JP2022553760A - Preparation method of antibacterial deodorant spandex - Google Patents

Abstract

An antibacterial deodorant spandex and its preparation method, adding an antibacterial deodorant to the spandex stock solution, stirring and aging, and dry spinning to obtain antibacterial deodorant spandex, the antibacterial deodorant being the solid content in the spandex stock solution accounts for 0.2-2% of The antibacterial deodorant means sepiolite chemically graft-modified with polyepichlorohydrin quaternary ammonium salt. The antibacterial deodorant can be evenly dispersed in the spandex stock solution, and does not affect the replacement cycle of production equipment after adding the antibacterial deodorant. Provide excellent antibacterial and deodorant function to spandex on the premise of maintaining high elasticity and high strength inherent in spandex. The antibacterial deodorant prepared by this method can be dispersed well in the spandex stock solution, exists stably, does not aggregate, and the antibacterial deodorant spandex prepared has better spandex fibers than conventional antibacterial spandex. It has excellent uniformity, antibacterial properties, deodorant performance, and excellent water washing resistance.

Description

TECHNICAL FIELD The present invention belongs to the technical field of polymer material preparation, and specifically relates to a method for preparing antibacterial deodorant spandex. The method of the present invention can effectively solve the problem of poor compatibility between the conventional inorganic antibacterial agent and spandex stock solution, the preparation process is simple, and the replacement cycle of production equipment is not affected. The performance of the prepared spandex has good uniformity and good antibacterial and deodorant properties.

Spandex is characterized by high breaking strength, high breaking elongation and high impact resilience, and is widely used in fields such as innerwear, sportswear, stockings, webbing, paper diapers, and medical sanitary products. Since such products come into direct contact with the human skin, their antibacterial and deodorant properties have received increasing attention. According to research, the polyurethane polymer chain in spandex itself does not have antibacterial and deodorant properties. Under suitable environmental conditions, some bacteria harmful to the human body can multiply and metabolize general spandex fibers. It disrupts the dynamic balance of the normal skin microbiome of the human body and harms the health of the human body. Most body odors are derived from ammonia gas, acetic acid and isovaleric acid formed by decomposition and metabolism of sweat or lipid-secreting substances by malodorous bacteria such as Staphylococcus epidermidis and Corynebacterium. In addition to preventing infections and skin diseases, the antibacterial treatment of fibers can also 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. In order to have a meaningful meaning, it is necessary to have these two functions at the same time.

Providing antibacterial performance to chemical fibers is mainly realized by adding an antibacterial agent to the fibers. Antimicrobial agents mainly include inorganic antimicrobial agents, organic antimicrobial agents, and minor amounts of natural antimicrobial agents. Among inorganic antibacterial agents, silver ions have the widest application, but are difficult to disperse and expensive. Among organic antibacterial agents, quaternary ammonium salts are widely used, but they have the problem of being easily washed away and having poor resistance to water washing.

In order to impart a deodorant function to chemical fibers, it is mainly realized by adding deodorants to the fibers, and the following three types of deodorants are always used. 1) They are aromatic substances. Such substances can mask or dilute odors to make them less offensive to humans, and mainly include rose, lily of the valley, cinnamon, turpentine, lemon oil, and the like. 2) It is a chemical deodorant. Such substances can chemically react with odor molecules to produce odorless substances, mainly including metal salt-based inorganic deodorants, mainly including nano-titania and nano-zinc oxide. 3) It is a physical adsorbent. It is a substance with large specific surface area, large pores, and strong adsorption ability that adsorbs malodorous substances.

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

Preparing the antibacterial deodorant spandex by the blending method means blending the antibacterial agent with the spandex stock solution or TPU slice, and preparing the antibacterial spandex by dry spinning or melt spinning. According to the report of patent CN102618962B, First, silver nitrate is added to DMAC and stirred, and stirred at 70° C. for 3 hours, after which a yellow silver sol is obtained, and silver nanoparticles are added to the spandex spinning stock solution as an antibacterial agent, and the addition amount is 0.01-1. % and obtain antibacterial spandex by dry spinning. However, it is necessary to add a reducing agent and a protective agent to prepare nano-silver with silver nitrate, otherwise the produced nano-silver tends to agglomerate. According to the report of patent CN107513776A, in the melt spinning process, the TPU slice and the silver-based inorganic antibacterial agent are heated and mixed in a screw machine, and the antibacterial spandex is obtained by melt spinning.

Using the skin-core structure composite spinning method to prepare antibacterial deodorant spandex is to coat the skin layer or the core layer with a functional material, and prepare the skin-core component with a special structure. Patent CN103194819B reports that the healthcare spandex is composed of a skin layer and a core layer, where the melt-spun material of the core layer comprises bamboo charcoal powder, polyhexamethylene biguanide hydrochloride, perfume, fiber-forming polymer. include. A spinneret plate assembly is used to extrude the melted spinning material of the core layer and the spinning dope of the skin layer through the hollow needles and pressing holes of the spinneret plate assembly, respectively, to prepare antibacterial deodorizing healthcare spandex.

According to the information analysis of the above-disclosed reports, there are three main problems in the whole process of preparing antimicrobial spandex by blending method: First, nano-silver is an inorganic particle with a large specific surface area, is in an unstable state at high energy, has poor interfacial compatibility with polyurethane polymer chains in spandex, is very prone to agglomeration, and is subject to modification treatment. If it is not treated or treated insufficiently, the raw solution filter will easily become clogged, and the pressure in the pipe will become too high. Second, unmodified nano-silver or inorganic antibacterial agents are not uniformly dispersed in the spandex stock solution, resulting in large spandex index fluctuations and affecting the use of spandex products in post-processes. Third, the disclosed antibacterial spandex only has a bactericidal effect against some common bacteria harmful to the human body, and the main odor molecules in the human body (ammonia gas, acetic acid, isovaleric acid, and 2-nonenal, etc.) are not effective. In general, in the microbial ecological environment of the human skin, the legs, armpits, and other parts in particular secrete a large amount of organic matter and sweat, which facilitates the growth of bacteria and the production of odorous low-molecular weight molecules. In the development of odorous textiles, the antibacterial and deodorizing properties need to be organically combined and cooperated to achieve good use effects. On the other hand, the skin-core composite spinning method has a complicated and complicated preparation process, and the whole spinning system is completely different from the traditional dry spinning process. , it is easy to cause yarn breakage during the spinning process, and furthermore, it has a large effect on physical property indicators such as elongation of spandex yarn. decrease significantly.

In the present invention, by synthesizing an antibacterial deodorant with a special structure, it is possible to impart antibacterial deodorant properties and washing resistance to spandex, and the antibacterial deodorant is uniformly dispersed in the spandex undiluted solution, It does not easily 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 an antibacterial deodorant spandex. The non-agglomerated antimicrobial deodorant spandex prepared has better spandex fiber uniformity, antimicrobial and deodorant performance, and superior water wash resistance compared to the disclosed antimicrobial spandex.

The method for preparing the antibacterial deodorant spandex according to the present invention includes adding an antibacterial deodorant to the spandex stock solution, stirring and aging, and dry spinning to obtain the antibacterial deodorant spandex, and the antibacterial deodorant is added to the spandex stock solution. It accounts for 0.2-2% of solids.

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

The preparation method of the antibacterial deodorant is as follows.

In step 1, nitrogen gas is passed through the reactor to protect it, solvent, hydroxyl-terminated polyepichlorohydrin, and tertiary amine are added to the reactor, and the nitrogen atoms in the tertiary amine and the hydroxyl-terminated polyepichlorohydrin are separated from each other. The molar ratio of the chlorine atoms in the 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-terminated polyepichlorohydrin quaternary ammonium salt is obtained. to get

In step 2, N,N-dimethylacetamide is added to the reactor, and the 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 40-60° C. for 1.5-3.5 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 30-40%.

In step 3, sepiolite treated with an inorganic acid is uniformly mixed with N,N-dimethylacetamide at a solid-liquid mass ratio of 1:10, polished for 2 to 6 hours, and then polished with sepiolite at a mass fraction of 30 to 30. 40% isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution is mixed, and the mass ratio of the sepiolite after polishing and the isocyanate-blocked polyepichlorohydrin quaternary ammonium salt is 1:30 to 1:200. , performing chemical grafting reaction at 40-60° C. for 2-4 h, filtering, 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 hydroxyl-terminated polyepichlorohydrin number-average molecular weight range used in step 1 is 500-1,000.

（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.

(where 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 according to step 1 is either acetone, n-propanol, ethanol, methanol, or isopropyl alcohol.

The antibacterial deodorant spandex prepared in the present invention is obtained by synthesizing an antibacterial deodorant material and adding it to the spandex stock solution, so that the surface of the structure of the material contains an organic long-chain polymer, and the spandex is mainly It is similar to the structure of polyurethane polymer, which is a component, and has good compatibility. It can be ensured that the period is not shortened. On the other hand, the side chains of the organic long-chain polymer on the surface of the structure of such an antibacterial deodorant material have many quaternary ammonium bases and have good antibacterial properties, and the inorganic part is sepiolite. , It is fibrous, has an extremely high porosity, a large specific surface area, and has good offensive odor low-molecular-weight adsorption performance. In comparison, it has good uniformity and antibacterial properties, and good deodorant performance is imparted.

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

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

In step 1, nitrogen gas is passed into the reactor to protect it, and solvent, hydroxyl-terminated polyepichlorohydrin, and tertiary amine are added to the reactor, wherein the nitrogen atoms in the tertiary amine and the hydroxyl-terminated The molar ratio of 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 to obtain hydroxyl-terminated polyepichlorohydrin quaternary. Obtain an ammonium salt.

In step 2, N,N-dimethylacetamide is added to the reactor, and the 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 40-60° C. for 1.5-3.5 hours to obtain an isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution with a mass fraction of 30-40%.

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

Specifically, the preparation method of the spinning dope is as follows.

A solvent is added to the first reactor, 4,4-diphenylmethane diisocyanate and polytetrahydrofuran ether glycol are mixed at a molar ratio of 1.5:1 to 1.8:1, and prepolymerized at 40 to 50° C. for 2 hours. After that, it is transferred to the second reactor, and the chain extender solution is gradually added dropwise to the second reactor. and aging for 24 hours to prepare a spinning stock solution with a mass fraction of 30-37 (wt)%, and the viscosity of the spinning stock solution is 3000-6000P (40° C.).

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

The spandex undiluted solution containing the antibacterial deodorant is precisely weighed with a gear pump, pushed into the spinning component, flowed out from the spinneret plate, the yarn is heated by hot air in the passage, the solvent is volatilized by flash evaporation, and the yarn is An antimicrobial deodorant spandex is prepared by coagulating, oiling and winding.

The following standards are referred to for detection methods of antibacterial performance and deodorant performance.

The invention will now be further described with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention. Also, after reading the contents described in the present invention, those skilled in the art may make various changes or modifications to the present invention, and equivalent forms thereof are likewise limited to the scope of the appended claims of this application. should be understood to be included.

(Example 1)
Nitrogen gas is passed through the reactor to protect it, and a solvent, hydroxyl-terminated polyepichlorohydrin (number average molecular weight: 500), and tertiary amine (N,N-dimethyldodecylamine) are added to the reactor, where , The molar ratio between the nitrogen atoms in the tertiary amine (N,N-dimethyldodecylamine) and the chlorine atoms in the hydroxyl-terminated polyepichlorohydrin was 1:2, and after refluxing at 60°C for 5 hours, the solvent was removed. was removed to obtain hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt.

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

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

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

(Example 2)
Nitrogen gas is introduced into the reactor to protect it, and a solvent, hydroxyl-terminated polyepichlorohydrin (number average molecular weight: 700), and tertiary amine (N,N-dimethyltetradecylamine) are added to the reactor. , the molar ratio between the nitrogen atoms in the tertiary amine (N,N-dimethyltetradecylamine) and the chlorine atoms in the hydroxyl-terminated polyepichlorohydrin is 1:4, and after refluxing at 70° C. for 6 hours, The solvent was removed to obtain hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt.

N,N-dimethylacetamide was added to the reactor, and the hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4,4-diphenylmethane diisocyanate were uniformly mixed at a molar ratio of 1:2.5, and preliminarily heated 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%.

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

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

(Example 3)
Nitrogen gas is introduced into the reactor to protect it, and a solvent, hydroxyl-terminated polyepichlorohydrin (number average molecular weight: 800), and tertiary amine (N,N-dimethylhexadecylamine) are added to the reactor. , the molar ratio of the nitrogen atoms in the tertiary amine (N,N-dimethylhexadecylamine) and the chlorine atoms in the hydroxyl-terminated polyepichlorohydrin is 1:6, and after refluxing at 80° C. for 7 hours, The solvent was removed to obtain hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt.

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

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

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

(Example 4)
Nitrogen gas was introduced into the reactor to protect it, and the solvent added in the reactor, hydroxyl-terminated polyepichlorohydrin (number average molecular weight: 1000), tertiary amine (didodecyl tertiary amine), where tertiary amine ( The molar ratio of the nitrogen atoms in the hydroxy-terminated polyepichlorohydrin) to the chlorine atoms in the hydroxyl-terminated polyepichlorohydrin is 1:10. A hydrin quaternary ammonium salt was obtained.

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

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

An antimicrobial deodorant was added to the spandex stock solution, the antimicrobial deodorant accounting for 0.5% solids of the spandex stock solution. An antibacterial deodorant spandex (designated as "Sample 4") was produced by dry spinning.

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

In the process of preparing the antibacterial deodorant spandex according to the present invention, the replacement cycles of the stock filter and the spinning component are as shown in Table 3.

Claims (7)

An antibacterial deodorant is added to the spandex stock solution, stirred and aged, and dry-spun to obtain an antibacterial deodorant spandex, and the antibacterial deodorant accounts for 0.2 to 2% of the solid content in the spandex stock solution.
A method for preparing an antibacterial deodorant spandex characterized by: The antibacterial deodorant means sepiolite chemically graft-modified with polyepichlorohydrin quaternary ammonium salt.
The method for preparing the antibacterial deodorant spandex according to claim 1, characterized in that: In step 1, nitrogen gas is passed through the reactor to protect it, solvent, hydroxyl-terminated polyepichlorohydrin, and tertiary amine are added to the reactor, and the nitrogen atoms in the tertiary amine and the hydroxyl-terminated polyepichlorohydrin are separated from each other. The molar ratio of the chlorine atoms in the chlorohydrin is 1:2 to 1:10, and after refluxing at 60 to 100° C. for 5 to 10 hours, the solvent is removed to obtain hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt. and get
In step 2, N,N-dimethylacetamide is added to the reactor, and the hydroxyl-terminated polyepichlorohydrin quaternary ammonium salt and 4,4-diphenylmethane diisocyanate are uniformly mixed at a molar ratio of 1:2 to 4, Preliminary polymerization 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 having a mass fraction of 30 to 40%,
In step 3, sepiolite treated with an inorganic acid is uniformly mixed with N,N-dimethylacetamide at a solid-liquid mass ratio of 1:10, polished for 2 to 6 hours, and then polished with sepiolite at a mass fraction of 30 to 30. 40% isocyanate-blocked polyepichlorohydrin quaternary ammonium salt solution is mixed, and the mass ratio of the sepiolite after polishing and the isocyanate-blocked polyepichlorohydrin quaternary ammonium salt is 1:30 to 1:200. and performing a chemical grafting reaction at 40-60° C. for 2-4 h, filtering, rinsing with N,N-dimethylacetamide, and drying to obtain a particulate antibacterial deodorant.
The method for preparing the antibacterial deodorant spandex according to claim 1 or 2, characterized in that: The particle size range of the antibacterial deodorant is 1 nm to 1000 nm,
The method for preparing the antibacterial deodorant spandex according to claim 3, characterized in that: The number average molecular weight range of the hydroxyl-terminated polyepichlorohydrin used in step 1 is 500 to 1000.
The method for preparing the antibacterial deodorant spandex according to claim 3, characterized in that: 4. The method for preparing antibacterial deodorant spandex according to claim 3, wherein the structural formula of the tertiary amine used in step 1 is as follows.

(where 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 according to step 1 is either acetone, n-propanol, ethanol, methanol, or isopropyl alcohol.
The method for preparing the antibacterial deodorant spandex according to claim 3, characterized in that: