Black antibacterial nylon 6 master batch with enhanced blackness and blue phase and preparation method thereof

Abstract

The application discloses a black antibacterial nylon 6 master batch with enhanced blackness and blue phase and a preparation method thereof, and belongs to the technical field of chemical fibers; in the process of preparing the nylon 6 master batch, colored carbon black powder and nano zinc oxide are added, the zinc oxide and the carbon black are premixed and melt-extruded in the preparation process to obtain the uniformly dispersed black master batch; the prepared black antibacterial nylon 6 master batch is introduced with a proper proportion of zinc oxide, the carrier resin is activated, the surface energy of the polyamide is enhanced, the compatibility of the carbon black and the polyamide is improved, the dispersibility of the carbon black in the polyamide is enhanced, the agglomeration of the colored carbon black powder is reduced, the black master batch is endowed with good blackness and gloss, the color phase is blue phase or blue phase, so that the coloring effect of the carbon black master batch is improved, and the free Zn 2+ Still has certain activity after being mixed with the carbon black powder, the prepared black antibacterial nylon 6 master batch can interact with electronegative bacteria to achieve the antibacterial effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of chemical fibers, and particularly relates to a black antibacterial nylon 6 master batch with enhanced blackness and blue phase and a preparation method thereof. BACKGROUND

[0002] Nylon 6 fiber is the second largest chemical fiber in the world, and has excellent performance, mainly characterized by high breaking strength, excellent wear resistance, low weight, good elasticity, etc. In recent years, people's awareness of health and environmental protection has been increasing, and the technology of solution-dyed nylon 6 fiber has also been developed rapidly. By adding color master batch in the melt spinning process, the fiber is given various colors, which saves the printing and dyeing process in the production process of downstream enterprises, and has outstanding environmental friendly characteristics. At present, black nylon 6 filament accounts for about 30% in the market of solution-dyed nylon 6, and is mainly used in swimwear, silk stockings and other close-fitting products, which has broad market prospects.

[0003] In the preparation process of black nylon 6 master batch, due to the small particle size and high specific surface area of carbon black, the compatibility of unmodified carbon black with the master batch polyamide is poor, and agglomeration phenomenon is easy to occur, which leads to the decrease of the uniform dispersion effect of carbon black in the carrier resin, and affects the blackness and color depth effect of the final spinning dyeing. On the other hand, people not only require textiles to have diversification, color beauty and environmental protection, but also increasingly demand functional clothing, among which the antibacterial function has attracted more and more attention from the industry. At present, silver-based antibacterial agents are commonly used in antibacterial fibers, but since nano-silver is easily accumulated in the body after being absorbed by the human body, the safety of the product has been controversial. Therefore, it is of wide practical value and broad application prospect to study a preparation method which can effectively enhance the blackness and blue phase of black nylon 6 master batch, overcome the defects of silver-based antibacterial agents, and endow the black nylon 6 master batch with antibacterial efficiency.

[0004] In patent CN115044071A, an antibacterial black nylon 6 master batch and a preparation method of antibacterial cool black nylon 6 filament are proposed. The invention reduces the addition amount of master batch by preparing high-concentration antibacterial black nylon 6 master batch, effectively improving the spinnability of the fiber. The method used is to replace part of silver with lower-cost TiO2, which cannot completely solve the potential harm of nanosilver being absorbed by the human body, and also has not solved the problem of poor compatibility of carbon black and polyamide, which ultimately affects the blackness and color depth effect of spinning coloring. The invention disclosed in CN111363346A discloses a method and product for preparing an antistatic black master batch using graphene-coated carbon black, comprising: (1) modifying carbon black with a dispersing agent to obtain modified carbon black; mixing graphene oxide with modified carbon black in a solvent, and post-treating to obtain graphene oxide-coated modified carbon black; the dispersing agent is one or more of sodium dodecylbenzenesulfonate, APS, DL-602, and sodium dodecyl sulfate; (2) reducing the obtained graphene oxide-coated modified carbon black with a reducing agent, and post-treating to obtain graphene-coated carbon black; (3) melting and uniformly mixing the obtained graphene-coated carbon black with the base master batch, granulating to obtain an antistatic black master batch. However, the black master batch described in the invention mainly solves the technical problems of how to greatly improve the dispersibility, color uniformity and antistatic property of carbon black in the base material, and does not involve the improvement of antibacterial performance. SUMMARY

[0005] To solve the problems in the prior art, the present application provides a black antibacterial nylon 6 master batch with enhanced blackness and blue phase and a preparation method thereof. In the process of preparing the nylon 6 master batch, colored carbon black powder and nano zinc oxide are added. The pre-mixing and melt extrusion of zinc oxide and carbon black during the preparation process result in a uniformly dispersed black master batch.

[0006] The technical solution of the present application is as follows:

[0007] One of the objects of the present application is to provide a preparation method of a black antibacterial nylon 6 master batch with enhanced blackness and blue phase. The preparation method adds spinning grade nylon 6 chips at the main feeding position of the twin-screw extruder, introduces a proper proportion of pre-mixed carbon black powder, additive powder and zinc oxide at the side feeding position, melts and plasticizes the main feeding and side feeding by controlling the temperature of each section of the twin-screw extruder, and finally obtains a composite black antibacterial nylon 6 master batch through drawing, water tank cooling, particle cutting vibration screening and vacuum constant temperature drying.

[0008] Further, the total mass of the spinning grade nylon 6 chips, zinc oxide, additive powder and carbon black powder is taken as the basis, and the spinning grade nylon 6 chips account for 56%-58%.

[0009] Further, the total mass of the spinning grade nylon 6 chips, zinc oxide, additive powder and carbon black powder is taken as the basis, and the zinc oxide accounts for 9%-11%.

[0010] Further, the carbon black powder accounts for 30-32% in total mass of the spinning grade nylon 6 chip, zinc oxide, auxiliary powder and carbon black powder.

[0011] Further, the auxiliary powder is dispersant JHX-100 / HD65 / 330.

[0012] Further, the auxiliary powder accounts for 1-3% in total mass of the spinning grade nylon 6 chip, zinc oxide, auxiliary powder and carbon black powder.

[0013] Further, the temperature of each section is: the first section is 225 DEG C, the second section is 225 DEG C, the third section is 230 DEG C, the fourth section is 230 DEG C, the fifth section is 230 DEG C, the sixth section is 225-230 DEG C, the seventh section is 210-215 DEG C, the eighth section is 200-205 DEG C, the ninth section is 195-205 DEG C, the tenth section is 185-195 DEG C, the eleventh section is 180-190 DEG C, and the head temperature is 230-240 DEG C.

[0014] Further, the melting temperature is 225 DEG C-230 DEG C.

[0015] Further, the granulating vibration screen is a screen with a pore size of 1-3 mm after granulation in a granulator with a rotation speed of 890 rpm, and the product with a suitable particle size is screened out.

[0016] The second object of the present application is to provide a black antibacterial nylon 6 master batch with enhanced blackness and blue phase.

[0017] Compared with the prior art, the present application has the following advantages:

[0018] 1. In the process of preparing the nylon 6 master batch, the appropriate amount of zinc oxide is introduced to effectively activate the carrier resin, enhance the surface energy of the polyamide, improve the compatibility of the carbon black and the polyamide, effectively reduce the agglomeration phenomenon caused by the poor compatibility of the unmodified carbon black and the master batch polyamide, and endow the black master batch with good blackness and gloss, the color phase is blue or blue phase, the coloring effect of the carbon black master batch is improved, and finally the black master batch with enhanced blackness and blue phase and uniform dispersion is prepared.

[0019] 2. In the preparation method, the zinc oxide can still maintain free Zn 2+The black nylon 6 master batch prepared by the method has certain activity, can enhance blackness and blue phase, has good antibacterial performance, can interact with electronegative bacteria, destroy cell activity, and thus has antibacterial effect, and is particularly excellent in inhibiting white Candida albicans, Escherichia coli and Staphylococcus aureus. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 A color measurement result chart of a corresponding sock belt of a fiber produced by the black antibacterial nylon 6 master batch prepared in examples 1-4 of the present application. DETAILED DESCRIPTION

[0021] The present application is further described in conjunction with preferred embodiments, and the endpoints of the ranges of the disclosed subject matter and any values that are expressed as ranges are intended to include the entire range specifically and not the precise values given, unless the context clearly indicates otherwise; that the endpoints of the ranges of values are not inclusive of the endpoints, that the ranges of values are continuous instead of discrete; that the various stated ranges or particular values are not to be construed as being mutually exclusive; and that specific embodiments disclosed can be combined or sub-combined into additional embodiments.

[0022] The experimental methods in the following examples are conventional methods, and are carried out according to the techniques or conditions described in the literature in the art or according to the product instructions, unless otherwise specified.

[0023] The materials, reagents and the like used in the following examples can be obtained commercially, unless otherwise specified.

[0024] Example 1

[0025] The present embodiment provides a preparation method of a black antibacterial nylon 6 master batch with enhanced blackness and blue phase, which specifically comprises the following steps:

[0026] S1, add spinning grade nylon 6 chips to the main feeding position of the twin-screw extruder, with a proportion of 63%, and add 30% carbon black powder, 3% dispersing agent JHX-100 / HD65 / 330 and 4% zinc oxide powder to the side feeding position;

[0027] S2, melt and plasticize the raw materials by controlling the temperature of each section of the twin-screw extruder, and the temperature of each section of the extruder is as follows: the first section is 225℃, the second section is 225℃, the third section is 230℃, the fourth section is 230℃, the fifth section is 230℃, the sixth section is 225℃, the seventh section is 215℃, the eighth section is 200℃, the ninth section is 205℃, the tenth section is 185℃, the eleventh section is 190℃, and the die temperature is 230℃;

[0028] S3, through the drawing, water tank cooling, cutting vibration screening, vacuum constant temperature drying, composite black antibacterial nylon 6 master batch is prepared.

[0029] Example 2

[0030] The embodiment provides a preparation method of black antibacterial nylon 6 master batch with enhanced blackness and blue phase, and specifically comprises the following steps:

[0031] S1, the spinning grade nylon 6 chip is added to the main feeding position of the double screw extruder, the proportion is 61%, 31% carbon black powder, 2% dispersing agent JHX-100 / HD65 / 330 and 6% zinc oxide powder are added to the side feeding position;

[0032] S2, the raw materials are melted and plasticized by controlling the temperature of each section of the double screw extruder, the first section temperature is 225 DEG C; the second section temperature is 225 DEG C, the third section temperature is 230 DEG C, the fourth section temperature is 230 DEG C, the fifth section temperature is 230 DEG C, the sixth section temperature is 230 DEG C, the seventh section temperature is 210 DEG C, the eighth section temperature is 205 DEG C, the ninth section temperature is 195 DEG C, the tenth section temperature is 195 DEG C, the eleventh section temperature is 180 DEG C, and the die temperature is 240 DEG C;

[0033] S3, through the drawing, water tank cooling, cutting vibration screening, vacuum constant temperature drying, composite black antibacterial nylon 6 master batch is prepared.

[0034] Example 3

[0035] The embodiment provides a preparation method of black antibacterial nylon 6 master batch with enhanced blackness and blue phase, and specifically comprises the following steps:

[0036] S1, the spinning grade nylon 6 chip is added to the main feeding position of the double screw extruder, the proportion is 61%, 31% carbon black powder, 2% dispersing agent JHX-100 / HD65 / 330 and 6% zinc oxide powder are added to the side feeding position;

[0037] S2, the raw materials are melted and plasticized by controlling the temperature of each section of the double screw extruder, the first section temperature is 225 DEG C; the second section temperature is 225 DEG C, the third section temperature is 230 DEG C, the fourth section temperature is 230 DEG C, the fifth section temperature is 230 DEG C, the sixth section temperature is 230 DEG C, the seventh section temperature is 215 DEG C, the eighth section temperature is 200 DEG C, the ninth section temperature is 195 DEG C, the tenth section temperature is 190 DEG C, the eleventh section temperature is 180 DEG C, and the die temperature is 235 DEG C;

[0038] S3, through the drawing, water tank cooling, cutting vibration screening, vacuum constant temperature drying, composite black antibacterial nylon 6 master batch is prepared.

[0039] Example 4

[0040] The embodiment provides a preparation method of black antibacterial nylon 6 master batch with enhanced blackness and blue phase, and specifically comprises the following steps:

[0041] S1, the spinning grade nylon 6 chip is added to the main feeding position of the double screw extruder, and the proportion is 57%, 30% carbon black powder, 3% dispersing agent JHX-100 / HD65 / 330 and 10% zinc oxide powder are added to the side feeding position;

[0042] S2, the raw materials are melted and plasticized by controlling the temperature of each section of the double screw extruder, the first section temperature is 225 DEG C; the second section temperature is 225 DEG C, the third section temperature is 230 DEG C, the fourth section temperature is 230 DEG C, the fifth section temperature is 230 DEG C, the sixth section temperature is 225 DEG C, the seventh section temperature is 210 DEG C, the eighth section temperature is 205 DEG C, the ninth section temperature is 200 DEG C, the tenth section temperature is 195 DEG C, the eleventh section temperature is 185 DEG C, and the die temperature is 230 DEG C;

[0043] S3, the composite black antibacterial nylon 6 master batch is prepared through drawing, water tank cooling, particle cutting, vibration screening and vacuum constant temperature drying.

[0044] Comparative example 1

[0045] The comparative example provides a preparation method of nylon 6 master batch, and specifically comprises the following steps:

[0046] S1, the spinning grade nylon 6 chip is added to the main feeding position of the double screw extruder, and the proportion is 67%, 30% carbon black powder and 3% dispersing agent JHX-100 / HD65 / 330 are added to the side feeding position;

[0047] S2, the raw materials are melted and plasticized by controlling the temperature of each section of the double screw extruder, the first section temperature is 225 DEG C; the second section temperature is 225 DEG C, the third section temperature is 230 DEG C, the fourth section temperature is 230 DEG C, the fifth section temperature is 230 DEG C, the sixth section temperature is 225 DEG C, the seventh section temperature is 215 DEG C, the eighth section temperature is 200 DEG C, the ninth section temperature is 205 DEG C, the tenth section temperature is 185 DEG C, the eleventh section temperature is 190 DEG C, and the die temperature is 230 DEG C;

[0048] S3, the composite black antibacterial nylon 6 master batch is prepared through drawing, water tank cooling, particle cutting, vibration screening and vacuum constant temperature drying.

[0049] Performance test

[0050] 1, the breaking strength, elongation at break and antibacterial performance of the fibers produced by the nylon 6 master batch prepared in the above examples 1-4 and comparative example 1 are detected, and the blackness is compared, and the results are shown in Table 1.

[0051] Table 1 Colorimetric results of corresponding sock bands of fibers produced in Examples 1-4 and Comparative Example 1

[0052]

[0053] From the hue in the comparison of the Lab test data of the sock bands, it can be seen that the hue of Examples 1-3 is bluer than that of Comparative Example 1, and the hue of Example 4 with the highest ZnO content in the yarn is redder than that of Comparative Example 1. In terms of blackness, with the same carbon black content in the yarn, the blackness of Examples 1-4 with the addition of ZnO is deeper than that of Comparative Example 1 without the addition of ZnO, and with the continuous increase of the amount of ZnO added, the blackness of the sock bands is deeper, but the degree of deepening gradually decreases, which can prove that the addition of ZnO can effectively deepen the blackness of the nylon 6 filaments.

[0054] 2, The fibers produced from the nylon 6 master batches prepared in Examples 1-4 and Comparative Example 1 were subjected to antibacterial performance testing according to "Evaluation of Antibacterial Properties of Textiles - Shake Flask Method (GB / T 20944.3-2008)", and the results are shown in Table 2.

[0055] Table 2 Antibacterial performance testing results of fibers produced in Examples 1-4 and Comparative Example 1

[0056]

[0057] The results show that the Candida albicans inhibition rate of the fibers produced in Comparative Example 1 only reaches the basic value (70%) of the national standard, and the fibers produced in Examples 1-4 have more excellent Candida albicans antibacterial performance with the increase of the ZnO content in the yarn, which is better than that of Comparative Example 1 (ZnO content 0‰), effectively improving the Candida albicans antibacterial effect; in addition, the Escherichia coli inhibition rate of the fibers produced in Examples 1-4 is improved by 6% compared with that of Comparative Example 1, and the Staphylococcus aureus inhibition rate of Examples 1-4 is basically the same as that of Comparative Example 1.

[0058] In summary, in terms of blackness, the blackness of Examples 3 and 4 is equivalent; in terms of antibacterial performance, the Candida albicans, Escherichia coli and Staphylococcus aureus inhibition rates of Examples 3 and 4 are basically the same; in terms of hue, the hue of Example 3 is obviously bluer than that of Example 4. Therefore, in the method for preparing black antibacterial nylon 6 fibers with enhanced blackness and blue hue in the present application, Example 3 can be preferably selected.

[0059] The above-described embodiments are merely examples of the present application, and do not limit the patent scope of the present application, and any equivalent structure or equivalent process conversion using the content of the present application specification, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A process for the preparation of black antibacterial nylon 6 masterbatch with enhanced blackness and blue phase, characterized by, The preparation method adds spinning grade nylon 6 chips at a main feeding position of a double screw extruder, introduces a proper proportion of premixed carbon black powder, additive powder and zinc oxide at a side feeding position, melts and plasticizes the main feeding and the side feeding by controlling the temperature of each section of the double screw extruder, and obtains the composite black antibacterial nylon 6 master batch through drawing, water tank cooling, granulation vibration screening and vacuum constant temperature drying; The spinning grade nylon 6 chips account for 56%-58% based on the total mass of the spinning grade nylon 6 chips, zinc oxide, additive powder and carbon black powder; The zinc oxide accounts for 9%-11% based on the total mass of the spinning grade nylon 6 chips, zinc oxide, additive powder and carbon black powder; The carbon black powder accounts for 30-32% based on the total mass of the spinning grade nylon 6 chips, zinc oxide, additive powder and carbon black powder.

2. The method for preparing a black antibacterial nylon 6 masterbatch with enhanced blackness and blue hue as described in claim 1, characterized in that, The additive powder is dispersant JHX-100 / HD65 / 330.

3. The method for preparing a black antibacterial nylon 6 masterbatch with enhanced blackness and blue hue as described in claim 1, characterized in that, The additive powder accounts for 1-3% based on the total mass of the spinning grade nylon 6 chips, zinc oxide, additive powder and carbon black powder.

4. The method for preparing a black antibacterial nylon 6 masterbatch with enhanced blackness and blue hue as described in claim 1, characterized in that, The temperature of each section is respectively: the first section temperature is 225℃; the second section temperature is 225℃, the third section temperature is 230℃, the fourth section temperature is 230℃, the fifth section temperature is 230℃, the sixth section temperature is 225-230℃, the seventh section temperature is 210-215℃, the eighth section temperature is 200-205℃, the ninth section temperature is 195-205℃, the tenth section temperature is 185-195℃, the eleventh section temperature is 180-190℃, and the head temperature is 230-240℃.

5. The method for preparing a black antibacterial nylon 6 masterbatch with enhanced blackness and blue hue as described in claim 1, characterized in that, The melting temperature is 225℃-230℃.

6. The method for preparing a black antibacterial nylon 6 masterbatch with enhanced blackness and blue hue as described in claim 1, characterized in that, The granulation vibration screening is carried out by a vibrating screen with a screen mesh with a pore size of 1-3mm after granulation by a granulator with a rotating speed of 890rpm to screen the finished product with a proper particle size.

7. A black antibacterial nylon 6 master batch with enhanced blackness and blue phase prepared by the method of any one of claims 1-6.

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