Mildew-proof anti-mite polyamide 6 master batch as well as preparation method and application thereof

Abstract

The invention relates to the technical field of functional master batch materials, in particular to a mould-proof and anti-mite polyamide 6 master batch and a preparation method and application thereof.The mould-proof and anti-mite polyamide 6 master batch is prepared from, by weight, 66.7-88.9 parts of polyamide 6 slices, 10-30 parts of nano cuprous oxide powder, 1-3 parts of dispersing agent powder and 0.1-0.3 part of antioxidant; the antioxidant is a mixture of a hindered phenol antioxidant and a phosphite ester antioxidant. The hindered phenol antioxidant and the phosphite antioxidant are added in the formula of the master batch, so that the reaction between cuprous oxide and polyamide 6 is effectively reduced, the mite repelling rate of the prepared polyamide 6 reaches 80% or above, and the mildew-proof effect is 0 grade; meanwhile, a twisting and stacking device is additionally arranged on a melt spinning system, so that the ordered structure of cuprous oxide in the chinlon 6 slices is constructed, the dispersity of cuprous oxide in the chinlon 6 slices is effectively improved, and the performance of fibers is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of functional masterbatch materials, and in particular to a mildew and mite-proof polyamide 6 masterbatch and a preparation method and application thereof. Background Art

[0002] Mites are abundant in households, including various species such as dust mites, grain mites, and spiny mites. These mites are typically 0.1mm long in their larval stage and 0.3-0.5mm in adult stage. Their tiny size makes them appear powdery to the naked eye. They feed on food scraps, dander, and hair, and thrive in a dark environment at 20-25°C and 60-80% humidity. They primarily parasitize mattresses, quilts, and other bedding, but also food, medicine, and small animals such as cats and mice. Their bodies, carcasses, and feces cling to clothing and bedding or float in the air, causing significant environmental pollution.

[0003] According to relevant research, mites can cause allergies, sebitis, infectious diseases, prurigo, etc. At the same time, the presence of mites can rapidly increase the incidence of allergic diseases such as asthma, especially for infants and young children. 90% of childhood asthma is caused by mites.

[0004] Studies have shown that cuprous oxide can release copper ions (Cu + These ions have certain biological toxicity and can interfere with the physiological metabolism of mites, thereby inhibiting their growth and reproduction. At the same time, cuprous oxide can adhere to the surface of the product, forming a physical barrier that hinders the movement and attachment of mites.

[0005] Chinese invention patent CN118879064A discloses a copper antibacterial polyamide 6 masterbatch and its preparation method and application. The antibacterial rate of the prepared product reaches more than 98%. However, the inventor tested the anti-mite performance of the product and found that the mite repellency rate was 55%. Summary of the Invention

[0006] The purpose of the present invention is to provide a mildew-proof and mite-proof polyamide 6 masterbatch and a preparation method and application thereof.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides a mildew-proof and mite-proof polyamide 6 masterbatch. The mildew-proof and mite-proof polyamide 6 masterbatch comprises the following components in parts by weight: 66.7 to 88.9 parts of polyamide 6 chips, 10 to 30 parts of nano-cuprous oxide powder, 1 to 3 parts of dispersant powder, and 0.1 to 0.3 parts of an antioxidant; the antioxidant is a mixture of a hindered phenol antioxidant and a phosphite antioxidant.

[0009] Furthermore, the hindered phenol antioxidant is one or both of antioxidant 1098 and antioxidant 1010; and the phosphite antioxidant is one or both of antioxidant 626 and antioxidant 168.

[0010] Furthermore, the dispersant is stearic acid.

[0011] Furthermore, the relative viscosity of the polyamide 6 slice is 2.46-2.47, the water content is 400-600ppm; the average particle size of the nano cuprous oxide is 350nm-1μm, the cuprous oxide content is ≥99%, and the specific surface area is ≥8m 2 / g, the surface morphology is spherical.

[0012] The present invention also includes a method for preparing the above-mentioned mildew-proof and mite-removing polyamide 6 masterbatch, comprising the following steps: feeding the polyamide 6 slices through a main feeding position; uniformly mixing the nano-cuprous oxide powder, dispersant powder and antioxidant and then feeding them through a side feeding position; after feeding, melt plasticizing, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying to obtain the mildew-proof and mite-removing polyamide 6 masterbatch.

[0013] Furthermore, the melt plasticization is carried out by a twin-screw extruder, and the temperature zones of each section are: the first section temperature zone is 220-230°C, the second section temperature zone is 230-240°C, the third section temperature zone is 230-240°C, the fourth, fifth and sixth section temperature zones are 200-220°C, the seventh section temperature zone is 190-200°C, the eighth section temperature zone is 180-190°C, the ninth section temperature zone is 180-190°C, and the head temperature zone is 230-240°C.

[0014] Furthermore, the moisture content of the mildew and mite-removing polyamide 6 masterbatch after the blast drying is 500-800 ppm, and the relative viscosity is 1.50-1.80.

[0015] The present invention also includes the use of any of the above-mentioned anti-mildew and anti-mite polyamide 6 masterbatches or any of the above-mentioned preparation methods in the preparation of anti-mildew and anti-mite nylon 6 fully drawn yarn.

[0016] Furthermore, the method for preparing mildew-proof and mite-proof nylon 6 fully drawn yarn as described above comprises the following steps: 90-99 parts of nylon 6 chips and 1-10 parts of mildew-proof and mite-proof polyamide 6 masterbatch are respectively introduced into a screw extruder from a chip storage tank and a masterbatch batching machine for melting to obtain a melt, the temperatures of the first, second, third, fourth and fifth zones of the screw extruder are 250-275°C, and the temperature of the biphenyl furnace is 260-270°C; the melt is divided, twisted 90 degrees and merged by a torsional lamination device, and this process is repeated at least three times; the melt after lamination and compounding is sent to a spinning manifold, metered by a metering pump in the spinning manifold and then enters a spinning assembly, the melt filtered by the filter material of the spinning assembly passes through the spinneret hole of the spinneret, and a single filament stream is formed from the spinneret hole; the single filament is cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare a mildew-proof and mite-proof nylon 6 fully drawn yarn (FDY).

[0017] Furthermore, the number of stackers in the torsional stacking device is 4-8.

[0018] Cuprous oxide undergoes an oxidation reaction in a high-temperature environment to produce cupric oxide. In the present invention, hindered phenolic antioxidants and phosphite antioxidants are added to the masterbatch formula. The hindered antioxidant can interrupt the oxidation reaction chain by capturing free radicals, and the phosphite antioxidant can decompose peroxides, reducing the generation of free radicals and effectively reducing the reaction between cuprous oxide and polyamide 6. As a result, the prepared nylon 6 has a mite repellency rate of over 80% and a level 0 mildew resistance. At the same time, a twisting and laminating device is added to the melt spinning system to construct an ordered structure of cuprous oxide in the nylon 6 slice, effectively improving the dispersibility of cuprous oxide in the nylon 6 slice and improving the performance of the fiber. DETAILED DESCRIPTION

[0019] The technical solutions of the present invention are further described below in conjunction with specific examples. It should be understood that the following examples are merely exemplary illustrations and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope that the present invention is intended to protect.

[0020] In the following embodiments and comparative examples, the temperatures of each section of melt plasticization are controlled as follows: 225°C in the first section, 235°C in the second section, 235°C in the third section, 215°C in the fourth section, 205°C in the fifth section, 200°C in the sixth section, 195°C in the seventh section, 185°C in the eighth section, 180°C in the ninth section, and 235°C in the die head section.

[0021] In the following examples and comparative examples, the temperatures of each zone of the screw extruder were controlled as follows: the temperatures of zone 1, zone 2, zone 3, zone 4, and zone 5 were 252, 266, 264, 266, and 270, respectively, and the biphenyl furnace temperature was 268°C.

[0022] Example 1

[0023] The mildew-proof and mite-proof polyamide 6 masterbatch 1 was prepared according to the following steps: 83.2 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder, 1.5 parts of stearic acid powder, 0.15 parts of antioxidant 1098 and 0.15 parts of antioxidant 168 were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, the mildew-proof and mite-proof polyamide 6 masterbatch 1 was prepared.

[0024] The fully stretched yarn 1 is prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of mildew and mite-proof polyamide 6 masterbatch 1 are respectively introduced into a screw extruder from a chip storage tank and a masterbatch batching machine for melting to obtain a melt; the melt is divided - 90-degree twisted - merged by a torsional stacking device, and this process is repeated 4 times (i.e., four stackings are performed), and the stacked and composited melt is sent to the spinning box, and then metered by a metering pump in the spinning box and enters the spinning assembly. The melt is precisely filtered by the filter sand and metal mesh of the spinning assembly and enters the spinneret of the spinneret, and a single filament stream is formed from the spinneret. The single filament is cooled by side blowing, bundled and oiled, shaped in a hot box, and stretched and wound to prepare sample 1.

[0025] Example 2

[0026] The mildew-proof and mite-proof polyamide 6 masterbatch 2 was prepared according to the following steps: 83.2 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder, 1.5 parts of stearic acid powder, 0.15 parts of antioxidant 1098 and 0.15 parts of antioxidant 626 were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, the mildew-proof and mite-proof polyamide 6 masterbatch 2 was prepared.

[0027] The fully stretched yarn 2 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of mildew and mite-proof polyamide 6 masterbatch 2 were respectively introduced into the screw extruder from the chip storage tank and the masterbatch batching machine for melting to obtain a melt; the melt was divided by a twisting stacking device - twisted 90 degrees - merged, and this process was repeated 4 times to achieve the stacked and composited melt sent to the spinning box, and then metered by a metering pump in the spinning box and entered the spinning assembly. The melt was precisely filtered by the filter sand and metal mesh of the spinning assembly and entered the spinneret of the spinneret, and a single filament stream was formed from the spinneret. The single filament was cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare sample 2.

[0028] Example 3

[0029] The mildew-proof and mite-proof polyamide 6 masterbatch 3 was prepared according to the following steps: 83.2 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder, 1.5 parts of stearic acid powder, 0.15 parts of antioxidant 1010 and 0.15 parts of antioxidant 168 were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, the mildew-proof and mite-proof polyamide 6 masterbatch 3 was prepared.

[0030] The fully stretched yarn 3 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of mildew and mite-proof polyamide 6 masterbatch 3 were respectively introduced into the screw extruder from the chip storage tank and the masterbatch batching machine for melting to obtain a melt; the melt was divided by a twisting stacking device - twisted 90 degrees - merged, and this process was repeated 4 times to achieve the stacked and composited melt sent to the spinning box, and then metered by a metering pump in the spinning box and entered the spinning assembly. The melt was precisely filtered by the filter sand and metal mesh of the spinning assembly and entered the spinneret of the spinneret, and a single filament stream was formed from the spinneret. The single filament was cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare sample 3.

[0031] Example 4

[0032] The mildew-proof and mite-proof polyamide 6 masterbatch 4 was prepared according to the following steps: 83.2 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder, 1.5 parts of stearic acid powder, 0.15 parts of antioxidant 1010 and 0.15 parts of antioxidant 626 were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, the mildew-proof and mite-proof polyamide 6 masterbatch 4 was prepared.

[0033] The fully stretched yarn 4 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of mildew and mite-proof polyamide 6 masterbatch 4 were respectively introduced into the screw extruder from the chip storage tank and the masterbatch batching machine for melting to obtain a melt; the melt was divided by a twisting stacking device - twisted 90 degrees - merged, and this process was repeated 4 times to achieve the stacked and composited melt sent to the spinning box, and then metered by a metering pump in the spinning box and entered the spinning assembly. The melt was precisely filtered by the filter sand and metal mesh of the spinning assembly and entered the spinneret of the spinneret, and a single filament stream was formed from the spinneret. The single filament was cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare sample 4.

[0034] Comparative Example 1

[0035] Comparative masterbatch 1 was prepared according to the following steps: 83.5 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder and 1.5 parts of stearic acid powder were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, comparative masterbatch 1 was prepared.

[0036] Comparative Example 2

[0037] Comparative masterbatch 2 was prepared according to the following steps: 83.2 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder, 1.5 parts of stearic acid powder and 0.30 parts of antioxidant 1098 were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, comparative masterbatch 2 was prepared.

[0038] Comparative Example 3

[0039] Comparative masterbatch 3 was prepared according to the following steps: 83.2 parts of polyamide 6 chips were passed through the main feeding position, 15 parts of nano-cuprous oxide powder, 1.5 parts of stearic acid powder and 0.30 parts of antioxidant 168 were mixed evenly, and then added through the side feeding position. After quantitative feeding, melt plasticization, screw transmission and shearing, water-cooled pelletizing, vibration screening and blast drying, comparative masterbatch 3 was prepared.

[0040] Comparative Example 4

[0041] The comparison fully stretched yarn 1 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of comparison masterbatch 1 were respectively introduced into a screw extruder from a chip storage tank and a masterbatch batching machine for melting to obtain a melt; the melt was divided by a twisting stacking device - twisted 90 degrees - merged, and this process was repeated 4 times to achieve the stacked and composited melt sent to the spinning manifold, and then metered by a metering pump in the spinning manifold and entered the spinning assembly. The melt was precisely filtered by the filter sand and metal mesh of the spinning assembly and entered the spinneret of the spinneret, and a single filament stream was formed from the spinneret. The single filament was cooled by side blowing, bundled and oiled, shaped in a hot box, and drawn and wound to prepare the comparison sample 1.

[0042] Comparative Example 5

[0043] The comparison fully stretched yarn 2 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of mildew and mite-proof polyamide 6 masterbatch 1 were respectively introduced into the screw extruder from the chip storage tank and the masterbatch batching machine for melting to obtain a melt; the melt passed through the spinning box, was metered by the metering pump and entered the spinning assembly, and the melt after precision filtration through the filter sand and metal mesh of the spinning assembly entered the spinneret hole of the spinneret, and a single filament stream was formed from the spinneret hole. The single filament was cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare the comparison sample 2.

[0044] Comparative Example 6

[0045] The comparison fully stretched yarn 3 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of comparison masterbatch 2 were respectively introduced into the screw extruder from the chip storage tank and the masterbatch batching machine for melting to obtain a melt; the melt was divided by a twisting stacking device - twisted 90 degrees - merged, and this process was repeated 4 times to achieve the stacked and composited melt sent to the spinning box, and then metered by a metering pump in the spinning box and entered the spinning assembly. The melt was precisely filtered by the filter sand and metal mesh of the spinning assembly and entered the spinneret of the spinneret, and a single filament stream was formed from the spinneret. The single filament was cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare the comparison sample 3.

[0046] Comparative Example 7

[0047] The comparison fully stretched yarn 4 was prepared according to the following steps: 95.5 parts of nylon 6 chips and 4.5 parts of comparison masterbatch 3 were respectively introduced into a screw extruder from a chip storage tank and a masterbatch batching machine for melting to obtain a melt; the melt was divided by a twisting stacking device - twisted 90 degrees - merged, and this process was repeated 4 times to achieve the stacked and composited melt sent to the spinning box, and then metered by a metering pump in the spinning box and entered the spinning assembly. The melt was precisely filtered by the filter sand and metal mesh of the spinning assembly and entered the spinneret of the spinneret, and a single filament stream was formed from the spinneret. The single filament was cooled by side blowing, bundled and oiled, hot-box shaped, and drawn and wound to prepare the comparison sample 4.

[0048] The performance of samples 1-4 and comparative samples 1-4 prepared above was tested. The results are shown in Table 1 below. The addition of hindered phenol antioxidants and phosphite antioxidants and the use of twisted micro-nano lamination technology greatly improved the mite removal effect.

[0049] Table 1

[0050]

[0051] Although the specific embodiments of the present invention are described above, those skilled in the art should understand that the specific embodiments described are merely illustrative and are not intended to limit the scope of the present invention. Any modifications and changes made by those skilled in the art in accordance with the spirit of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A mildew and mite-proof polyamide 6 masterbatch, characterized by: The mildew-proof and mite-proof polyamide 6 masterbatch includes the following components in parts by weight: 66.7 to 88.9 parts of polyamide 6 chips, 10 to 30 parts of nano-cuprous oxide powder, 1 to 3 parts of dispersant powder, and 0.1 to 0.3 parts of antioxidant; the antioxidant is a mixture of a hindered phenol antioxidant and a phosphite antioxidant.

2. The mildew-proof and mite-proof polyamide 6 masterbatch according to claim 1, characterized in that: The hindered phenol antioxidant is one or both of antioxidant 1098 and antioxidant 1010; the phosphite antioxidant is one or both of antioxidant 626 and antioxidant 168.

3. The mildew-proof and mite-proof polyamide 6 masterbatch according to claim 1, characterized in that: The dispersant is stearic acid.

4. The mildew-proof and mite-proof polyamide 6 masterbatch according to claim 1, characterized in that: The relative viscosity of the polyamide 6 slice is 2.46-2.47, and the water content is 400-600ppm; the average particle size of the nano cuprous oxide is 350nm-1μm, the cuprous oxide content is ≥99%, and the specific surface area is ≥8m 2 / g, the surface morphology is spherical.

5. A method for preparing the mildew-proof and mite-removing polyamide 6 masterbatch according to claim 1, characterized in that: The following steps are involved: The polyamide 6 slices are fed through a main feeding position; the nano cuprous oxide powder, dispersant powder and antioxidant are mixed evenly and then fed through a side feeding position; after feeding, the mixture is melt-plasticized, screw-transmitted and sheared, water-cooled pelletized, vibrated and screened, and air-dried to obtain a mildew-proof and mite-removing polyamide 6 masterbatch.

6. The preparation method according to claim 5, characterized in that: The melt plasticization is carried out by a twin-screw extruder, and the temperature zones of each section are: the first section temperature zone is 220-230°C, the second section temperature zone is 230-240°C, the third section temperature zone is 230-240°C, the fourth, fifth and sixth section temperature zones are 200-220°C, the seventh section temperature zone is 190-200°C, the eighth section temperature zone is 180-190°C, the ninth section temperature zone is 180-190°C, and the head temperature zone is 230-240°C.

7. The preparation method according to claim 5, characterized in that: The moisture content of the mildew-proof and mite-removing polyamide 6 masterbatch after the blast drying is 500-800 ppm, and the relative viscosity is 1.50-1.

80.

8. Use of the mildew-proof and mite-removing polyamide 6 masterbatch according to any one of claims 1 to 4 or the mildew-proof and mite-removing polyamide 6 masterbatch prepared by the preparation method according to any one of claims 5 to 7 in the preparation of mildew-proof and mite-removing nylon 6 fully drawn yarn.

9. A method for preparing mildew-proof and mite-proof nylon 6 fully drawn yarn according to claim 8, characterized in that: The method comprises the following steps: 90-99 parts of nylon 6 chips and 1-10 parts of mildew-proof and mite-proof polyamide 6 masterbatch are respectively introduced into a screw extruder from a chip storage tank and a masterbatch batching machine for melting to obtain a melt; the melt is divided, twisted 90 degrees, and converged by a twisting and laminating device, and this process is repeated at least three times; the melt after lamination and compounding is sent to a spinning manifold, metered by a metering pump in the spinning manifold, and then enters a spinning assembly; the melt filtered by a filter material of the spinning assembly passes through the spinneret holes of a spinneret, and forms a single filament stream from the spinneret holes; the single filament is cooled by side-blowing air, bundled and oiled, shaped in a hot box, and drawn and wound to obtain a mildew-proof and mite-proof nylon 6 fully drawn yarn.

10. The method for preparing mildew-proof and mite-proof nylon 6 fully drawn yarn according to claim 9, characterized in that: The stackers in the twisted stacking device have 4 to 8 sections.

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