WO2020073782A1 - Melt-blown nonwoven fabric and preparation method therefor - Google Patents

Abstract

A melt-blown nonwoven fabric, comprising an antibacterial polymer, the antibacterial polymer being formed by polymerizing a polyol and a guanidine salt and having a structure of formula (I). The antibacterial master batch preparation method uses a non-toxic and non-irritating polyol as raw material, being friendly to the environment and human body.

Description

Melt-blown non-woven fabric and preparation method thereof One technical field

The present application belongs to the field of textile materials and the field of environmental protection. Specifically, the present application provides a melt-blown non-woven fabric and a preparation method thereof, in which the antibacterial masterbatch is polymerized using a non-toxic / non-stimulating polyol and a guanidine salt.

Two background technologies

Due to its short production process, relatively simple equipment, high output, low cost, and many sources of raw materials, non-woven fabrics have been widely used in various fields, especially disposable bags and disposable hygiene products used in daily life As well as some clothing linings, the use of these daily life fields requires that non-woven fabrics be kept as clean and hygienic as possible. Since the non-woven fabric has insufficient water and washing resistance, adding an antibacterial agent to the non-woven fabric to develop a non-woven fabric with antibacterial properties has become an important way to solve this problem.

Antibacterial agents used in antibacterial nonwoven fabrics can be classified as inorganic, organic, and natural. There are many problems in the source, price and stability of natural antibacterial agents, and they cannot become the mainstream antibacterial materials in the nonwoven fabric industry. Inorganic antibacterial agents, such as the commonly used nano silver materials, have problems including complex processes, large product size, easy agglomeration, inadequate contact between silver-containing parts and bacteria, and limited types of antibacterial (especially poor anti-fungal effects). The problem of organic antibacterial agents is mainly that the types of antibacterial agents are limited and stable, especially the stability of chemical products such as water, heat and detergents (may be due to the chemical changes of organic antibacterial agents or new antibacterial products The formation of the surface layer isolates the contact between the antibacterial substance and the external bacterial cells). These problems are not enough when used in water resistance and washing durability. However, in actual use, there are unavoidable contact with water or non-woven fabrics that are accidentally washed.

The inventors previously polymerized polyamines and guanidine salts to obtain an antibacterial masterbatch and obtained the Chinese patent CN1111556C. In subsequent applications, the masterbatch was actually used in plastics, fibers, coatings, etc., and achieved good practice. effect. However, although the masterbatch has a good anti-fungal effect, it has the same problem of insufficient water and washing resistance as most organic antibacterial agents (the water solubility of the guanidine structure makes this problem more significant). When it is used in non-woven materials, The amount of non-woven fabrics that will achieve antimicrobial function will be significantly reduced. Moreover, the existing antibacterial masterbatches, including CN1111556C, mostly use toxic / irritating raw materials such as polyamines, and the waste water generated is not environmentally friendly and the possible residues on the products will irritate human skin. Therefore, the polymerization of guanidine-containing structures There is a need for further improvement of antimicrobial agents.

Three summary

In response to the above problems, the inventors further improved the polymer antibacterial agent containing a guanidine structure of CN1111556C, and prepared a new type of antibacterial polymer by polymerizing a polyhydric alcohol and a guanidine salt. The polymer maintained the antibacterial performance similar to that of the CN1111556C antibacterial polymer. It has achieved a significant increase in heat resistance, water resistance, and detergent resistance. It can be used to prepare antibacterial nonwoven materials. While maintaining basic antibacterial and mechanical properties, antibacterial nonwoven fabrics have certain water and detergent resistance. It can withstand general immersion in water \ wrong washing, the application range and adaptability are greatly improved; and the use of non-toxic / non-irritating polyol as raw material is more environmentally friendly than polyamines, and makes non-woven products more suitable as non-woven products. Clothing or bags that come into contact with the human body.

In one aspect, the present application provides a melt-blown non-woven fabric, which includes an antibacterial polymer, which is formed by polymerizing a polyhydric alcohol or a polyamine and a guanidinium salt.

Further, the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:

Wherein n = 5-10, m = 50-150; Y - is selected from _{^{Cl -, NO 3 -, HCO}} 3 -, CH 3 COO -, HSO 4 - or H ₂ PO ₄ ^- anion; X is containing 1- 5 reactive unsaturated double bond C5-C20 ester or ether groups; Z is H or X.

Further, in the antibacterial polymer, X is selected from acrylate group, methacrylate group, crotonate group, undecylenate group, ethyl acrylate group, propyl acrylate group or hydroxypropyl methacrylate group Ester group.

Further, the antibacterial polymer is prepared by the following method: the polyol and the guanidine salt are mixed in a molar ratio of 1: 0.8-1.8. Add to the reactor, adjust the pH to acidic under the protection of nitrogen, heat to 120-180 ℃, react for 1-4 hours, and then add 5% -25% by weight of polyol and guanidine salt containing active unsaturated double bond C3- The C20 compound undergoes esterification or ring-opening condensation reaction, and the reaction is terminated after 10 to 120 minutes.

Further, the molar ratio of polyol to guanidine salt is 1: 1 to 1.5.

Further, the polyhydric alcohol is selected from ethylene glycol, propylene glycol, butylene glycol, pentanediol, 1,6-hexanediol, 1,10-decanediol; the guanidine salt is selected from guanidine carbonate, guanidine hydrochloride, guanidine nitrate, Guanidine sulfate, guanidine phosphate, guanidine acetate; C3-C20 compounds containing active unsaturated double bonds are selected from acrylic acid, methacrylic acid, epoxyethyl acrylate, glycidyl acrylate, epoxybutyl acrylate, methacrylic acid ring Oxypropyl ester, epoxy ethyl methacrylate, epoxy butyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxypropyl ester, glycidyl methacrylate, 2-hydroxypropyl methacrylate, maleic anhydride, fumarate, itaconic acid.

Further, the preparation method specifically includes:

Take 124g of ethylene glycol and 260g of guanidine nitrate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 5 with hydrochloric acid, heat to 120 ° C, react for 3h, then add 30g of acrylic acid, perform esterification reaction for 1h, and end the reaction .

Further, the preparation method specifically includes:

Take 152g of propylene glycol and 254g of guanidine carbonate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 4 with hydrochloric acid, heat to 130 ° C, react for 2.5h, then add 25g of methacrylic acid, and perform the esterification reaction for 1.5h. End the reaction.

Four specific embodiments

Example 1 Preparation of antibacterial masterbatch of this application

1.1 Take 124g of ethylene glycol and 260g of guanidine nitrate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 5 with hydrochloric acid, heat to 120 ° C, react for 3h, then add 30g of acrylic acid, and perform the esterification reaction for 1h. reaction. Granulation.

The molecular weight of the product is about 8300, the thermal decomposition temperature is about 340 ℃, and the infrared spectrum shows the characteristic absorption peak.

1.2 Take 152g of propylene glycol and 254g of guanidine carbonate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 4 with hydrochloric acid, heat to 130 ° C, react for 2.5h, then add 25g of methacrylic acid, and perform the esterification reaction for 1.5h To end the reaction. Granulation.

The molecular weight of the product is about 10600, the thermal decomposition temperature is about 300 ℃, and the infrared spectrum shows the characteristic absorption peak.

Example 2 Preparation of the melt-blown non-woven material of the present application

The specific preparation of the meltblown nonwoven fabric is completed by the cooperative enterprise; the antibacterial masterbatch of CN1111556C is prepared according to Example 1 in this publication; the antibacterial masterbatch of this application is prepared according to the method of Example 1 (1.1); the nonwoven polypropylene Masterbatch particles are conventional types purchased from Jiande Junjie Plastic Materials Co., Ltd .; the pp meltblown nonwoven fabric production line used by the cooperative enterprise is produced and assembled by Wuxi Anji.

Take 100 parts by weight of polypropylene masterbatch particles, optional 8 parts by weight of this application antibacterial masterbatch / CN1111556C antibacterial masterbatch fully mixed as a raw material for melt-blown nonwoven fabric, using conventional melt-blown process to prepare melt-blown nonwoven fabric (extrusion Machine temperature 200 ℃, extrusion die temperature 240 ℃, traction hot air temperature 270 ℃, pressure 0.4MPa).

Material 1: Add antibacterial masterbatch of this application;

Material 2: Add CN1111556C antibacterial masterbatch;

Material 3: No antibacterial masterbatch is added;

The non-woven fabrics of materials 1-3 have a grammage of about 35g / m ² , a longitudinal tensile strength of 390-420CN, and a transverse tensile strength of 190-200CN.

In order to test the washing / soaking resistance of the antibacterial nonwoven material of this application, materials 1 and 2 were further processed

Material 1-1: Material 1 is soaked in a solution of 3% by volume of laundry liquid (blue moon, unscented) for 4 hours, rinsed and dried;

Material 2-1: Material 2 was soaked in a 3% volume laundry detergent (blue moon, unscented) solution for 4 hours, rinsed and dried;

Material 1-2: Material 1 is soaked in purified water for 4 hours and dried;

Material 2-2: Material 2 is soaked in purified water for 4 hours and dried;

The damage situation of the treated materials is similar. The decrease in longitudinal tensile strength and transverse tensile strength are similar, about 20% -30%.

Example 3 Detection of antibacterial properties of non-woven materials

The antibacterial performance test is carried out by the Antibacterial Material Testing Center of the Institute of Physics and Chemistry, Chinese Academy of Sciences. The antibacterial and Candida albicans performance is according to GB / T 20944.3-2008 Shaking method: Place the sample in the flask, add the inoculated bacterial liquid, shake, and absorb the liquid in the bottle , Place on plate for 48 hours (72 hours for Candida albicans), record the number of colonies (cfu / ml) to calculate the inhibition rate. The anti-fungal performance refers to the agar plate method in AATCC30: the mold inoculum was evenly added to the disc sample, and cultured for 14 days to observe the mold coverage.

Test subjects include Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231 and the fungus Aspergillus niger ATCC 6275.

Table 1 Anti-bacterial / candida albicans performance of non-woven materials

* Reference standard, below 90% cannot be said to have antibacterial effect.

Table 2. Anti-fungal properties of non-woven materials

Sample serial number	Aspergillus niger growth
Material 1	No growth
Material 2	No growth
Material 3	Macro growth
Material 1-1	No growth
Material 2-1	Macro growth
Material 1-2	No growth

Material 2-2

Macro growth

* Three growth criteria: no growth: invisible, microscopic growth: visible under the microscope, macroscopic growth: visible to the naked eye.

The data of Examples 2 and 3 show that the antibacterial performance of the antibacterial masterbatch of this application is similar to that of CN1111556C antibacterial masterbatch, but when prepared as a nonwoven material, the anti-soaking / detergent ability is significantly higher than that of CN1111556C antibacterial masterbatch. After immersing in a degree of detergent (simulating low-intensity washing / miswashing or water immersion), the non-woven fabric material prepared by the antibacterial masterbatch of this application has little or no effect on the performance of anti-bacterial fungi, except for the physical properties of CN1111556C. The non-woven fabric material prepared from the masterbatch has almost lost all antibacterial properties, especially resistance to mold and Candida albicans.

Additional experiments have shown that the non-woven fabric material containing the antibacterial polymer of Example 1 (1.2) has similar mechanical and antibacterial properties as that of the non-woven fabric containing Example 1 (1.1), and the non-woven fabric made has similar resistance to water immersion. And washing capacity (to save time and cost, no full test is commissioned).

The above-mentioned characteristics of the nonwoven fabric material of the present application make it more suitable for the preparation of daily necessities such as inner layers of clothing and bags. These articles are inevitably exposed to water or lightly washed during use. The nonwoven fabric material of the present application is still in these cases Can basically maintain antibacterial ability.

The non-woven fabric formulation and preparation process in the above embodiments are just for example, the technical solutions of the remaining non-woven fabric masterbatch, auxiliary materials and antibacterial masterbatch of this application and other types of non-woven fabrics, such as spunbond non-woven fabrics The antibacterial effects of the technical solutions can be reasonably expected from Examples 2 and 3, and these technical solutions are also within the scope of the disclosure and protection of the present application.

Claims (2)

1. A melt-blown non-woven fabric, characterized in that it includes an antibacterial polymer, which is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:

   

   Wherein n = 5-10, m = 50-150; Y - is selected from _{^{Cl -, NO 3 -, HCO}} 3 -, CH 3 COO -, HSO 4 - or H ₂ PO ₄ ^- anion; X is containing 1- 5 active unsaturated double bond C5-C20 ester or ether groups; Z is H or X; the antibacterial polymer is prepared according to the following method:

   Take 124g of ethylene glycol and 260g of guanidine nitrate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 5 with hydrochloric acid, heat to 120 ° C, react for 3h, then add 30g of acrylic acid, perform esterification reaction for 1h, and end the reaction .
2. A melt-blown non-woven fabric, characterized in that it includes an antibacterial polymer, which is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:

   

   Wherein n = 5-10, m = 50-150; Y - is selected from _{^{Cl -, NO 3 -, HCO}} 3 -, CH 3 COO -, HSO 4 - or H ₂ PO ₄ ^- anion; X is containing 1- 5 active unsaturated double bond C5-C20 ester or ether groups; Z is H or X; the antibacterial polymer is prepared according to the following method:

   Take 152g of propylene glycol and 254g of guanidine carbonate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 4 with hydrochloric acid, heat to 130 ° C, react for 2.5h, then add 25g of methacrylic acid, and perform the esterification reaction for 1.5h. End the reaction.