Antibacterial skin-friendly functional master batch and preparation method thereof

Abstract

The invention relates to the field of functional master batch preparation, and particularly discloses an antibacterial skin-friendly functional master batch and a preparation method thereof.The functional master batch is prepared from, by weight, 20-30 parts of polyester, 2-5 parts of modified far-infrared ceramic powder, 4-8 parts of tourmaline, 1-3 parts of modified nano-silver and 0.5-2 parts of other auxiliaries. The functional master batch disclosed by the invention has a certain health-care effect and good antibacterial performance, and is suitable for manufacturing various skin-friendly articles.

Description

Technical Field

[0001] The invention relates to the field of functional masterbatch preparation, and specifically discloses an antibacterial and skin-friendly functional masterbatch and a preparation method thereof. Background Art

[0002] Functional masterbatch is an aggregate obtained by uniformly loading an extraordinary amount of functional powder into a resin. Functional masterbatch is usually prepared by melt blending. The carrier resin and functional powder are uniformly mixed at high temperature by relying on the strong shear force provided by the mixing equipment, so that the functional powder is stably and uniformly dispersed in the carrier resin with a certain particle size. Since the dispersion of functional powder in the high-viscosity carrier resin melt in the melt blending method mainly relies on the mechanical shear force provided by the mixing equipment, it is difficult to achieve highly uniform dispersion of functional powder in the carrier resin melt with a smaller scale, resulting in the functional masterbatch prepared by melt blending being difficult to apply to the preparation of fine or ultrafine functional polyester fibers with high functional powder content.

[0003] In order to increase the functionality of the masterbatch, some functional additives such as antibacterial agents are often further mixed with the functional masterbatch for preparation. The invention patent with publication number CN105462044A discloses an antibacterial functional masterbatch and its preparation method and application, which includes the following raw materials by weight: 10 to 20 parts of silver ion antibacterial agent, 70 to 90 parts of thermoplastic resin, 0.1 to 1 part of dispersant, and 1 to 5 parts of colorant; the antibacterial functional masterbatch of the present invention, the addition of silver ion antibacterial agent makes the functional masterbatch have good antibacterial function, and the antibacterial function is sustained and stable. The antibacterial functional masterbatch of the invention is applied to the preparation of activated carbon rods in water purification equipment, so that the activated carbon rods have good antibacterial ability and have no adverse effects on water quality. In addition, the antibacterial functional masterbatch of the invention has a wide range of uses and can be applied to food, water purification, clothing, packaging and other fields that require antibacterial.

[0004] However, the simple mixing and adding of additives such as antibacterial agents into the antibacterial functional masterbatch disclosed in the invention is likely to cause degradation of the functional masterbatch, and may also be affected by the dispersion effect, resulting in unstable antibacterial efficiency. Summary of the invention

[0005] In view of the defects of the prior art, the present invention discloses an antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The functional masterbatch disclosed in the present invention has certain health benefits and good antibacterial properties, and is suitable for the manufacture and use of various skin-friendly products.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] On one hand, the present invention provides an antibacterial and skin-friendly functional masterbatch, which comprises the following raw materials in parts by weight: 20 to 30 parts of polyester, 2 to 5 parts of modified far-infrared ceramic powder, 4 to 8 parts of tourmaline, 1 to 3 parts of modified nano silver and 0.5 to 2 parts of other additives.

[0008] In some embodiments of the present invention, the polyester is polyethylene terephthalate.

[0009] Preferably, the intrinsic viscosity of the polyethylene terephthalate is 0.62-0.70 dL / g at 25°C.

[0010] More preferably, the intrinsic viscosity of the polyethylene terephthalate is 0.66 dL / g at 25°C.

[0011] In some embodiments of the present invention, the particle size of the modified far-infrared ceramic powder is 40 to 60 nm.

[0012] Preferably, the particle size of the modified far-infrared ceramic powder is 50 nm.

[0013] In some embodiments of the present invention, the preparation steps of the modified far-infrared ceramic powder are as follows:

[0014] The far-infrared ceramic powder is added to an organic solvent, ultrasonically dispersed for 1 to 2 hours, then phosphate is added, the temperature is raised to 70 to 100° C., stirred for 1 to 2 hours, sulfonate is added, stirred for 1 to 2 hours, the temperature is lowered to 70 to 80° C., and a silane coupling agent is added, stirred for 10 to 30 minutes, and the modified far-infrared ceramic powder is obtained by suction filtration, washing, drying and grinding.

[0015] Preferably, the far-infrared ceramic powder comprises the following raw materials based on 100% by mass: 15-30% manganese dioxide, 8-10% titanium dioxide, 14-20% silicon dioxide, and the balance is zirconium dioxide.

[0016] Further preferably, the far-infrared ceramic powder comprises the following raw materials based on 100% by mass: 25% manganese dioxide, 9% titanium dioxide, 16% silicon dioxide and 50% zirconium dioxide.

[0017] In some embodiments of the present invention, the mass ratio of the far-infrared ceramic powder, sulfonate and silane coupling agent is 10:(0.5-0.9):(0.05-0.1).

[0018] Preferably, the mass ratio of the far-infrared ceramic powder, sulfonate and silane coupling agent is 10:0.7:0.07.

[0019] Preferably, the sulfonate is trimethylsilyl methanesulfonate.

[0020] Preferably, the silane coupling agent is KH550.

[0021] Within the infrared wavelength range, far-infrared materials can produce a strong resonance effect on human cells. They are a widely available functional material, and far-infrared ceramic powder is the most common far-infrared material. They can penetrate into the subcutaneous tissue of the human body, promote blood circulation, improve the circulatory system, enhance metabolism, and improve immune function. Far-infrared rays have anti-inflammatory functions, can promote the absorption of inflammation, and have an analgesic effect.

[0022] The invention modifies the far-infrared ceramic powder raw material by adding trimethylsilyl methanesulfonate and silane coupling agent KH550, thereby increasing the specific surface area of ​​the far-infrared ceramic powder, and further radiating more far-infrared rays; when the far-infrared ceramic powder is added into the antibacterial skin-friendly functional masterbatch system, under the compatibility promoting effect of the silane coupling agent KH550, the polyester adheres to the surface of the modified far-infrared ceramic powder, and at this time, it may be due to the occurrence of heterogeneous nucleation, thereby promoting the appearance of more crystal regions in the system, improving the crystallinity, ensuring the comprehensive mechanical properties of the antibacterial skin-friendly functional masterbatch of the invention, and greatly improving the stability thereof.

[0023] In some embodiments of the present invention, the preparation steps of the modified nanosilver are as follows:

[0024] 3-Mercaptopropyltrimethoxysilane and anhydrous ethanol are mixed, hexadecyltrimethylammonium chloride is added, and the mixture is ultrasonically dispersed for 1 to 5 hours. Nanosilver is added and the mixture is ultrasonically dispersed for 1 to 3 hours. The mixture is centrifuged, washed, dried and ground to obtain the modified nanosilver.

[0025] In some embodiments of the present invention, the mass ratio of the 3-mercaptopropyltrimethoxysilane to the nanosilver is (0.05-0.1):1.

[0026] Preferably, the mass ratio of the 3-mercaptopropyltrimethoxysilane to the nanosilver is 0.07:1.

[0027] In some embodiments of the present invention, the particle size of the modified nanosilver is 10 to 20 nm.

[0028] Preferably, the particle size of the modified nanosilver is 15 nm.

[0029] In the prior art, nanosilver is one of the most commonly used antibacterial functional additives. However, when preparing polyester masterbatch, due to the high processing temperature during its application, simply melt-blending nanosilver with other components to prepare polyester functional masterbatch will not only cause degradation of polyester and loss of mechanical properties, but may also be affected by poor dispersion of nanosilver, resulting in low antibacterial efficiency when the polyester functional masterbatch is used.

[0030] In the present invention, the applicant introduces 3-mercaptopropyltrimethoxysilane to modify the nanosilver, and then blends it with other components to obtain an antibacterial and skin-friendly functional masterbatch with a smooth surface and no degradation, and no loss of mechanical properties. The possible reason is that the introduction of 3-mercaptopropyltrimethoxysilane increases the affinity and compatibility of nanosilver, avoiding its agglomeration in the system, and the presence of the polar group mercapto also increases its interaction with polyester, maintaining the viscosity of the system, while avoiding the degradation of polyester and the loss of performance.

[0031] In some embodiments of the present invention, the other auxiliary agent is a dispersant and / or a lubricant.

[0032] Preferably, the other auxiliary agent is a dispersant.

[0033] Further preferably, the dispersant is fatty alcohol polyoxyethylene ether sulfate.

[0034] On the other hand, the present invention also provides a method for preparing an antibacterial and skin-friendly functional masterbatch, comprising the following steps: mixing polyester, modified far-infrared ceramic powder, tourmaline, modified nano silver and other additives, and granulating them by melt extrusion at 210-230° C. through a twin-screw extruder to obtain the antibacterial and skin-friendly functional masterbatch.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The functional masterbatch obtained by adding modified far-infrared ceramic powder, modified nanosilver and other specific components in the present invention has certain health benefits and good antibacterial properties, and is suitable for the manufacture and use of various skin-friendly products.

[0037] (2) The present invention modifies the specific far-infrared ceramic powder raw material by adding trimethylsilyl methanesulfonate and silane coupling agent KH550, thereby increasing the specific surface area of ​​the far-infrared ceramic powder, thereby radiating more far-infrared rays; at the same time, the comprehensive mechanical properties of the functional masterbatch are guaranteed, and its stability is greatly improved.

[0038] (3) The present invention introduces 3-mercaptopropyltrimethoxysilane to modify the nanosilver, thereby increasing the affinity and compatibility of the nanosilver and avoiding its agglomeration in the system; the presence of the polar group mercapto also increases the interaction between the modified nanosilver and the polyester, maintains the viscosity of the system, and avoids the degradation of the polyester and the loss of its performance. DETAILED DESCRIPTION

[0039] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0040] Unless otherwise specified, the reagents used below can be easily obtained from commercial companies.

[0041] Unless otherwise specified, the post-processing steps such as "ultrasonic dispersion", "filtration", "washing", "drying", "grinding" and "centrifugation" used below are routine operations of those skilled in the art and can be selected according to actual operations.

[0042] Unless otherwise specified, the particle size of zirconium dioxide-1 used below is 50 nm, and the particle size of zirconium dioxide-2 is 70 nm, and they can be purchased from any manufacturer.

[0043] Preparation Example 1

[0044] The preparation steps of modified far-infrared ceramic powder are as follows:

[0045] 40 g of far-infrared ceramic powder (100% by mass, containing 25% manganese dioxide, 9% titanium dioxide, 16% silicon dioxide and 50% zirconium dioxide-1) was added to 160 mL of xylene, and ultrasonically dispersed for 1.5 hours. Then, 2 g of NP-10 phosphate was added, the temperature was raised to 85°C, stirred for 1.5 hours, 2.8 g of trimethylsilyl methanesulfonate was added, stirred for 1.5 hours, the temperature was lowered to 75°C, 0.28 g of KH550 was added, stirred for 20 minutes, and the modified far-infrared ceramic powder was obtained after filtration, washing, drying and grinding.

[0046] Preparation Example 2

[0047] The preparation steps of the modified far-infrared ceramic powder are the same as those of Preparation Example 1, except that the amount of trimethylsilyl methanesulfonate added is 4 g.

[0048] Preparation Example 3

[0049] The preparation steps of the modified far-infrared ceramic powder are the same as those in Preparation Example 1, except that the amount of KH550 added is 0.48 g.

[0050] Preparation Example 4

[0051] The preparation steps of the modified far-infrared ceramic powder are the same as those of Preparation Example 1, except that zirconium dioxide-2 is used in an equal amount to replace zirconium dioxide-1 in the modified far-infrared ceramic powder.

[0052] Preparation Example 5

[0053] The preparation steps of modified nanosilver are as follows:

[0054] 0.7 g of 3-mercaptopropyltrimethoxysilane and 20 mL of anhydrous ethanol were mixed, 1 g of hexadecyltrimethylammonium chloride was added, and ultrasonic dispersion was performed for 3 h. 10 g of nanosilver was added and ultrasonic dispersion was performed for another 2 h. After centrifugation, washing, drying and grinding, modified nanosilver with a particle size of 15 nm was obtained.

[0055] Preparation Example 6

[0056] The preparation steps of modified nanosilver are the same as those in Preparation Example 5, except that the amount of 3-mercaptopropyltrimethoxysilane added is 1.2 g.

[0057] Preparation Example 7

[0058] The preparation steps of modified nano silver are the same as those of Preparation Example 5, except that the particle size of the modified nano silver is 30 nm.

[0059] Unless otherwise specified, the polyesters used in the following examples and comparative examples are all polyethylene terephthalate (with a characteristic viscosity of 0.66 dL / g at 25°C), the dispersants used are all sodium fatty alcohol polyoxyethylene ether sulfate (70 wt% AES, purchased from Jinan Daorong Chemical Co., Ltd.), and the tourmalines used are all tourmaline powder (with a particle size of 10 μm).

[0060] Example 1

[0061] An antibacterial and skin-friendly functional masterbatch comprises the following raw materials in parts by weight: 25 parts of polyester, 3.5 parts of modified far-infrared ceramic powder, 6 parts of tourmaline, 2 parts of modified nano silver and 1.3 parts of a dispersant.

[0062] The preparation method of the antibacterial and skin-friendly functional masterbatch of the present embodiment comprises the following steps: mixing polyester, modified far-infrared ceramic powder, tourmaline, modified nano silver and a dispersant, and granulating the mixture by melt extrusion at 220° C. through a twin-screw extruder to obtain the antibacterial and skin-friendly functional masterbatch.

[0063] The modified far-infrared ceramic powder used in this embodiment is obtained from Preparation Example 1, and the modified nano silver used is obtained from Preparation Example 5.

[0064] Example 2

[0065] An antibacterial and skin-friendly functional masterbatch comprises the following raw materials in parts by weight: 30 parts of polyester, 5 parts of modified far-infrared ceramic powder, 8 parts of tourmaline, 3 parts of modified nano silver and 2 parts of dispersant.

[0066] The preparation method of the antibacterial and skin-friendly functional masterbatch of this embodiment comprises the following steps: mixing polyester, modified far-infrared ceramic powder, tourmaline, modified nano silver and a dispersant, and granulating them by melt extrusion at 230° C. through a twin-screw extruder to obtain the antibacterial and skin-friendly functional masterbatch.

[0067] The modified far-infrared ceramic powder used in this embodiment is obtained from Preparation Example 1, and the modified nano silver used is obtained from Preparation Example 5.

[0068] Example 3

[0069] An antibacterial and skin-friendly functional masterbatch comprises the following raw materials in parts by weight: 20 parts of polyester, 2 parts of modified far-infrared ceramic powder, 4 parts of tourmaline, 1 part of modified nano silver and 0.5 part of a dispersant.

[0070] The preparation method of the antibacterial and skin-friendly functional masterbatch of the present embodiment comprises the following steps: mixing polyester, modified far-infrared ceramic powder, tourmaline, modified nano silver and a dispersant, and granulating the mixture by melt extrusion at 210° C. through a twin-screw extruder to obtain the antibacterial and skin-friendly functional masterbatch.

[0071] The modified far-infrared ceramic powder used in this embodiment is obtained from Preparation Example 1, and the modified nano silver used is obtained from Preparation Example 5.

[0072] Example 4

[0073] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the modified far-infrared ceramic powder used is obtained from Preparation Example 2.

[0074] Example 5

[0075] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the modified far-infrared ceramic powder used is obtained from Preparation Example 3.

[0076] Example 6

[0077] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the modified far-infrared ceramic powder used is obtained from Preparation Example 4.

[0078] Example 7

[0079] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified nanosilver used is obtained from Preparation Example 6.

[0080] Example 8

[0081] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the modified nanosilver used is obtained from Preparation Example 7.

[0082] Comparative Example 1

[0083] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified far-infrared ceramic powder is replaced by an equal amount of far-infrared ceramic powder (100% by mass, containing 25% manganese dioxide, 9% titanium dioxide, 16% silicon dioxide and 50% zirconium dioxide-1).

[0084] Comparative Example 2

[0085] An antibacterial and skin-friendly functional masterbatch and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of nanosilver is used to replace the modified nanosilver.

[0086] Performance Test:

[0087] The functional masterbatch prepared in the above Examples 1-8 and Comparative Examples 1-2 was subjected to the following performance tests. The specific test results are shown in Table 1:

[0088] (1) Far infrared emissivity: far infrared test is performed using an infrared spectrometer;

[0089] (2) Antibacterial performance: Referring to the antibacterial performance test related content disclosed in the invention patent CN117646289B, each functional masterbatch was made into fiber (containing 2wt% functional masterbatch) and then woven into a fabric sample. The antibacterial rate was calculated by comparing the number of Escherichia coli colonies cultured in agar medium for 16 h using the oscillation method with reference to GB / T20944.3-2018.

[0090]

[0091] As can be seen from Table 1, the functional masterbatch disclosed in Examples 1-3 of the present invention has a high far-infrared emissivity, indicating that it has a high health-care effect and good antibacterial performance.

[0092] By comparing Examples 4 and 5 with Example 1, it can be seen that when the addition amounts of trimethylsilyl methanesulfonate and KH550 are changed respectively when preparing the modified far-infrared ceramic powder, the far-infrared emissivity of the functional masterbatch will decrease. The former may be due to the excessively high crystallinity, which affects the stability of the functional masterbatch and causes the antibacterial property to decrease. In Example 6, the particle size of the modified far-infrared ceramic powder is changed, and its far-infrared emissivity also decreases.

[0093] By comparing Example 7 with Example 1, it can be seen that when the amount of 3-mercaptopropyltrimethoxysilane added is changed during the preparation of modified nano-silver, the affinity and compatibility of the modified nano-silver will decrease, thereby causing the antibacterial performance of the functional masterbatch to deteriorate;

[0094] By comparing Example 8 with Example 1, it can be seen that when the particle size of the modified nanosilver is changed, the modification effect is reduced, the inhibition effect on the agglomeration phenomenon is weakened, and finally the antibacterial performance of the functional masterbatch is deteriorated;

[0095] By comparing Comparative Example 1 with Example 1, it can be seen that when the modified far-infrared ceramic powder is replaced by an equal amount of far-infrared ceramic powder, the far-infrared emissivity of the functional masterbatch is reduced;

[0096] From the comparison between Comparative Example 2 and Example 1, it can be seen that when the modified nanosilver is replaced by an equal amount of nanosilver, the antibacterial performance of the functional masterbatch will decrease, and its far-infrared emissivity will also decrease to a certain extent due to the uneven dispersion of the system.

[0097] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. An antibacterial and skin-friendly functional masterbatch, characterized in that: The functional masterbatch comprises the following raw materials in parts by weight: 20-30 parts of polyester, 2-5 parts of modified far-infrared ceramic powder, 4-8 parts of tourmaline, 1-3 parts of modified nano silver and 0.5-2 parts of other additives.

2. The antibacterial and skin-friendly functional masterbatch according to claim 1, characterized in that: The polyester is polyethylene terephthalate.

3. The antibacterial and skin-friendly functional masterbatch according to claim 1, characterized in that: The particle size of the modified far-infrared ceramic powder is 40-60 nm.

4. The antibacterial and skin-friendly functional masterbatch according to claim 1, characterized in that: The preparation steps of the modified far-infrared ceramic powder are as follows: The far-infrared ceramic powder is added to an organic solvent, ultrasonically dispersed for 1 to 2 hours, then phosphate is added, the temperature is raised to 70 to 100° C., stirred for 1 to 2 hours, sulfonate is added, stirred for 1 to 2 hours, the temperature is lowered to 70 to 80° C., and a silane coupling agent is added, stirred for 10 to 30 minutes, and the modified far-infrared ceramic powder is obtained by suction filtration, washing, drying and grinding.

5. The antibacterial and skin-friendly functional masterbatch according to claim 4, characterized in that: The mass ratio of the far-infrared ceramic powder, sulfonate and silane coupling agent is 10:(0.5-0.9):(0.05-0.1).

6. The antibacterial and skin-friendly functional masterbatch according to claim 1, characterized in that: The preparation steps of the modified nano silver are as follows: 3-Mercaptopropyltrimethoxysilane and anhydrous ethanol are mixed, hexadecyltrimethylammonium chloride is added, and the mixture is ultrasonically dispersed for 1 to 5 hours. Nanosilver is added and the mixture is ultrasonically dispersed for 1 to 3 hours. The mixture is centrifuged, washed, dried and ground to obtain the modified nanosilver.

7. The antibacterial and skin-friendly functional masterbatch according to claim 6, characterized in that: The mass ratio of the 3-mercaptopropyltrimethoxysilane to nano-silver is (0.05-0.1):

1.

8. The antibacterial and skin-friendly functional masterbatch according to claim 1, characterized in that: The particle size of the modified nano silver is 10 to 20 nm.

9. The antibacterial and skin-friendly functional masterbatch according to claim 1, characterized in that: The other auxiliary agents are dispersants and / or lubricants.

10. A method for preparing the antibacterial skin-friendly functional masterbatch according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing polyester, modified far-infrared ceramic powder, tourmaline, modified nano silver and other additives, and performing melt extrusion granulation at 210-230° C. through a twin-screw extruder to obtain the antibacterial and skin-friendly functional masterbatch.

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