CN101139748B - Fine denier or ultra-fine denier nylon fibre and production method thereof - Google Patents

Abstract

The invention relates to a fine denier or ultrafine denier nylon fiber and a production method thereof. The technical problem to be solved by the present invention is to provide a fine denier or ultrafine denier nylon fiber with a fineness less than 1 denier and a production method thereof. The fiber of the present invention is characterized in that the fiber contains nylon, an effective amount of a compound of a second main group metal and an effective amount of an auxiliary agent-antioxidant. The production method of the present invention is characterized in that the compound of the second main group metal and nylon are melted, blended and extruded in advance to obtain the additive in the form of a masterbatch, wherein the compound of the second main group metal accounts for 5 to 50% of the total weight of the additive; and then The additive masterbatch is melt-spun together with nylon, and the amount of the additive masterbatch should make the ratio of the weight of the second main group metal element to the weight of nylon consistent.

Description

A kind of fine denier or superfine denier nylon fiber and its production method

technical field

The invention relates to the field of spinning materials, in particular to a fine-denier or ultra-fine-denier nylon fiber and a production method thereof. the

Background technique

Generally speaking, the polymer materials that can be spun include nylon (polyamide), polypropylene (polypropylene), polyester (polyethylene terephthalate) and acrylic (polyacrylonitrile). These materials can be spun to form filaments for use in the textile industry. Melt spinning is a commonly used spinning method, and fiber filaments suitable for spinning can be obtained by melt spinning. Generally, fiber filaments obtained by the melt spinning method can reach a fineness degree (fineness) of several deniers. The products obtained by weaving and weaving with such fiber filaments, such as clothing fabrics, have many advantages, so the market application space is broad. the

Yet along with the raising of people's living standard, also more and more higher to the requirement of textile, it is very necessary to be able to overcome some existing defects of textile. For example, the above-mentioned products such as clothing fabrics have rough hand feeling, poor softness, poor air permeability, poor water absorption, and are easy to fluff and pill due to their thick fiber filaments. In order to solve these problems, the fine or ultra-fine denier of textile fibers has become an important research topic. the

At present, many researches on the fine or ultra-fine denier of textile fibers have been carried out, and there are many related reports. For example, as far as China is concerned, polyester fiber fine or ultra-fine denier technology was successfully developed in the 1980s. The fine or ultra-fine denier of polypropylene fiber was developed in the 1990s by academician Xu Duanfu of the Institute of Chemistry, Chinese Academy of Sciences. This technology has been industrialized. describe. the

However, for nylon, the technology of producing (super) fine-denier nylon fibers by conventional melt spinning method is not yet mature. the

Nylon fiber fabric has the characteristics of sweat absorption, light weight, good toughness, good resilience, acid and alkali resistance, etc. It is one of the most suitable artificial fabrics for human wear. The application in clothing is also one of the main uses of nylon fiber. The thickness of nylon fiber can be characterized by single filament fineness. Generally, chemical fibers with a single filament fineness of about 1 denier are called fine denier fibers, and chemical fibers with a single filament fineness of about 0.5 denier are called ultrafine denier fibers. The finer the nylon fiber, the higher the wearing comfort of its fabric. Fine denier or ultra-fine denier fibers can be woven into high-grade textiles that are soft to the touch and comfortable to wear, and have high economic value. Therefore, the development of fine-denier fiber and ultra-fine-denier fiber manufacturing technology is a high-tech that all countries have paid attention to in recent years. If nylon fibers can be made fine or ultrafine, it will open up another broad application field for the textile industry. the

The diameter of fine denier fiber and ultrafine denier fiber is much thinner than that of conventional chemical fiber (single filament fineness is generally about 3-6 denier). agent. It is also necessary to reasonably select the spinning technical scheme and strictly control the spinning, drafting and other production processes. the

However, so far, there are not many research reports on improving the spinnability of nylon through modification. The main aspect of modification is to reduce the molecular orientation of nylon during winding by copolymerization or adding additives to improve the elongation of monofilament. ability. For example, (1) introduce asymmetric units by copolymerization to reduce the ability of molecular orientation, such as adding asymmetric dibasic acid, diamine or caprolactam and nitrogen cyclohexane with side groups when ordinary nylon is polymerized; ( 2) Add acrylic acid derivatives, such as methyl methacrylate polymer, during spinning; (3) Use long-chain nylon for spinning or add long-chain nylon and its salts when the monomer of matrix nylon is polymerized. the

On the other hand, the improvement in the spinning process mainly includes the following aspects: (1) reduce the aperture of the spinneret, such as using a spinneret with a diameter of 0.2 mm or even a finer aperture, and increase the spinneret accordingly (2) Improve the purity of the spinning melt through high-precision filtration; (3) Reduce the degree of stretching and molecular orientation of the tow from spinning to winding to retain more extension ability of the tow ; (4) take a higher draft multiple. the

Nylon fiber fabric has the characteristics of sweat absorption, light weight, good toughness, good resilience, acid and alkali resistance, etc. It is one of the most suitable artificial fabrics for human wear. Therefore, it is very important to make nylon fiber monofilament fine or ultrafine. It is undoubtedly very important to propose suitable spinning raw materials to be able to produce fine denier or ultrafine denier nylon fibers. the

However, as far as the mentioned prior art is concerned, nylon fibers cannot be reasonably fine-denier or ultra-fine denier, and the fineness of the obtained fibers is still generally at least greater than 1 denier. the

Contents of the invention

The technical problem to be solved by the present invention is to provide a fine denier or super fine denier nylon fiber whose fineness can be less than 1 denier. the

Another technical problem to be solved by the present invention is to provide a method capable of producing fine denier or ultrafine denier nylon fibers with deniers less than 1 denier. the

The fine denier or ultrafine denier nylon fiber of the present invention is characterized in that the fiber contains nylon and an effective amount of a compound of a second main group metal and an effective amount of auxiliary agent-antioxidant. Effective amounts of metal compounds and additives can be determined with limited experimentation. the

As preferably, the weight of the second main group metal element in the compound of the second main group metal is 80ppm～10% of the nylon weight, and the weight of the antioxidant is 0.001%～1% of the nylon weight; the second main group metal element Selected from magnesium, calcium or strontium, the compound of the second main group metal is the second main group metal salt or/and complex, wherein the anion of the metal salt or the ligand of the complex is selected from phosphate, carbonate, carboxylate Acid, nitrate, sulfate, sulfonate, sulfite, halide anions, pseudohalide ions, and other nitrogen- and/or oxygen- and/or sulfur-containing organic ligands. The above "other nitrogen-containing and/or oxygen-containing and/or sulfur-containing organic ligands" all refer to organic ligands that have been disclosed before the filing date of the present invention. the

The compound of the second main group metal can be, for example: magnesium carbonate, calcium carbonate, strontium carbonate; magnesium phosphate, calcium phosphate, strontium phosphate; magnesium acetate, calcium acetate, strontium acetate; magnesium sulfate, calcium sulfate, strontium sulfate; magnesium sulfonate , calcium sulfonate, strontium sulfonate; magnesium fluoride, calcium fluoride, strontium fluoride; magnesium chloride, calcium chloride, strontium chloride; magnesium bromide, calcium bromide, strontium bromide, etc. the

Nylon is the basic component of the fiber, common nylon for spinning can be used in the present invention, there is no particular limitation, for example, nylon 6, nylon 66, etc. can be used. the

Adding the compound of the second main group metal will make the nylon fiber show good properties in the melt spinning process, such as high strength, high viscosity, high spinnability and textile safety, etc., so that the present invention can be spun into fineness Fine-denier or ultra-fine-denier fibers less than 1 denier. Although there is no existing applicable theory to explain it, the applicant believes that the possible mechanism is as follows: the compound of the second main group metal can increase the strength of the nylon melt, improve the viscosity of the melt, reduce the melt index MFR, So that it can withstand a large tensile force, even when the melt becomes a semi-molten body after spinning, it still has good strength, so it can withstand a large tensile force, so that the fiber filaments are melted During the spinning process, it can withstand the force in the drawing step without breaking, thereby improving the spinnability of nylon fibers and obtaining fine or ultrafine denier fibers. But the effect of the present invention is not bound by this theory. the

In order to ensure the effect of being able to be spun into fine denier or superfine denier nylon fibers, the effective amount of the compound of the second main group metal is as follows: the weight of the second main group metal element in the compound of the second main group metal is 80ppm of nylon weight ~10%. If the use amount of the metal element of the second main group in the compound of the second main group metal is lower than 80ppm, then its modification effect on nylon is not good enough, causing the composition to be difficult to be spun into fine denier or superfine denier fiber; If the amount is greater than 10%, the amount of the compound of the second main group metal added is too much, so that the spinning effect of the composition is poor, resulting in poor quality of fiber filaments, and the fineness will be higher than 1 denier. The weight of the metal element of the second main group is preferably 0.01% to 5% of the nylon weight, more preferably 0.1% to 5%, and particularly preferably 0.3% to 2%. the

Also in the nylon fiber of the present invention: one or more in antioxidant, ultraviolet absorber, antistatic agent, wherein,

The antioxidants are (hindered phenols and phosphites): antioxidant 1010, antioxidant CA, antioxidant 163, antioxidant 168, antioxidant 3114, antioxidant DLTP and antioxidant TNP One or more of them, the amount of antioxidant added is 0.001% to 1% of the weight of nylon;

The ultraviolet absorber is organic aromatic substances such as benzotriazoles and benzophenones, such as 2-(2-hydroxyl-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole , 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-n-octyloxybenzophenone,: 2-(2- Hydroxy-5-octylphenyl)-benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-benzotriazole, 2-(2-hydroxy-5-methyl Phenyl)-benzotriazole, one or more of carbon black, zinc oxide, and titanium dioxide, and the amount of ultraviolet absorber added is 0.001% to 1% of the weight of nylon;

The antistatic agent is fatty alcohol phosphate, fatty alcohol oxyalkylene ether phosphate salt, fatty alcohol phosphate potassium, lauryl sulfate sodium salt, stearic acid monoglyceride, lauryl alcohol oxyethylene ether phosphate potassium salt , one or more of polyethylene glycol, and the antistatic agent is added in an amount of 0.001% to 10% of the nylon weight. the

The above-mentioned auxiliary agents all refer to the auxiliary agents disclosed before the application date of the present invention. the

A kind of production method of fine denier or superfine denier nylon fiber of the present invention, adopt melt spinning method, it is characterized in that adding a kind of compound of second main group metal and auxiliary agent-antioxidant in the melt spinning process of nylon . the

The above "melt spinning method" refers to heating and melting the raw materials for spinning, extruding the molten body through a screw extruder and sending it to the spinning machine, and quantitatively pressing the molten body into the spinning part through a metering pump. The spinneret holes on the wire plate make the molten body flow out in a filament state, oiled and wound, or also subjected to hot drafting to obtain fine or ultrafine denier nylon fibers. the

The above-mentioned "melt spinning process" includes all processes from raw material to filament formation, such as a pretreatment process of the raw material to be spun, a melting process of the raw material, and a filamentation process of the melt. the

In the production method of the fine-denier or ultra-fine-denier nylon fiber of the present invention, the compound of the second main group metal can be added at any time during the melt spinning process, and there is no special limitation on this. However, in view of the convenience of addition, it is preferable to add the compound before or during heat-melting of nylon. The method of adding this compound is not particularly limited, and it can be added directly, but it is preferably added after it is made into an additive (master batch) of a compound containing a second main group metal with part of nylon. the

Another production method of the fine denier or superfine denier nylon fiber of the present invention is that the compound of the second main group metal and the nylon are pre-melted, blended and extruded to obtain the additive in the form of a masterbatch, wherein the compound of the second main group metal Accounting for 5-50% of the total weight of the additive; then melt-spinning the additive masterbatch and nylon together; the amount of the additive masterbatch should make the ratio of the weight of the second main group metal element to the weight of nylon 80ppm-10%, Or 0.1% to 5%, or 0.3% to 2%, which can be obtained by calculation. the

The additive masterbatch can also contain 0.001% to 10% of auxiliary agent by weight of nylon. the

The above-mentioned melt-spun additive masterbatch and nylon are also added with additives and/or compounds of the second main group metal, wherein the amount of additives added is to make the ratio of the total amount of additives in the nylon fiber to the weight of nylon Consistent (that is to say, the total weight of the additives contained in the additive masterbatch and the additives added later should be consistent with the weight of nylon, that is, at least 0.001% of one kind to 3% of all three kinds. ), the addition of the compound of the second main group metal should make the ratio of the total amount of the second main group metal element in the nylon fiber to the weight of the nylon 80ppm to 10%, or 0.1% to 5%, or 0.3% to 2%. Consistent (that is to say, the total weight of the second main group metal element contained in the second main group metal compound in the additive masterbatch and the second main group metal element contained in the second main group metal compound added later, and The ratio of nylon weight should be consistent). This can be obtained by calculation. the

The additive masterbatch can be viewed as a dispersion of a high concentration of a Group II metal compound in nylon. Melt blending and extrusion molding can be carried out, for example, through equipment such as a single-screw extruder and a twin-screw extruder. the

In the method for producing fine denier or superfine denier nylon fiber of the present invention, like the compound of second main group metal, described auxiliary agent such as antioxidant, ultraviolet absorber, light stabilizer and/or antistatic agent etc. can be melted It is added at any time during the spinning process, and it is not particularly limited. These functional additives can be added simultaneously with the compound of the second main group metal, or can be added before or after the addition; if multiple additives are used at the same time, they can be added simultaneously or sequentially. In order to improve the ease of operation, it is preferred that these additives are added and used simultaneously with the compound of the second main group metal. the

For example, in a preferred scheme, an additive containing a compound of the second main group metal is obtained from a compound of the second main group metal, an auxiliary agent and part of nylon by melt blending, and then the additive is combined with the rest of the nylon Melt spinning is performed. the

In another preferred solution, the compound containing the second main group metal, the auxiliary agent and nylon are melt-spun together. the

If one, several or all of the nylon, the compound of the second main group metal, the additive masterbatch and the auxiliary agent are dried to remove moisture and small molecular substances before melting, the effect will be better. The drying temperature is 90-100°C, and the drying time is 24-48 hours. the

During the spinning process, the temperature of the nylon melt is 130-320°C, more preferably in the range of 160-280°C, most preferably in the range of 250-270°C, and the number of holes in the spinneret is 30-200 , the hole diameter is 0.1-0.6 mm, and the winding speed is preferably 100-8000 m/min. the

In a preferred embodiment, the process preferably further includes thermally drawing the obtained fine-denier or ultra-fine-denier nylon fiber filaments, which is carried out after oiling and winding to obtain coiled filaments. The temperature may be in the range of 50-160°C. the

The production method of the present invention has simple procedures and is easy to operate, and the fineness of the obtained fine denier or superfine denier nylon fiber can reach about 0.25 denier at least, and in the production process, the nylon fiber filament will not break substantially, and the obtained fine denier or ultrafine denier nylon fiber will not break. Ultrafine denier fibers have good mechanical properties, high strength and high elongation at break. the

Detailed ways

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, and are used for explaining the present invention, and 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 this invention. within the scope of the claimed invention. the

raw materials used

Nylon 6 slices: high-speed spinning pure nylon 6 slices produced by Ningbo Hengrun Company

Example 1

Prepare the _MgCl2 additive masterbatch using the twin-screw extruder according to the ratio in Table 1, where the temperature of each zone of the extruder is: 265°C for zone I; 305°C for zone II; 295°C for zone III; 295°C for zone IV ℃.

Table 1: Additive masterbatch formulations containing _MgCl2

ingredients parts by mass Nylon 6 slices 80 Metal salt MgCl ₂ 20 Antioxidant (Antioxidant 1010/Antioxidant 168) 1   Antistatic agent PEG400 12   Antistatic agent PEG20000 5

The obtained MgCl ₂ additive masterbatch and nylon 6 slices were dried in a vacuum oven to remove moisture and small molecular substances. The drying temperature is between 90-100°C, and the drying time is 24-48 hours.

Then mix the additive masterbatch of _MgCl2 with nylon 6 slices at a weight ratio of 5:1000 and then carry out melt spinning. The temperatures of the melt in each zone of the screw extruder are 250°C, 270°C, 270°C, 275°C, respectively. °C, the spinning temperature is 255 °C. The hole diameter of the spinneret used is 0.35mm, the length is 0.7mm, and the winding speed is 1400m/min, and the fine-denier nylon fiber with a winding fineness of 0.79 denier can be obtained. The strength of the mechanical property test can reach 3.7cN/dtex, and the fracture The elongation is at 41%.

Example 2

Prepare fine denier or superfine denier nylon fiber according to the method for _embodiment 1, difference is, use the ratio of following table 2 to use twin-screw extruder to prepare CaCl Additive masterbatch, the weight ratio of additive masterbatch and nylon 6 chips is 1 : 1000 The spinning temperature is 255° C., the winding speed is 1400 m/min, and the obtained winding yarn is thermally drawn 1.20 times on the drawing machine. A fine-denier nylon fiber with a fineness of 0.70 denier was obtained. In the mechanical property test, the fiber filament strength reaches 4.0cN/dtex, and the elongation at break is 19%.

Table 2: CaCl ₂ Additive Masterbatch Formulation

ingredients parts by mass Nylon 6 slices 80 Metal salt CaCl ₂ 70 Antioxidant (Antioxidant 1010) 1

Example 3

Prepare fine denier or superfine denier nylon fiber according to the method for embodiment 1, difference is, use twin-screw extruder to prepare Sr(Ac) in the ratio of following table 3 ₂ additive master batches, the weight of additive master batches and nylon 6 chips The ratio was 5:100, the spinning temperature was 255°C, and the winding speed was 1500 m/min. A fine-denier nylon fiber with a fineness of 0.40 denier was obtained. In the mechanical property test, the fiber filament strength reaches 3.8cN/dtex, and the elongation at break is 28%.

Table 3: Sr(Ac) ₂ Additive Masterbatch Formulation

ingredients parts by mass

Nylon 6 slices 80 Metal salt Sr(Ac) ₂ 40 Antioxidant (Antioxidant 1010) 1

Example 4

Use 6 parts of calcium phosphate and 100 parts (all by weight), nylon 6 chips, 1 part of antioxidant (antioxidant 1010) to carry out melt spinning together, the temperature of melt in each district in the screw extruder is respectively 260 °C, 280 °C, 280 °C, 285 °C, the spinning temperature is 260 °C. The hole diameter of the spinneret used is 0.35mm, the length is 0.7mm, and the winding speed is 1300m/min, and the fine-denier nylon fiber with a winding fineness of 0.30 denier can be obtained. The mechanical property test strength can reach 3.8cN/dtex, and the fracture The elongation is at 38%. the

Comparative example 1

Without adding any other substances, only nylon 6 chips are used for melt spinning. The temperatures of the melt in each zone of the screw extruder are 260°C, 305°C, 290°C, and 290°C, and the spinning temperature is 295°C. The speed is 900 m/min, the number of spinneret holes is 48, the hole diameter is 0.3 mm, and the aspect ratio is 3:1. Obtained the nylon 6 coiling yarn that monofilament fineness is 2.7 deniers. Carry out 3 times thermal drafting to the obtained nylon 6 wound silk, roller temperature 90 degree, hot plate temperature 160 degree, try to manufacture the nylon 6 fine-denier fiber that monofilament fineness is 0.9 denier, experimental result shows, wound silk The strips break every few minutes, nylon 6 fine denier fibers cannot be obtained, and stable production cannot be achieved. the

Comparative example 2

After mixing 1000 parts of nylon 6 chips, 1 part of antioxidant (antioxidant 1010/antioxidant 168), 12 parts of PEG400 and 3 parts of PEG20000, melt spinning was carried out according to the method of Example 1. A fine-denier nylon fiber with a fineness of winding yarn of 10 denier was obtained, and thermal drawing was performed at 100° C. with a mechanical force of 3.3 times to obtain a nylon fiber filament of 3 denier. Performance test Its strength is 3.6cN/dtex, and its elongation at break is 35%. the

Comparative example 3

Nylon 6 chips were melt-spun according to the method of Example 4, and the winding speed was 3000 m/min. The fineness of the obtained fiber filaments was 3 deniers. The strength is 4.3cN/dtex, and the elongation at break is 28%. the

By comparing Examples 1-4, especially Examples 1 and 4, and Comparative Examples 1-3, it can be seen that the nylon added with the compound of the second main group metal can be spun into a fine denier or ultra-fine denier with a fineness less than 1 denier. denier nylon fiber, and the nylon without the compound of the second main group metal can only be spun out of a nylon fiber with a fineness of about 3 denier, such as Comparative Examples 2 and 3, but it is impossible to spin a fine or ultra-fine denier nylon fiber at all. For example Comparative Example 1. the

Claims (6)

1. the production method of thin dawn or superfine denier nylon fibre, it is characterized in that compound and auxiliary agent and nylon 6 or nylon 66 melt blending extrusion molding in advance with second main group metal, obtain additive and become the master batch shape, wherein the compound of second main group metal accounts for 5～50% of additive gross weight; And then the additive master batch carried out melt spinning with nylon 6 or nylon 66, the consumption of additive master batch will make wherein that the weight of the second main group metal element and the ratio of nylon 6 or nylon 66 weight are 80ppm～10%;

The described second main group metal element is selected from magnesium, calcium or strontium, the compound of second main group metal is the second main group metal salt or/and complex compound, and it is nitrogenous and/or contain oxygen and/or sulfur-bearing organic ligand that wherein the part of the anion of slaine or complex compound is selected from phosphate radical, carbonate, carboxylate radical, nitrate radical, sulfate radical, sulfonate radical, inferior sulfate radical, halide anion, pseudohalogen ion and other;

One of described auxiliary agent antioxidant is: one or more among antioxidant 1010, antioxidant CA, antioxidant 163, antioxidant 168, antioxidant 3114, anti-oxidant DLTP and the antioxidant TNP, the weight of antioxidant are 0.001%～1% of nylon weight;

Described auxiliary agent also has antistatic additive, described antistatic additive is one or more in fatty alcohol phosphate potassium, lauryl sodium sulfate salt, stearic acid monoglyceride, laruyl alcohol oxygen vinethene phosphate kalium salt, the polyethylene glycol, and the consumption of antistatic additive is 0.001%～10% of a nylon weight.

2. production method according to claim 1 is characterized in that the weight of the second main group metal element in the compound of described second main group metal is 0.1%～5% of nylon weight.

3. production method according to claim 2 is characterized in that the weight of the second main group metal element in the compound of described second main group metal is 0.3%～2% of nylon weight.

4. according to claim 1 or 2 or 3 described production methods, it is characterized in that before fusion to nylon the compound of second main group metal, a kind of, several in additive master batch and the auxiliary agent or all carry out drying.

5. according to claim 1 or 2 or 3 described production methods, it is characterized in that in spinning process the temperature of nylon molten mass is 130～320 ℃, the hole count of spinnerets is 30～200, the aperture is 0.1～0.6mm, and the speed of coiling is preferably 100～8000 meters/minute.

6. production method according to claim 4 is characterized in that in spinning process, and the temperature of nylon molten mass is that the hole count of 130～320 ℃ of spinneretss is 30～200, and the aperture is 0.1～0.6mm, and the speed of coiling is preferably 100～8000 meters/minute.