CN116496617B

CN116496617B - Antibacterial nylon composition and preparation method and application thereof

Info

Publication number: CN116496617B
Application number: CN202310460488.5A
Authority: CN
Inventors: 许建稳; 张永; 叶士兵; 刘纪庆; 王飞; 肖军华; 安朋; 邱志强; 付大炯; 林洁龙
Original assignee: Shanghai Kingfa Science and Technology Co Ltd; Jiangsu Kingfa New Material Co Ltd
Current assignee: Shanghai Kingfa Science and Technology Co Ltd; Jiangsu Kingfa New Material Co Ltd
Priority date: 2023-04-26
Filing date: 2023-04-26
Publication date: 2024-03-26
Anticipated expiration: 2043-04-26
Also published as: CN116496617A

Abstract

The invention provides an antibacterial nylon composition, and a preparation method and application thereof. The antibacterial nylon composition comprises the following components in parts by weight: 60 to 70 parts of aliphatic polyamide, 20 to 35 parts of high-strength glass fiber, 1 to 3 parts of antibacterial agent, 0.5 to 3 parts of odor adsorbent and 0.5 to 2 parts of auxiliary agent; wherein the antibacterial agent is selected from one or more of zinc pyrithione and copper pyrithione. The antibacterial nylon composition provided by the invention has the characteristics of excellent mechanical property, excellent antibacterial property and low odor.

Description

Antibacterial nylon composition and preparation method and application thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an antibacterial nylon composition and a preparation method and application thereof.

Background

The war between human beings and harmful microorganisms has been extended for thousands of years, along with the continuous improvement of the living standard of human beings, people increasingly pay attention to the durable sterility of clothing and eating operations, household appliances, work and home environments, and in the automobile industry, the requirements of people on safety and comfort are higher and higher, the requirement of the antibacterial property of automobile interior materials is also growing, and the inhibition and even the elimination of harmful bacteria have become an important subject related to human health.

Nylon, also known as Polyamide (PA), is a generic term for thermoplastic resins containing recurring amide groups (-NHCO-) in the molecular backbone, and includes aliphatic nylon, aromatic nylon, semi-aromatic nylon, and specialty nylon new varieties. The nylon material has excellent mechanical properties, and has huge application in the automobile industry, but the nylon material does not have antibacterial properties, so that the nylon material needs to be subjected to antibacterial modification, and meanwhile, the requirements of the nylon material on low odor and high strength are met.

Most of the traditional antibacterial nylon materials are applied to the textile field, the antibacterial nylon materials which can be applied to the automobile industry are fewer, and the requirements of the existing automobile main machine factory are combined, so that the nylon materials meeting the requirements of high strength, low odor and antibacterial property are fewer.

Disclosure of Invention

Based on the above, the invention provides an antibacterial nylon composition which has the characteristics of excellent mechanical property, excellent antibacterial property and low odor.

The invention is realized by the following technical scheme.

The antibacterial nylon composition comprises the following components in parts by weight:

wherein the antibacterial agent is selected from one or more of zinc pyrithione and copper pyrithione.

In one embodiment, the antimicrobial nylon composition further comprises 0.1 to 1.5 parts zinc oxide.

In one embodiment, the antimicrobial agent is a mixture of zinc pyrithione and copper pyrithione;

preferably, the antibacterial agent is a mixture of zinc pyrithione and copper pyrithione in a mass ratio of 1 (0.5-1.5).

In one embodiment, the aliphatic polyamide has a relative viscosity of 2.5 to 3;

preferably, the relative viscosity of the aliphatic polyamide is 2.7 to 2.9.

In one embodiment, the aliphatic polyamide is selected from one or more of polycaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide and polyhexamethylene sebacamide.

In one embodiment, the high strength glass fibers have an average diameter of 6 μm to 15 μm.

In one embodiment, the high strength glass fibers have an average diameter of 8 μm to 10 μm.

In one embodiment, the high-strength glass fiber is subjected to surface treatment by a silane coupling agent; the mass of the silane coupling agent is 0.4-0.6% of the mass of the high-strength glass fiber.

In one embodiment, the odor adsorbent is a molecular sieve adsorbent.

In one embodiment, the adjuvant includes one or more of 0.1 to 0.5 part antioxidant, 0.3 to 1 part lubricant, and 0.1 to 0.5 part nucleating agent.

In one embodiment, the antioxidant is selected from one or more of hindered phenolic antioxidants and phosphite antioxidants.

In one embodiment, the lubricant is selected from one or more of esters, montanates, ethylene bis-stearamide, and polyethylene wax.

In one embodiment, the nucleating agent is selected from one or more of nanosilica and nanosilica composites.

The invention also provides a preparation method of the antibacterial nylon composition, which comprises the following steps:

mixing the aliphatic polyamide, the odor adsorbent, the antibacterial agent, the antioxidant, the lubricant and the nucleating agent, plasticizing, then mixing with the high-strength glass fiber, and granulating.

The invention also provides application of the antibacterial nylon composition, and the technical scheme is as follows:

an automotive interior material comprising the antimicrobial nylon composition described above.

The antibacterial nylon composition has at least the following beneficial effects:

according to the invention, one or a mixture of zinc pyrithione and copper pyrithione is selected as an antibacterial agent, and the antibacterial agent is compounded with the aliphatic polyamide, so that the antibacterial performance of the nylon material can be effectively improved. The antibacterial agent can also be synergistic with high-strength glass fibers to further improve the mechanical properties of nylon materials, including strength and toughness. In addition, the invention also adds an odor adsorbent into the composition, thus optimizing and improving the overall odor of the material.

In conclusion, the antibacterial nylon composition disclosed by the invention has the characteristics of excellent mechanical property, excellent antibacterial property and low odor.

Detailed Description

In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. Preferred embodiments of the present invention are shown in the examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the invention, the meaning of "plurality" means at least two, for example, two, three or more, etc., and the meaning of "plurality" means at least two, for example, two, three or more, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.

The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.

All percentages, fractions and ratios are calculated on the total mass of the composition of the invention, unless otherwise indicated. All of the mass of the ingredients listed, unless otherwise indicated, are given to the active substance content and therefore they do not include solvents or by-products that may be included in commercially available materials. The term "mass percent" herein may be represented by the symbol "%". All molecular weights herein are weight average molecular weights expressed in daltons, unless indicated otherwise. All formulations and tests herein take place in an environment of 25 ℃, unless otherwise indicated. The terms "comprising," "including," "containing," "having," or other variations thereof herein are intended to cover a non-closed inclusion, without distinguishing between them. The term "comprising" means that other steps and ingredients may be added that do not affect the end result. The compositions and methods/processes of the present invention comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as additional or optional ingredients, components, steps, or limitations of any of the embodiments described herein. The terms "efficacy," "performance," "effect," "efficacy" are not differentiated herein.

The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the present invention may be mass units known in the chemical industry field such as μ g, mg, g, kg.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.

The invention provides an antibacterial nylon composition, which comprises the following components in parts by weight:

Compared with the traditional silver ion antibacterial agent, the antibacterial agent provided by the invention has higher antibacterial efficiency in a nylon composition and better cost performance. The antibacterial agent can also be synergistic with high-strength glass fibers to further improve the mechanical properties of nylon materials, including strength and toughness.

In a specific example, the antimicrobial nylon composition further comprises 0.1 to 1.5 parts zinc oxide.

The addition of zinc oxide helps to further enhance the antimicrobial effect of the material.

In a specific example, the antimicrobial agent is a mixture of zinc pyrithione and copper pyrithione.

Zinc pyrithione and copper pyrithione are taken as an ion carrier, can penetrate through cell membranes, carry protons into cells and carry potassium ions to leave, so that the ion gradient of the cell membranes is destroyed, nutrients cannot be transported to cause death, the whole process is free or little, and the sterilization mechanism is to balance ions in bacterial cell fluid through ion exchange to play a role in sterilization.

In a preferred example, the antibacterial agent is a mixture of zinc pyrithione and copper pyrithione in a mass ratio of 1 (0.5 to 1.5).

It is understood that in the present invention, the mass ratio of zinc pyrithione to copper pyrithione includes, but is not limited to, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5.

In a specific example, the aliphatic polyamide has a relative viscosity of 2.5 to 3.

It is understood that in the present invention, the relative viscosity of the aliphatic polyamide includes, but is not limited to, 2.5, 2.6, 2.7, 2.8, 2.9, 3.

In a preferred example, the aliphatic polyamide has a relative viscosity of 2.7 to 2.9.

It will be appreciated that in the present invention, the relative viscosity of the aliphatic polyamide is tested by the following method/standard: measurement of the viscosity of the polyamide the PA resin was dissolved with 96% concentrated sulfuric acid to prepare a 1%g/ml nylon solution according to the standard of ISO 307-2007, and the viscosity of the material was measured with a wu viscometer.

The relative viscosity of polyamide is positively correlated with the molecular weight of the material and directly affects the performance of the material, and when the viscosity is too low, the tensile strength and impact strength of the material are reduced; when the viscosity is too high, the processing of the material is affected, the dispersion of the material is difficult during the processing of the material, and various substances cannot be effectively mixed together, so that the performance of the composite material is reduced.

In a specific example, the aliphatic polyamide is selected from one or more of polycaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide and polyhexamethylene sebacamide.

In a specific example, the high strength glass fibers have an average diameter of 6 μm to 15 μm.

In a specific example, the high strength glass fibers have an average diameter of 8 μm to 10 μm.

In a specific example, the high strength glass fiber is surface treated with a silane-based coupling agent; the mass of the silane coupling agent is 0.4-0.6% of the mass of the high-strength glass fiber.

More specifically, the mass of the silane coupling agent is 0.5% of the mass of the high-strength glass fiber.

More specifically, the high-strength glass fiber is subjected to surface treatment by an amino silane coupling agent. More specifically, the high strength glass fiber is surface treated with a KH-550 coupling agent.

In a specific example, the odor adsorbent is a molecular sieve adsorbent. More specifically, the molecular sieve adsorbent is selected from silicate-based adsorbents. More specifically, the molecular sieve adsorbent is magnesium silicate powder.

In one specific example, the adjuvant includes one or more of 0.1 to 0.5 part of an antioxidant, 0.3 to 1 part of a lubricant, and 0.1 to 0.5 part of a nucleating agent.

In a specific example, the antimicrobial nylon composition comprises the following components in parts by weight:

preferably, the antibacterial nylon composition comprises the following components in parts by weight:

in a specific example, the antioxidant is selected from one or more of hindered phenolic antioxidants and phosphite antioxidants.

In a more specific example, the antioxidant is selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine, and tris (2, 4-di-tert-butylphenyl) phosphite.

In a specific example, the lubricant is selected from one or more of esters, montanates, ethylene bis-stearamide, and polyethylene wax, and silicone.

In a more specific example, the lubricant is selected from one or more of silicone masterbatch, TAF, polyethylene wax, PETS, and calcium stearate.

In one specific example, the nucleating agent is nanosilica.

mixing aliphatic polyamide, odor adsorbent, antibacterial agent, antioxidant, lubricant and nucleating agent, plasticizing, mixing with high-strength glass fiber, and granulating.

In a specific example, the preparation method of the antibacterial nylon composition includes the following steps:

mixing aliphatic polyamide, odor adsorbent, antibacterial agent, antioxidant, lubricant and nucleating agent, plasticizing with twin screw, mixing with high-strength glass fiber, traction, cooling, granulating, and drying.

More specifically, conditions for twin screws include: the temperature is 240-280 deg.c and the rotation speed is 300-400 rpm.

In a more specific example, the preparation method of the antibacterial nylon composition comprises the following steps:

premixing dried aliphatic polyamide, an odor adsorbent, an antibacterial agent, an antioxidant, a lubricant and a nucleating agent according to a certain proportion, plasticizing by a double screw, adding high-strength glass fibers treated by an amino silane coupling agent into the mixture by a side feeding port according to a certain proportion, and obtaining granules after traction, cooling, granulating and drying.

The invention also provides application of the antibacterial nylon composition. The technical proposal is as follows:

It will be appreciated that the automotive interior material includes, but is not limited to, air outlet blades, switch panels.

The antibacterial nylon composition and the preparation method thereof according to the present invention are described in further detail below with reference to specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.

PA6 resin: the relative viscosity at 25 ℃ is 2.8, and the brand is HY 2800A;

PA6 resin: the relative viscosity at 25 ℃ is 2.0, and the brand is HY 2000A from sea-yang chemical fiber;

PA6 resin: the relative viscosity at 25 ℃ is 2.2, and the brand is HY 2200A from sea-yang chemical fiber;

PA6 resin: the relative viscosity at 25 ℃ is 2.5, and the brand is HY 2500A from sea-yang chemical fiber;

PA6 resin: the relative viscosity is 3.2 at 25 ℃ and is from sea-yang chemical fiber with the brand of HY 3200A;

aromatic polyamide: C1504T, PA6T/PA66 copolymer from Shandong Guangdong boundary;

high strength glass fiber 1: HMG436S-10-4.0 (length 4mm, diameter 10 μm) is from Taishan glass fiber;

high strength glass fiber 2: e225 (long glass fibers, diameter 7-8 μm), from the boulder group;

high strength glass fiber 3: ECS303A-3-K (3.0 mm in length, 13 μm in diameter) from Chongqing International;

high strength glass fiber 4: DE300 (long glass fibers, diameter 6 μm), from the boulder group;

common glass fiber: EDR17-2400-988A (long glass fiber, diameter 17 μm), from the boulder group;

odor adsorbent 1: commercially available molecular sieve odor adsorbent, with the designation MACROSORB MS 10E; PQ Corporation;

odor adsorbent 2: commercially available zinc ricinoleate odor adsorbent, brand TEGO Sorb PY88TQ; win the creation;

antibacterial agent: commercially available zinc pyrithione and copper pyrithione;

zinc oxide: are commercially available;

an antioxidant: is derived from Li Anlong, brand SONOX 1010;

and (3) a lubricant: silicone-based lubricants on the market;

nucleating agent: nano SiO ₂ And is commercially available.

The formulation amounts (parts by weight) of the specific examples 1 to 20 described in tables 1 to 2 and the comparative examples 1 to 10 described in table 3 were respectively pre-mixed with the dried aliphatic PA resin, the odor adsorbent, the antibacterial agent, the antioxidant, the lubricant and the nucleating agent in a certain ratio, plasticized by twin screws, and added in a side feeding port in a certain ratio to obtain pellets after traction, cooling, pelleting and drying. The temperature of the twin-screw extruder is 240-280 ℃, and the screw rotating speed is 300-400 rpm.

TABLE 1

TABLE 2

TABLE 3 Table 3

Effect verification test

The antibacterial nylon compositions prepared in examples 1 to 20 and comparative examples 1 to 10 were subjected to an effect verification experiment including measurement of tensile properties, notched impact strength, antibacterial effect and odor grade, and were specifically as follows:

tensile strength: the sample was injection molded into a 170mm x 10mm x 4mm dumbbell bar, tested according to ISO 527 method, with a tensile rate of 5mm/min;

notched impact strength of simply supported beams: the sample is molded into a spline with the thickness of 80mm multiplied by 10mm multiplied by 4mm, the notch is 8mm thick, and the pendulum energy is 4J according to the ISO 179/1eA method;

odor rating test: placing about 20g of particles into a clean odor bottle according to the requirements of an automobile host factory, placing the particles in the middle of an oven at 80 ℃ for 2 hours, and then testing the odor level of the material; evaluation was performed according to the standards of the public PV 3900.

Antibacterial test: the samples were injection molded into 50mm by 3mm templates, and tested for antimicrobial effect according to GB/31402-2015 standards, and the antimicrobial rates of the materials against E.coli and Staphylococcus aureus, respectively.

The results of the effect verification experiments are shown in tables 4 to 5.

TABLE 4 Table 4

TABLE 5

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According to the test results of Table 4, the antibacterial nylon composition prepared in the examples of the present application has the characteristics of excellent mechanical properties, excellent antibacterial properties and low odor. The tensile strength is more than 179MPa, and the highest tensile strength can reach 208MPa; notched impact strength of 12.8KJ/m ² ～16.8KJ/m ² Within the range, the antibacterial effect on escherichia coli and staphylococcus aureus can reach more than 97%, and the odor grade is below 3.7.

It can be seen from tables 4 and 5 that the antibacterial effect is obviously reduced after the zinc pyrithione and copper pyrithione composite antibacterial agent is replaced by the silver ion antibacterial agent, and meanwhile, the mechanical property of the composition material is obviously improved by adding the zinc pyrithione and copper pyrithione. The use of high-strength glass fiber obviously improves the mechanical properties of the material; meanwhile, the addition of zinc oxide is helpful to the improvement of the antibacterial effect of the material. In addition, the replacement of aliphatic polyamides with aromatic polyamides also results in reduced mechanical properties and antibacterial effects.

The present invention is illustrated by the above examples to describe the detailed scheme and process flow of the present invention, but the present invention is not limited to the above detailed scheme and process flow, i.e., it does not mean that the present invention must be implemented depending on the above detailed scheme and process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent of the invention should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.

Claims

1. The antibacterial nylon composition is characterized by comprising the following components in parts by weight:

60-70 parts of aliphatic polyamide,

30-35 parts of high-strength glass fiber,

1 to 3 parts of antibacterial agent,

0.5-3 parts of odor adsorbent

0.5-2 parts of auxiliary agent;

wherein the antibacterial agent is a mixture of zinc pyrithione and copper pyrithione in a mass ratio of 1 (0.5-1.5); or the antibacterial agent is a mixture of zinc pyrithione and copper pyrithione in a mass ratio of 1:2;

the relative viscosity of the aliphatic polyamide is 2.5-3 under the condition of 25 ℃;

the average diameter of the high-strength glass fiber is 6-15 mu m.

2. The antimicrobial nylon composition of claim 1, further comprising 0.1 parts to 1.5 parts zinc oxide.

3. The antimicrobial nylon composition of claim 1, wherein the antimicrobial agent is zinc pyrithione to copper pyrithione in a mass ratio of 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5.

4. The antimicrobial nylon composition of claim 1, wherein the aliphatic polyamide satisfies one or both of the following conditions:

(1) The relative viscosity at 25 ℃ is 2.7-2.9;

(2) The aliphatic polyamide is selected from one or more of polycaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide and polyhexamethylene sebacamide.

5. The antimicrobial nylon composition of claim 1, wherein the high strength glass fiber is surface treated with a silane-based coupling agent; the mass of the silane coupling agent is 0.4% -0.6% of the mass of the high-strength glass fiber.

6. The antimicrobial nylon composition of claim 1, wherein the odor adsorbent is a molecular sieve adsorbent.

7. The antimicrobial nylon composition of any one of claims 1-6, wherein the adjuvant comprises one or more of 0.1-0.5 parts of an antioxidant, 0.3-1 parts of a lubricant, and 0.1-0.5 parts of a nucleating agent.

8. The antimicrobial nylon composition of claim 7, wherein the antioxidant is selected from one or more of hindered phenolic antioxidants and phosphite antioxidants; and/or

The lubricant is selected from one or more of esters, montanate, ethylene bis-stearamide and polyethylene wax; and/or

The nucleating agent is nano silicon dioxide.

9. A method of preparing the antimicrobial nylon composition of claim 7 or 8, comprising the steps of:

10. An automotive interior material comprising the antimicrobial nylon composition according to any one of claims 1 to 8.