesium stearate or copper stearate; Ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer or polyethylene wax (PEG), preferably tristearin (HTG).

When preparing the blended spinning masterbatch, it is difficult to make the blended spinning masterbatch reach a certain hardness simply by mechanically pressing the main material of the blended spinning masterbatch, so it is necessary to add a binder to the masterbatch main material to make the masterbatch The material has viscosity, which is convenient for subsequent press molding. The present invention selects: starch, protein, dextrin, animal glue, shellac, hide glue or rosin; asphalt; water glass; polyethylene, polypropylene, polystyrene, poly Vinyl chloride, silicone rubber, fluororubber, polysulfide rubber, epichlorohydrin rubber, nitrile rubber, polyacrylate rubber, polyurethane rubber or butyl rubber; polyvinyl alcohol, carboxymethyl cellulose, polyurethane, polystyrene, polyvinyl alcohol Acrylic ester, ethylene-vinyl acetate copolymer, butyl rubber, vinyl resin, acrylic resin, chlorinated rubber, epoxy resin, silicone oil or simethicone oil are used alone or in combination, preferably acrylic resin.

In order to make the blended spinning masterbatch disintegrate smoothly in the nylon raw material, the melt-spinning additive and disintegrant are released, selected from: dry starch or sodium carboxymethyl starch (CMS-Na); low-substituted hydroxypropyl cellulose (L-HPC), effervescent disintegrant, crospovidone or croscarmellose sodium (CCNa).

In the process of melt spinning, the role of the co-solvent is to make the melt spinning additive released from the disintegration of the blended spinning masterbatch dissolve more fully in the molten nylon raw material, so that it can modify the molten nylon raw material. The cosolvent used in the present invention is selected from: sodium benzoate, sodium salicylate or p-aminobenzoic acid; urea, nicotinamide or acetamide; borax or potassium iodide.

In the process of preparing the blended spinning masterbatch under pressure, the lubricant can play a role in increasing the fluidity of the blended spinning masterbatch raw material in the compression molding/tabletting process, thereby improving the efficiency of pressure molding. Animal or vegetable oils are good natural lubricants; synthetic oils can work the same because they also have a similar structure to natural oils; and some inorganic substances that have a layered phosphorus structure, such as graphite fluoride, also Can play the effect of lubrication, therefore, the lubricant used in the present invention is selected from: machine oil, loom oil, spindle oil, rail oil, rolling oil, gas turbine oil, compressor oil, refrigerating machine oil, cylinder oil, marine oil , gear oil, machine pressure gear oil, axle oil, instrument oil or vacuum pump oil; castor oil or tallow; silicone oil, fatty acid amide, oleic acid, polyester, synthetic fat or carboxylic acid; graphite, molybdenum disulfide, polytetrafluoroethylene , nylon, boron nitride or graphite fluoride, preferably silicone oil or graphite fluoride.

In order to make the blended spinning masterbatch product after pressurized molding easy to demold, in the process of pressurized preparation of the blended spinning masterbatch, it is necessary to add a substance with low viscosity between the mold and the mold, that is, a coating agent, so that the blended spinning masterbatch The silk masterbatch maintains a good shape during the demoulding process, and the coating agent selected in the present invention is selected from: hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), acrylic resin No. IV or polyethylene Pyrrolidone (PVP), Cellulose Acetate Phthalate (CAP), Hydroxypropyl Methyl Cellulose Phthalate (HPMCP), Polyvinyl Alcohol Phthalate (PVAP), Styrene Maleic Acid Copolymer (StyMA), acrylic resins, ethyl cellulose, cellulose acetate, hydroxypropyl cellulose, hypromellose, microcrystalline cellulose, povidone, polyethylene glycol, or polyvinyl alcohol alone or in combination Use, preferably hydroxypropyl methylcellulose or hydroxypropyl cellulose alone or in combination.

The role of the blended spinning masterbatch is to disintegrate in the molten nylon raw material during melt spinning, so that the melt spinning additive in it is added to the nylon raw material to modify the nylon raw material. The silk additive is added more uniformly in the nylon raw material, and it is necessary to control the local concentration of the melt-spinning additive in the molten nylon raw material so that it cannot be too high, otherwise it will easily cause uneven quality of the produced nylon fiber, thereby reducing the performance of nylon, so control The weight ratio of nylon powder to melt-spinning additives does not exceed 10:1; the amount of melt-spinning additives added to nylon raw materials can be adjusted by adding the amount of blended spinning masterbatch, and the content of additives should not be too low to prevent nylon Too much auxiliary material is introduced into the raw material to reduce the performance of nylon fiber, so the weight ratio of nylon powder and melt spinning additive is controlled not less than 1:10.

The blended spinning masterbatch provided by the present invention is prepared through the following steps:

A. Nylon crushing: at a temperature of -200 to 100°C, preferably -200 to -10°C, the nylon particles are crushed to obtain nylon powder with a diameter of less than 5 μm, and the obtained nylon powder is melt-spun at normal temperature and pressure. The silk additive is mixed in a weight ratio of 1:10 to 10:1 and stirred evenly to obtain the main material of the masterbatch;

B. Pressure molding: under normal temperature and pressure, fully mix the masterbatch main material and auxiliary materials prepared in step A in a weight ratio of 1:1 to 100:0.5 to obtain the blended masterbatch raw material; Under the conditions of 0-200°C and a pressure of 0.1-10 MPa, pressurize the raw material of the blended masterbatch to obtain the blended spinning masterbatch.

In step A, in order to prevent nylon raw materials and melt spinning additives from melting due to frictional heat during the pulverization process of nylon, resulting in uneven mixing of nylon powder and melt spinning additives and poor formability, a cooling device, such as liquid The nitrogen cooling device keeps the nylon particles in a low-temperature environment and forms a nylon powder with good dispersibility, which is convenient for subsequent mixing with melt spinning additives and pressure molding. Since the melting point of different types of nylon is in the range of 200-300 ° C, the temperature is controlled at -200～100℃.

Since the nylon blended spinning masterbatch provided by the present invention is prepared by cold pressing method, that is, nylon powder is directly mixed with melt spinning additives and auxiliary materials at normal temperature and pressure, and then directly formed blended spinning masterbatch by mechanical pressure, without After the high-temperature melting process, the particle size of the nylon powder and the closeness to the particle size of the melt spinning additives/auxiliary materials directly affect the uniformity of mixing the nylon powder with the melt spinning additives and auxiliary materials in the blended spinning masterbatch and the prepared The molding effect of the blended spinning masterbatch, and the uniformity of the components in the blended spinning masterbatch directly affects its dispersion in the molten nylon raw material during the melt spinning process. Nylon powder and melt spinning additives The more uniformly the /auxiliary materials are mixed, the better the degree of dispersion in the molten nylon raw material, and the better the quality of the produced nylon fiber; at the same time, the more uniformly the nylon powder is mixed with various additives/auxiliary materials, the better it is in the preparation of blended spinning masterbatches. The easier it is to operate when granulating, the easier it is to form the blended spinning masterbatch; and because the particle size of the additives and auxiliary materials selected in the present invention is micron, the particle size of the nylon powder selected in the present invention is below 5 μm. Since the particle size of nylon powder, melt-spinning additives and auxiliary materials are all on the micron scale, there is no need for high-temperature melt-mixing, and the temperature range of 0-200°C is selected to directly mix the above three into tablets to make blended spinning masterbatches. And because the blended spinning masterbatch needs to be disintegrated in the molten nylon raw material to provide melt spinning additives, the blended spinning masterbatch should not only be easy to disintegrate, but also need to have a certain hardness to facilitate packaging and transportation. Therefore, this The invention selects a pressure range of 0.1-10 MPa for press molding, and pressurizes the blended masterbatch raw material prepared in step A to prepare the blended spinning masterbatch.

The fine-denier nylon raw material blended spinning masterbatch provided according to the present invention has the following advantages:

First, the effective concentration of melt-spinning additives and auxiliary materials in blended spinning masterbatches has been significantly increased;

Second, the types and contents of various additives and auxiliary materials in the blended spinning masterbatch are easier to control, and the components are evenly dispersed;

Third, the size of the blended masterbatch is uniform, which is convenient for packaging, and can realize accurate and quantitative addition of the masterbatch in the subsequent melt spinning process;

Fourth, there is no high-temperature melting process in the preparation process of the blended spinning masterbatch, which effectively avoids the thermal degradation of nylon, thereby ensuring the quality of the nylon fiber obtained by spinning;

Fifth, the preparation process of blended spinning masterbatch does not require high-temperature operation, which reduces energy consumption, is environmentally friendly, reduces production costs, and makes the production, processing, and preparation processes safer and more reliable.

Example

Experimental part

1. Terminology used:

(1) The "parts" mentioned in the examples are all "parts by weight".

(2) The "hardness" involved in the examples refers to the ultimate pressure when the blended spinning masterbatch is broken after being tested by a flat plate upper and lower tablet tester.

2. Source of raw materials used:

(1) Nylon 6 slices: high-speed spinning pure nylon 6 slices produced by Ningbo Hengrun Company;

(2) LaCl ₃ (anhydrous lanthanum chloride): Huizhou Geili Technology Co., Ltd.;

(3) Y(NO ₃ ) ₃ (anhydrous yttrium nitrate): Zibo Lanthanide Industry and Trade Co., Ltd.;

(4) Ce ₂ (SO ₄ ) ₃ (anhydrous cerium sulfate): Zibo Ruibokang Rare Earth Materials Co., Ltd.

Example 1

Nylon 6 slices were pulverized together by a grinder to obtain nylon powder with a diameter of 5 μm, and the prepared nylon powder was mixed with melt spinning additive Y(NO ₃ ) ₃ (anhydrous yttrium nitrate) in a weight ratio of 9:1, Make the main material of the masterbatch, according to the weight ratio of the main material of the masterbatch and the auxiliary material of 100:1 and 100:3 respectively, add the dispersant tristearin (HTG) Dry starch, prepared as blended masterbatch raw material.

The prepared blended masterbatch raw material was pressurized by a manual tablet press, and shaped under the condition of a pressure of 1 MPa to obtain a tablet-shaped blended spinning masterbatch.

Take 10 pieces of blended spinning masterbatches prepared in this experimental example for analysis and testing, and the relevant experimental test data are shown in Table 1 below.

Table 1

Example 2

Nylon 6 slices were pulverized together by a grinder to obtain nylon powder with a diameter of 2 μm, and the prepared nylon powder was mixed with melt spinning additive Y(NO ₃ ) ₃ (anhydrous yttrium nitrate) in a weight ratio of 9:1, Make the main material of the masterbatch, according to the weight ratio of the main material of the masterbatch and the auxiliary material of 100:1 and 100:0.5 respectively, add the dispersant glyceryl tristearate (HTG) and the cosolvent borax to the main material of the masterbatch , Prepared into blended masterbatch raw materials.

The prepared blended masterbatch raw material was pressurized by an automatic tablet press, and shaped under the condition of a pressure of 1.2 MPa to obtain a tablet-shaped blended spinning masterbatch.

Take 10 pieces of blended spinning masterbatches prepared in this experimental example for analysis and testing, and the relevant experimental test data are shown in Table 2 below.

Table 2

Example 3

Nylon 6 slices are crushed together by a grinder to obtain nylon powder with a diameter of 1 μm, and the prepared nylon powder is mixed with melt spinning additive Ce ₂ (SO ₄ ) ₃ (anhydrous cerium sulfate) in a weight ratio of 7:3 , to make the main material of the master batch, according to the weight ratio of the main material of the master batch and the auxiliary material of 100:2 and 100:0.5, add lubricant silicone oil and acrylic resin of the adhesive to the main material of the master batch, and prepare a blend Masterbatch raw material.

The prepared blended masterbatch raw material was pressurized by a manual tablet press, and shaped under the condition of a pressure of 0.4 MPa to obtain a tablet-shaped blended spinning masterbatch.

Take 10 pieces of the blended spinning masterbatch prepared in this experimental example for analysis and testing, and the relevant experimental test data are shown in Table 3 below.

table 3

Example 4

Nylon 6 slices are crushed together by a grinder to obtain nylon powder with a diameter of 0.5 μm, and the prepared nylon powder is mixed with melt spinning additive Ce ₂ (SO ₄ ) ₃ (anhydrous cerium sulfate) in a weight ratio of 7:3 Mix to make the main material of the master batch, respectively according to the ratio of 100:3 and 100:1 by the weight ratio of the main material of the master batch and the auxiliary material, add lubricant graphite fluoride and sodium benzoate as a cosolvent to the main material of the master batch, and prepare Blend masterbatch raw materials.

The prepared blended masterbatch raw material is pressurized by an automatic tablet press, and shaped under the condition of a pressure of 0.5 MPa to obtain a tablet-shaped blended spinning masterbatch.

Take 10 pieces of blended spinning masterbatches prepared in this experimental example for analysis and testing, and the relevant experimental test data are shown in Table 4 below.

Table 4

Example 5

Nylon 6 slices were pulverized by a grinder to obtain nylon powder with a diameter of 0.2 μm, and the prepared nylon powder was mixed with melt spinning additive LaCl ₃ (anhydrous lanthanum chloride) in a weight ratio of 1:1 to make a master The main material of the masterbatch, according to the weight ratio of the main material of the masterbatch and the auxiliary material is 100:5 and 100:0.5, add lubricant silicone oil and coating agent hydroxypropyl methylcellulose (HPMC) to the main material of the masterbatch, Prepared as blended masterbatch raw materials.

The prepared blended masterbatch raw material was pressurized by a manual tablet press, and shaped under the condition of a pressure of 0.3 MPa to obtain a tablet-shaped blended spinning masterbatch.

Take 10 pieces of blended spinning masterbatches prepared in this experimental example for analysis and testing, and the relevant experimental test data are shown in Table 5 below.

table 5

Example 6

Nylon 6 slices were pulverized by a grinder to obtain nylon powder with a diameter of 0.1 μm, and the prepared nylon powder was mixed with melt spinning additive LaCl ₃ (anhydrous lanthanum chloride) in a weight ratio of 1:1 to make a master The main material of the granules is respectively according to the weight ratio of the main material of the master batch and the auxiliary material of 100:2 and 100:0.5, and the lubricant silicone oil and the coating agent hydroxypropyl cellulose (HPC) are added to the main material of the master batch to prepare Blend masterbatch raw materials.

The prepared blended masterbatch raw material was pressurized by an automatic tablet press, and shaped under the condition of a pressure of 0.4 MPa to obtain a tablet-shaped blended spinning masterbatch.

Take 10 pieces of the blended spinning masterbatch prepared in this experimental example for analysis and testing, and the relevant experimental test data are shown in Table 6 below.

Table 6

comparative example

Comparative example 1

LaCl ₃ (anhydrous lanthanum chloride) and nylon 6 chips are used in the following weight ratio to produce blended spinning masterbatch by conventional melt blending method.

Three of the blended spinning masterbatches prepared by each mass ratio were analyzed and tested, and the experimental data are shown in Table 7 below.

Table 7

Experimental example

The spinning masterbatches prepared in the above-mentioned Examples 1 to 6 and Comparative Example 1 are used for melt spinning, and the technological parameters of the spinning process are shown in Table 8 below:

Table 8

The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions and implementations of the present invention, all of which fall within the scope of the present invention. The protection scope of the present invention shall be determined by the appended claims.

Claims (14)

1. Fine denier nylon raw material blended spinning masterbatch, it is characterized in that, this blended spinning masterbatch comprises: (1) masterbatch main material, including: nylon and melt spinning additive, wherein, the weight ratio of nylon and melt spinning additive is 1:10～10:1; The nylon includes: nylon 6, nylon 66, nylon 10, nylon 12, nylon 1212 and nylon 610; The melt-spinning additive is selected from compounds formed by cations of the following metals and anions of the following, The metal is selected from: Magnesium, calcium, strontium, aluminum, gallium, indium, germanium, tin, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, molybdenum, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; The anion is selected from: phosphate, carbonate, carboxylate, nitrate, sulfate, sulfonate, sulfite, halide anion, pseudohalide ion and other nitrogen-containing and/or oxygen-containing and/or sulfur-containing organic compounds Body or multiple ligands, and derivatives of the aforementioned groups; (2) The auxiliary material is selected from at least one of dispersants, binders, disintegrants, cosolvents, lubricants and coating agents; in, Described dispersing agent is selected from: hexenyl bis stearamide, monoglyceride stearate, glyceryl tristearate, hydrocarbon paraffin or mixture thereof; Barium stearate, zinc stearate, calcium stearate , cadmium stearate, magnesium stearate or copper stearate; ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer or polyethylene wax; The binder is selected from: starch, protein, dextrin, animal glue or rosin; asphalt; water glass; polyethylene, polypropylene, polystyrene, polyvinyl chloride, silicon rubber, fluororubber, polysulfide rubber, chlorine Alcohol rubber, nitrile rubber or butyl rubber; polyvinyl alcohol, carboxymethylcellulose, polyurethane, polyacrylate, ethylene-vinyl acetate copolymer, acrylic resin, chlorinated rubber, epoxy resin, silicone oil, alone or Mixed use; The disintegrant is selected from: dry starch, sodium carboxymethyl starch; low-substituted hydroxypropyl cellulose, effervescent disintegrant, cross-linked polyvinylpyrrolidone or cross-linked sodium carboxymethyl cellulose; The co-solvent is selected from: sodium benzoate, sodium salicylate, p-aminobenzoic acid; urea, nicotinamide or acetamide; borax or potassium iodide; The lubricant is selected from: mechanical oil, rail oil, steam turbine oil, compressor oil, refrigerating machine oil, cylinder oil, marine oil, gear oil, vacuum pump oil; castor oil or tallow; silicone oil, fatty acid amide, oleic acid, polyester , synthetic fat or carboxylic acid; graphite, molybdenum disulfide, polytetrafluoroethylene, nylon or boron nitride; The coating agent is selected from: hydroxypropylmethylcellulose, hydroxypropylcellulose, polyvinylpyrrolidone, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, phthalic acid Polyvinyl alcohol ester, styrene-maleic acid copolymer, acrylic resin, ethyl cellulose, cellulose acetate, microcrystalline cellulose, povidone, polyethylene glycol or polyvinyl alcohol, alone or in combination; Wherein, the weight ratio of main material and auxiliary material of masterbatch is 1:1～100:0.5. 2. The fine-denier nylon raw material blended spinning masterbatch according to claim 1, characterized in that, in the masterbatch main material, the weight ratio of the nylon and the melt spinning additive is 1:3 to 3:1. 3. The blended spinning masterbatch of fine denier nylon raw material according to claim 1, characterized in that the weight ratio of the main material of the masterbatch to the auxiliary material is 10:1 to 100:2. 4. fine denier nylon raw material blend spinning masterbatch according to claim 1, is characterized in that, described dispersant is glyceryl tristearate. 5. fine denier nylon raw material blend spinning masterbatch according to claim 1 is characterized in that, described binding agent is acrylic resin. 6. fine denier nylon raw material blend spinning masterbatch according to claim 1 is characterized in that, described disintegrant is dry starch. 7. fine-denier nylon raw material blend spinning masterbatch according to claim 1, is characterized in that, described cosolvent is selected from sodium benzoate or borax. 8. The fine-denier nylon raw material blended spinning masterbatch according to claim 1, characterized in that, the lubricant is selected from silicone oil. 9. The fine-denier nylon raw material blended spinning masterbatch according to claim 1, characterized in that, the coating agent is selected from hydroxypropyl methylcellulose or hydroxypropyl cellulose and used alone or in combination. 10. fine-denier nylon raw material blend spinning masterbatch according to claim 1, is characterized in that, described blending spinning masterbatch obtains by following steps preparation: A. Nylon pulverization: at a temperature of -200 to 100°C, pulverize nylon particles to obtain nylon powder with a diameter of less than 5 μm. ～10:1 mixing and stirring evenly to make the main material of masterbatch; B. Pressure molding: under normal temperature and pressure, fully mix the masterbatch main material and auxiliary materials prepared in step A in a weight ratio of 1:1 to 100:0.5 to obtain the blended masterbatch raw material; Under the conditions of 0-200°C and a pressure of 0.1-10 MPa, pressurize the raw material of the blended masterbatch to obtain the blended spinning masterbatch. 11. fine denier nylon raw material blend spinning masterbatch according to claim 1, it is characterized in that, The binder is selected from simethicone; The lubricant is selected from: loom oil, spindle oil, steel rolling oil, extreme pressure gear oil, axle oil, instrument oil; fluorinated graphite. 12. The fine-denier nylon raw material blended spinning masterbatch according to claim 1, characterized in that, the melt spinning additive is selected from the complexes formed by the cations of the above metals and the above anions. 13. The fine-denier nylon raw material blended spinning masterbatch according to claim 1, characterized in that, the binder is selected from: shellac, hide glue, polyacrylate rubber, polyurethane rubber, used alone or in combination . 14. The fine-denier nylon raw material blended spinning masterbatch according to claim 1, characterized in that, the coating agent is selected from No. IV acrylic resin.