JP7352024B2 - How to prepare antibacterial deodorizing spandex - Google Patents

Description

The present invention belongs to the technical field of polymer material preparation, and specifically relates to a method for preparing antibacterial and deodorizing spandex. The method of the present invention can effectively improve the problem of poor compatibility between conventional inorganic antibacterial agents and spandex stock solutions, has a simple preparation process, does not affect the replacement cycle of production equipment, The performance of the prepared spandex has good uniformity and good antibacterial and deodorizing properties.

Spandex has the characteristics of high breaking strength, high breaking elongation, and high impact resilience, and is widely used in fields such as innerwear, sportswear, stockings, webbing, disposable diapers, and medical hygiene products. Since such products come into direct contact with human skin, their antibacterial and deodorizing properties are attracting increasing attention. Studies have shown that the polyurethane polymer chains within spandex themselves do not have antibacterial and deodorizing properties, and under suitable environmental conditions, some bacteria harmful to the human body can grow and metabolize on common spandex fibers. It destroys the dynamic balance of the human body's normal skin microbial ecology and causes damage to human health. Most body odor is derived from ammonia gas, acetic acid, and isovaleric acid formed by odoriferous bacteria such as Staphylococcus epidermidis and Corynebacterium decomposing and metabolizing sweat or lipid secreted substances. By applying antibacterial treatment to fibers, in addition to preventing infections and skin diseases, it is also possible to effectively prevent body odor caused by bacteria. At the same time, other sources of body odor are ammonia gas, acetic acid, isovaleric acid, 2-nonenal, etc. produced by the human body's own metabolism, so antibacterial and deodorizing are closely related, and textiles are not practical. In order to have meaningful meaning, it is necessary to have these two functions at the same time.

Providing antibacterial properties to chemical fibers is mainly achieved by adding antibacterial agents to the fibers. Antibacterial agents mainly include inorganic antibacterial agents, organic antibacterial agents, and small amounts of natural antibacterial agents. Among inorganic antibacterial agents, silver ions have the widest application, but they are difficult to disperse and are expensive. Among organic antibacterial agents, quaternary ammonium salts are widely used, but they have the problem of being easily washed away and having poor washing resistance.

In order to impart a deodorizing function to chemical fibers, this is mainly achieved by adding deodorants to the fibers, and the following three types of deodorizers are always employed. 1) It is an aromatic substance. Such substances can mask the odor or dilute the odor so that people do not feel any strange odor, and mainly include rose, lily of the valley, laurel, turpentine oil, lemon oil, etc. 2) It is a chemical deodorant. Such substances can chemically react with odor molecules to produce odorless substances, and mainly include metal salt-based inorganic deodorants, mainly nano titania and nano zinc oxide. 3) It is a physical adsorbent. It adsorbs malodorous substances with materials that have a large specific surface area, large pores, and strong adsorption ability, and mainly includes activated carbon, silica gel, zeolite, activated clay, diatomaceous earth, etc., but it also has the disadvantage of being prone to agglomeration.

According to the disclosed report, the preparation method of antibacterial deodorant spandex mainly includes blending method and skin-core structure composite spinning method.

Preparing antibacterial deodorizing spandex by blending method means blending an antibacterial agent with spandex stock solution or TPU slice and preparing antibacterial spandex by dry spinning or melt spinning, as reported in patent CN102618962B. First, silver nitrate was added to DMAC and stirred, and after stirring at 70°C for 3 hours, a yellow silver sol was obtained, and silver nanoparticles were added to the spandex spinning dope as an antibacterial agent, and the amount added was 0.01 to 1. % and obtain antibacterial spandex by dry spinning. However, in order to prepare nanosilver with silver nitrate, it is necessary to add a reducing agent and a protective agent, and if they are not added, the generated nanosilver is likely to aggregate. According to the report of patent CN107513776A, in the melt-spinning process, TPU slices and a silver-based inorganic antibacterial agent are heated and mixed in a screw machine, and antibacterial spandex is obtained by melt-spinning.

Preparing antibacterial deodorizing spandex using skin-core structure composite spinning method is to coat the functional material on the skin layer or core layer and prepare it with a special structure of the skin-core component. According to a report in Patent CN103194819B, the healthcare spandex is composed of a skin layer and a core layer, where the melt-spun material of the core layer contains bamboo charcoal powder, polyhexamethylene biguanide hydrochloride, fragrance, and fiber-forming polymer. include. Using the spinneret plate assembly, the molten spun body of the core layer and the spinning dope of the skin layer are extruded through the hollow needles and pressing holes of the spinneret plate assembly, respectively, to prepare healthcare spandex with antibacterial deodorization.

According to the information analysis of the above disclosed reports, there are the following three main problems in the whole process of preparing antibacterial spandex by blending method. First, nanosilver is an inorganic particle with a large specific surface area, is not stable at high energy, has poor interfacial compatibility with the polyurethane polymer chains in spandex, and is extremely prone to agglomeration. If the treatment is not carried out or the treatment is insufficient, the raw solution filter is likely to become clogged, and the pressure in the pipes will become too high. In severe cases, this will cause a stoppage of production equipment, resulting in a large economic loss to production. Second, unmodified nanosilver or inorganic antibacterial agents are not uniformly dispersed in the spandex stock solution, leading to large fluctuations in the spandex index, which affects the use of spandex products in subsequent processes. Third, the antibacterial spandex in the disclosed report only has a bactericidal effect against some common bacteria that are harmful to the human body, and the main odor molecules in the human body (ammonia gas, acetic acid, isovaleric acid, and 2-nonenal). In general, in the microbial ecological environment of the human skin, areas such as the feet and axilla secrete large amounts of organic matter and sweat, which makes it easy for bacteria to multiply and produce odorless low molecules. In the development of odor fabrics, in order to achieve good use effects, antibacterial properties and deodorizing properties need to be organically combined and act cooperatively. On the other hand, in the skin-core composite spinning method, the preparation process is complicated and complicated, the entire spinning system is completely different from the conventional dry spinning process, and the content of inorganic materials in the core layer is extremely high, causing clogging of production equipment. , it is easy to cause yarn breakage during the spinning process, and it also greatly affects physical property indicators such as elongation of spandex yarn.Since the core layer is coated with an antibacterial deodorizing substance, the actual antibacterial deodorizing effect of spandex is Significant decline.

The present invention can impart antibacterial deodorizing properties and washability to spandex by synthesizing an antibacterial deodorant with a special structure, and the antibacterial deodorant is uniformly dispersed in the spandex stock solution. It is not easy to agglomerate, the preparation process is simple, and it does not adversely affect the replacement cycle of production equipment.

The problem to be solved by the present invention is to provide a method for preparing antibacterial deodorizing spandex, and the antibacterial deodorant prepared by this method can be well dispersed in the spandex stock solution, exists stably, The antibacterial deodorizing spandex prepared without agglomeration has better uniformity, antibacterial properties, and deodorizing performance of the spandex fibers, and has excellent washing resistance compared to the disclosed antibacterial spandex.

The method for preparing antibacterial deodorizing spandex according to the present invention involves adding an antibacterial deodorizing agent to a spandex stock solution, stirring and aging, and obtaining an antibacterial deodorizing spandex by dry spinning. It accounts for 0.2-2% of the solid content.

The antibacterial deodorant refers to sepiolite chemically graft-modified with polyepichlorohydrin quaternary ammonium salt.

The method for preparing the antibacterial deodorant is as follows.

In step 1, the reactor is protected by passing nitrogen gas, and a solvent, hydroxyl-terminated polyepichlorohydrin, and tertiary amine are added to the reactor, and the nitrogen atoms in the tertiary amine and hydroxyl-terminated polyepichlorohydrin are added to the reactor. The molar ratio of chlorine atoms in chlorohydrin is 1:2 to 1:10, and after refluxing at 60 to 100°C for 5 to 10 hours, the solvent is removed and hydroxyl group-terminated polyepichlorohydrin quaternary ammonium salt is obtained. get.

In step 2, N,N-dimethylacetamide is added to the reactor, and hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4,4-diphenylmethane diisocyanate are uniformly mixed at a molar ratio of 1:2 to 4; Prepolymerization is carried out at 40 to 60° C. for 1.5 to 3.5 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 30 to 40%.

In step 3, the sepiolite treated with an inorganic acid is uniformly mixed with N,N-dimethylacetamide at a solid-liquid mass ratio of 1:10, and after polishing for 2 to 6 hours, the sepiolite after polishing and the mass fraction of 30 to 30% are polished. A 40% isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution is mixed, and the mass ratio of sepiolite and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt after polishing is 1:30 to 1:200. A chemical grafting reaction is carried out at 40 to 60° C. for 2 to 4 hours, followed by filtration, rinsing with N,N-dimethylacetamide, and drying to obtain a particulate antibacterial deodorant.

The particle size range of the antibacterial deodorant is 1 nm to 1000 nm.

The number average molecular weight of the hydroxyl-terminated polyepichlorohydrin used in step 1 is in the range of 500 to 1,000.

（ただし、Ｒ_１は炭素数１２～１８の直鎖アルキル基であり、Ｒ_２は炭素数１～１８の直鎖アルキル基である。） The structural formula of the tertiary amine used in step 1 is as follows.

(However, R ₁ is a straight chain alkyl group having 12 to 18 carbon atoms, and R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms.)

The solvent added to the reactor in Step 1 as described in Step 1 is either acetone, n-propanol, ethanol, methanol, or isopropyl alcohol.

The antibacterial deodorizing spandex prepared in the present invention is produced by synthesizing an antibacterial deodorizing material and adding it to the spandex stock solution. Because it is similar in structure to the component polyurethane polymer and has good compatibility, antibacterial deodorizers are added to the spandex stock solution to ensure it has good stable dispersion, and replacement of the stock filter and spinning components. It is possible to ensure that the cycle does not become short. On the other hand, the side chains of organic long-chain polymers on the surface of the structure of such antibacterial deodorizing materials have many quaternary ammonium bases, which have good antibacterial properties, and the inorganic part is sepiolite. The antibacterial deodorizing spandex prepared by the present invention is superior to the disclosed antibacterial spandex because it is fibrous, has extremely high porosity, and has a large specific surface area, and has good adsorption performance for low-molecular-weight molecules with off-flavors. In comparison, it has good uniformity, antibacterial properties, and good deodorizing performance.

The steps of the method for preparing antibacterial and deodorizing spandex according to the present invention are as follows.
(1) Prepare an antibacterial deodorant.
(2) Prepare a spinning stock solution.
(3) Prepare antibacterial deodorant spandex.

A specific method for preparing the antibacterial deodorant is as follows.

In step 1, the reactor is protected by passing nitrogen gas, and a solvent, a hydroxyl-terminated polyepichlorohydrin, and a tertiary amine are added to the reactor, where the nitrogen atoms in the tertiary amine and the hydroxyl-terminated The molar ratio to the chlorine atoms in polyepichlorohydrin is 1:2 to 1:10, and after refluxing at 60 to 100°C for 5 to 10 hours, the solvent is removed and the hydroxyl group-terminated polyepichlorohydrin quaternary Obtain ammonium salts.

In step 2, N,N-dimethylacetamide is added to the reactor, and hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4,4-diphenylmethane diisocyanate are uniformly mixed at a molar ratio of 1:2 to 4; Prepolymerization is carried out at 40 to 60° C. for 1.5 to 3.5 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 30 to 40%.

In step 3, the sepiolite treated with an inorganic acid is uniformly mixed with N,N-dimethylacetamide at a solid-liquid mass ratio of 1:10, and after polishing for 3 hours, the mass fraction of the sepiolite after polishing is 30 to 40%. isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution, and here, the mass ratio of sepiolite after polishing and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt is 1:30 to 1: 200, carry out chemical grafting reaction at 40~60°C for 2 hours, filter, rinse with N,N-dimethylacetamide, and dry to obtain an antibacterial deodorant.

The specific method for preparing the spinning dope is as follows.

A solvent was added to the first reactor, 4,4-diphenylmethane diisocyanate and polytetrahydrofuran ether glycol were mixed at a molar ratio of 1.5:1 to 1.8:1, and prepolymerization was performed at 40 to 50°C for 2 hours. After that, it was transferred to a second reactor, and the chain extender solution was gradually dropped into the second reactor, and after the dropping was completed for 1.5 to 2.5 hours, it was transferred to an aging tank, where antibacterial deodorant and other Each auxiliary agent is added, and aging is performed for 24 hours to prepare a spinning stock solution with a mass fraction of 30 to 37 (wt)%, and the viscosity of the spinning stock solution is 3000 to 6000P (40° C.).

(3) The method for preparing antibacterial deodorizing spandex is as follows.

Spandex stock solution containing antibacterial deodorant is precisely metered by a gear pump and forced into the spinning component and out of the spinneret plate, where the yarn is heated by hot air and the solvent is volatilized by flash evaporation, forming the yarn. Antibacterial and deodorizing spandex is prepared by coagulating, applying oil and winding.

The methods for detecting antibacterial and deodorizing performance refer to the following standards.

The present invention will be further described below with reference to specific examples. It should be understood that these examples are merely illustrative of the invention and are not intended to limit the scope of the invention. In addition, after reading the content described in this invention, those skilled in the art can make various changes or modifications to this invention, and these equivalent forms may also be considered within the scope of the appended claims of this application. It should be understood that this includes:

(Example 1)
The reactor was protected by passing nitrogen gas, and a solvent, hydroxyl-terminated polyepichlorohydrin (number average molecular weight 500), and tertiary amine (N,N-dimethyldodecylamine) were added to the reactor. The molar ratio of the nitrogen atom in the tertiary amine (N,N-dimethyldodecylamine) to the chlorine atom in the hydroxyl-terminated polyepichlorohydrin was 1:2, and after refluxing at 60°C for 5 hours, the solvent was removed. This was removed to obtain a hydroxyl group-terminated polyepichlorohydrin quaternary ammonium salt.

N,N-dimethylacetamide was added to the reactor, hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt, and 4,4-diphenylmethane diisocyanate were uniformly mixed at a molar ratio of 1:2, and prepolymerization was carried out at 40°C. This was carried out for 2 hours, and an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 35% was obtained.

Sepiolite treated with inorganic acid is mixed with isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution having a mass fraction of 35%, and sepiolite treated with inorganic acid and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution are mixed. The mass ratio with the ammonium salt was 1:30, and a chemical graft reaction was performed at 40° C. for 4 hours to obtain an antibacterial deodorant.

An antibacterial deodorant was added to the spandex stock solution, and the antibacterial deodorant accounted for 2.0% of the solids content of the spandex stock solution. Antibacterial and deodorizing spandex (referred to as "Sample 1") was produced by dry spinning.

(Example 2)
The reactor was protected by introducing nitrogen gas, and a solvent, hydroxyl-terminated polyepichlorohydrin (number average molecular weight 700), and tertiary amine (N,N-dimethyltetradecylamine) were added to the reactor. The molar ratio between the nitrogen atom in the tertiary amine (N,N-dimethyltetradecylamine) and the chlorine atom in the hydroxyl-terminated polyepichlorohydrin was 1:4, and after refluxing at 70°C for 6 hours, The solvent was removed to obtain a hydroxyl group-terminated polyepichlorohydrin quaternary ammonium salt.

N,N-dimethylacetamide was added to the reactor, and hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4,4-diphenylmethane diisocyanate were uniformly mixed at a molar ratio of 1:2.5, and preheated at 45°C. Polymerization was carried out for 2.5 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 35%.

Sepiolite treated with inorganic acid is mixed with isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution having a mass fraction of 35%, and sepiolite treated with inorganic acid and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution are mixed. The mass ratio with the ammonium salt was 1:90, and a chemical graft reaction was performed at 40° C. for 4 hours to obtain an antibacterial deodorant.

An antibacterial deodorant was added to the spandex stock solution, and the antibacterial deodorant accounted for 1.5% of the solids content of the spandex stock solution. An antibacterial and deodorizing spandex (denoted as "Sample 2") was produced by dry spinning.

(Example 3)
The reactor was protected by introducing nitrogen gas, and a solvent, hydroxyl-terminated polyepichlorohydrin (number average molecular weight 800), and tertiary amine (N,N-dimethylhexadecylamine) were added to the reactor. The molar ratio between the nitrogen atom in the tertiary amine (N,N-dimethylhexadecylamine) and the chlorine atom in the hydroxyl-terminated polyepichlorohydrin is 1:6, and after refluxing at 80°C for 7 hours, The solvent was removed to obtain a hydroxyl group-terminated polyepichlorohydrin quaternary ammonium salt.

N,N-dimethylacetamide was added to the reactor, hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt, and 4,4-diphenylmethane diisocyanate were uniformly mixed at a molar ratio of 1:3, and prepolymerization was carried out at 50°C. This was carried out for 2.5 hours, and an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 35% was obtained.

Sepiolite treated with inorganic acid is mixed with isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution having a mass fraction of 35%, and sepiolite treated with inorganic acid and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution are mixed. The mass ratio with the ammonium salt was 1:150, and a chemical graft reaction was performed at 40° C. for 4 hours to obtain an antibacterial deodorant.

An antibacterial deodorant was added to the spandex stock solution, and the antibacterial deodorant accounted for 1.0% of the solids content of the spandex stock solution. Antibacterial and deodorizing spandex (denoted as "Sample 3") was produced by dry spinning.

(Example 4)
The reactor was protected by passing nitrogen gas into the reactor, and the solvent, hydroxyl group-terminated polyepichlorohydrin (number average molecular weight 1000), tertiary amine (didodecyl tertiary amine), and tertiary amine (didodecyl tertiary amine) were added into the reactor. The molar ratio of the nitrogen atom in the hydroxyl-terminated polyepichlorohydrin (didodecyl tertiary amine) to the chlorine atom in the hydroxyl-terminated polyepichlorohydrin was 1:10, and after refluxing at 90°C for 8 hours, the solvent was removed and the hydroxyl-terminated polyepichlorohydrin A hydrin quaternary ammonium salt was obtained.

N,N-dimethylacetamide was added to the reactor, hydroxyl group-terminated polyepichlorohydrin quaternary ammonium salt, and 4,4-diphenylmethane diisocyanate were uniformly mixed at a molar ratio of 1:4, and prepolymerization was carried out at 60°C. This was carried out for 3 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 35%.

Sepiolite treated with inorganic acid is mixed with isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution having a mass fraction of 35%, and sepiolite treated with inorganic acid and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution are mixed. The mass ratio with the ammonium salt was 1:200, and a chemical graft reaction was performed at 40° C. for 4 hours to obtain an antibacterial deodorant.

An antibacterial deodorant was added to the spandex stock solution, and the antibacterial deodorant accounted for 0.5% of the solids content of the spandex stock solution. Antibacterial and deodorizing spandex (denoted as "Sample 4") was produced by dry spinning.

The antibacterial performance and deodorizing performance of the antibacterial deodorizing spandex (40D) prepared according to the present invention are as shown in Tables 1 and 2 below.

In the process of preparing antibacterial and deodorizing spandex according to the present invention, the replacement cycle of the stock solution filter and spinning components is as shown in Table 3.

Claims (6)

The antibacterial deodorant is added to the spandex stock solution, stirred and aged, and the antibacterial deodorant spandex is obtained by dry spinning.The antibacterial deodorizer accounts for 0.2-2% of the solid content in the spandex stock solution .
The antibacterial deodorant refers to sepiolite chemically graft modified with polyepichlorohydrin quaternary ammonium salt;
The sepiolite chemically graft-modified with polyepichlorohydrin quaternary ammonium salt is obtained by a chemical graft reaction between an isocyanate-capped polyepichlorohydrin quaternary ammonium salt and sepiolite treated with an inorganic acid.
A method for preparing antibacterial and deodorizing spandex, characterized by: In step 1, the reactor is protected by passing nitrogen gas, and a solvent, hydroxyl-terminated polyepichlorohydrin, and tertiary amine are added to the reactor, and the nitrogen atoms in the tertiary amine and hydroxyl-terminated polyepichlorohydrin are added to the reactor. The molar ratio with chlorine atoms in chlorohydrin is 1:2 to 1:10, and after refluxing at 60 to 100°C for 5 to 10 hours, the solvent is removed and the hydroxyl group-terminated polyepichlorohydrin quaternary ammonium salt is obtained. get
In step 2, N,N-dimethylacetamide is added to the reactor, and hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4,4-diphenylmethane diisocyanate are uniformly mixed at a molar ratio of 1:2 to 4; Perform prepolymerization at 40 to 60°C for 1.5 to 3.5 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 30 to 40%,
In step 3, the sepiolite treated with an inorganic acid is uniformly mixed with N,N-dimethylacetamide at a solid-liquid mass ratio of 1:10, and after polishing for 2 to 6 hours, the sepiolite after polishing and the mass fraction of 30 to 30% are polished. A 40% isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution is mixed, and the mass ratio of sepiolite and isocyanate-blocked polyepichlorohydrin quaternary ammonium salt after polishing is 1:30 to 1:200. and carry out a chemical grafting reaction at 40-60°C for 2-4 hours, filter, rinse with N,N-dimethylacetamide, and dry to obtain particulate antibacterial deodorant.
The method for preparing antibacterial and deodorizing spandex according to claim 1 . The particle size range of the antibacterial deodorant is 1 nm to 1000 nm.
The method for preparing antibacterial and deodorizing spandex according to claim 2 . The number average molecular weight of the hydroxyl-terminated polyepichlorohydrin used in step 1 is in the range of 500 to 1000.
The method for preparing antibacterial and deodorizing spandex according to claim 2 . The method for preparing antibacterial and deodorizing spandex according to claim 2 , wherein the structural formula of the tertiary amine used in step 1 is as follows.

(However, R ₁ is a straight chain alkyl group having 12 to 18 carbon atoms, and R ₂ is a straight chain alkyl group having 1 to 18 carbon atoms.) The solvent added to the reactor in step 1 as described in step 1 is either acetone, n-propanol, ethanol, methanol, or isopropyl alcohol.
The method for preparing antibacterial and deodorizing spandex according to claim 2 .