JPH0291209A - Synthetic fibers having deodorant properties - Google Patents

Abstract

PURPOSE:To obtain a synthetic fiber of deodorizing properties, which is suitably used in the fields of diapers, carpets, curtains and sheets in hospitals, by adding amorphous inorganic fine particles of specific zinc silicate to a thermoplastic polymer having a melting point over a certain temperature. CONSTITUTION:The objective synthetic fiber is composed of (A) a thermoplastic polymer of 150 deg.C and higher melting point and good fiber-forming properties and (B) 0.1 to 10wt.% of substantially amorphous inorganic fine particles of zinc silicate where the average particle size is less than 5 microns, the weight ratio of zinc oxide to silicon dioxide is 1:5 to 5:1, and almost all of the part has the amorphous structure.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides synthetic fibers with excellent deodorizing performance suitable for use in diapers, carpets, curtains, hospital sheets, and other applications where bad odors are averse. It is related to.

More specifically, it is also effective against basic gases such as ammonia, which is the main component of the rotten smell of meat, etc., which is said to be the four major odors in the world, and trimethylamine, which is the main component of the rotten smell of fish, etc.
It is also effective against a wide range of odor components, and is effective against methyl mercaptan, which is the product of rotten odors in vegetables, etc., and acid gases, such as hydrogen sulfide, which is the main component of rotten odors in eggs and milk. The present invention relates to fibers having odor performance.

(Prior Art) Among synthetic fibers, polyester fibers, polyamide fibers, etc. have become indispensable as clothing materials due to their excellent dimensional stability, chemical resistance, strength, and durability.

However, depending on the intended use, it has been desired to provide more special functions. For example, in applications such as hospital sheets, diapers, and carpets where bad odors are averse, textile products that retain the ability to reduce the causing bad odors as much as possible have been desired. Most conventional products are made by attaching natural needles, extracts from broad-leaved trees, extracts from green tea, etc. to the surface of textile products using post-processing methods, but they are not durable. There was a drawback that was enough. In particular, there has been a problem in that the deodorizing performance is extremely reduced when the product is washed repeatedly or when the textile product is dyed.

In addition, there are deodorant types that are kneaded into resin for the purpose of improving durability, such as those containing a divalent iron ion compound and L-ascorbic acid, but in order to be oriented into polyester, heat resistance is required. There have been problems in that it is insufficient, or when it is made into textile products, it changes color after deodorizing the malodorous substances, so that it can only be used for specific purposes as a textile material.

Under these circumstances, the inventors of the present invention conducted intensive studies to solve this problem, and as a result, they arrived at the present invention.

(Problems to be Solved by the Invention) In other words, an object of the present invention is to apply a deodorant to fibers in order to fundamentally solve the drawbacks of the conventional post-processing method of attaching the deodorant to the surface of fibers. When incorporated into fibers, the fibers have durability such as durability against washing, are effective in deodorizing a wide range of malodorous components, and do not cause defects such as discoloration of textile products. In order to achieve this, what kind of materials should be used and what kind of configuration and conditions should be used?The present invention has clarified this point.

(Means for Solving the Problems) The synthetic fiber of the present invention contains a thermoplastic polymer having a melting point of 150° C. or higher, such as polyester and/or polyamide.
This is a fiber having deodorizing performance characterized by containing 0.1 to 10% by weight of inorganic fine powder having an average particle diameter of 5 microns or less and having excellent deodorizing performance.

Hereinafter, the fiber of the present invention and its manufacturing method will be explained in detail.

The inorganic fine particles used in the present invention preferably have an average particle diameter of 5 microns or less. If the particle size exceeds 5 microns, filter clogging and fluff breakage tend to occur during melt spinning, making it difficult to use. Especially when considering application to various clothing materials, bedding products, etc., fine denier yarn with a single fiber denier of around 1 denier is also required, and the larger the particle size, the more likely the thread will break during drawing, so it is not preferable. do not have. Therefore, it is desirable that the inorganic fine particles used in the present invention have an average particle size of 5 microns or less, more preferably 1 micron or less.

The inorganic fine particles used in the present invention are substantially made of zinc silicate, which has a mostly amorphous structure in which the ratio of zinc oxide to silicon dioxide is in the range of 1:5 to 5.1 by weight. Amorphous fine particles are preferred. The ratio of zinc oxide to silicon dioxide is preferably in the range of 1:4 to 4:1, more preferably in the range of 1:3 to 3:1.

Zinc silicate is naturally produced in large quantities, but most have a crystalline structure. Surprisingly, when it has this crystal structure, it exhibits almost no deodorizing performance. However, it has been found that excellent deodorizing performance is achieved only when the material has a substantially amorphous structure, and that sufficient deodorizing performance is maintained when it is contained and dispersed in a thermoplastic resin. Moreover, it has been found that a good deodorizing effect is exhibited against basic gases such as ammonia and trimethylamines, as well as against acidic gases such as hydrogen sulfide and methyl mercaptan.

The substantially amorphous structure mentioned here refers to a state in which virtually no crystalline peaks appear in X-ray diffraction analysis, and by creating such an inorganic structure, excellent This means that the deodorizing performance was achieved.

In addition, although the mechanism by which the inorganic fine particles of the present invention have deodorizing performance is currently unknown, there is a certain type of nutrient-forming reaction caused by zinc oxide in zinc silicate against amphoteric gases such as basic gases and acidic gases. At the same time, the amorphous structure of the inorganic fine particles also exerts a gas physical adsorption effect, and it is thought that excellent deodorizing performance will be developed due to a comprehensive synergistic effect. An even more significant feature is that it has been confirmed that sufficient deodorizing performance is maintained even in the form of fibers made by incorporating the inorganic particles into a thermoplastic polymer and using the inorganic particles to form fibers. usually,
When a deodorizing agent is internally added to a resin, its deodorizing performance tends to be inhibited and its effectiveness decreases, and in particular, it is common for the deodorizing performance of acidic gases such as hydrogen sulfide to be significantly reduced. However, a major feature is that the deodorizing performance does not deteriorate when the inorganic fine particles of the present invention are internally added. The reason for this is not yet clear.

Furthermore, the inorganic fine particles of the present invention are kneaded into, for example, polyethylene terephthalate polymer and made into fibers, and the deodorizing performance is maintained without any decrease even after being subjected to high-temperature dyeing treatment at 130°C in the post-processing process. Understood. Furthermore, when the fibers are washed after deodorizing gases such as ammonia, the complexes of inorganic fine particles that exhibit deodorizing performance and deodorized gas molecules are destroyed, and the deodorizing gas components are washed away during washing, causing the fibers to deteriorate. As a result, it was found that the deodorizing performance can be regenerated almost completely again, and that by repeated washing operations, it is possible to use the fiber semi-permanently, which has virtually no lifespan, as a fiber that retains its deodorizing performance. Understood.

The amount of the inorganic fine particles of the present invention added to the thermoplastic polymer is preferably 0.1 to 10% by weight. More preferably 0
．． 5 to 10% by weight is good. When the amount added is less than 0.1%, it is difficult to say that the fiber has sufficient deodorizing performance. If the amount added is 10% or more, the deodorizing performance is sufficient, but the processability during fiberization becomes extremely poor, which is not preferable. In particular, during spinning, single filament breakage and yarn breakage occur frequently due to the occurrence of dirt around the nozzle hole, and the drawability deteriorates significantly, causing fuzz and yarn breakage to occur frequently. Furthermore, the thread path of the equipment during the thread running during the process will be severely worn out, which is undesirable.

The inorganic particles of the present invention are characterized in that they are essentially amorphous substances such as zinc silicate, and various methods can be considered for producing the inorganic particles. It can also be produced by quantitatively mixing, then firing at a high temperature, and immediately quenching and pulverizing.

An example of measuring deodorizing performance is shown in Figure 1. In the case of ammonia,
Ammonia sensor l (A E-2 manufactured by Toa Denpa Co., Ltd.)
35) and ion meter 3 (IM-1 manufactured by Toa Denpa Co., Ltd.)
E) is connected to the recorder 4, and the change over time in the ammonia gas concentration in the container 5 is read. 500 ppffi in container 5
A predetermined amount of ammonia gas was put into the container using a syringe so that the amount of ammonia gas was added, then measurement sample 2 was set, and the ammonia concentration in the container was measured after being left for 2 hours.

In the case of hydrogen sulfide, add a specified amount of sodium bisulfide, distilled water, and agricultural hydrochloric acid to a specified container to generate a certain amount of hydrogen sulfide gas, suspend the measurement sample in the container, and after storing it at 25°C, remove the head space in the flask. A 24-hour discharge displacement measurement was performed using a north-side gas detection tube.

As the thermoplastic resin of the present invention, a polymer having a melting point of 150° C. or higher and excellent fiber-forming properties is preferable.

Particularly preferred are polyester or polyamide.

Polyester is a polyester whose main component is polyethylene terephthalate or polybutylene terephthalate, and includes terephthalic acid, isophthalic acid, naphthalene 2.6 dicarboxylic acid, phthalic acid, α,β-(4-carboxyphenoxy)ethane, 4', Aromatic dicarboxylic acids such as 4°-dicarboquine diphenyl, 5-sodium sulfoisophthalic acid or aliphatic dicarboxylic acids such as anopic acid, sebacic acid, or esters thereof, and ethylene glycol, ethylene glycol, 14
- A fiber-forming polyester synthesized from a nool compound such as butanediol, neopentyl glycol, cyclohexane-1,4-dimetatool, polyethylene glycol, polytetramethylene glycol, etc., in which 80 mol% or more of its constituent units are particularly is preferably a polyester in which 90 mol% or more is polyethylene terephthalate units or polybutylene terephthalate units, and desirably has a melting point of 150° C. or higher. If the melting point is low, the use as a fiber material for clothing etc. will be somewhat limited due to insufficient heat resistance etc., which is not preferable ('). The polyester may also contain small amounts of additives, such as matting agents such as titanium oxide, antioxidants, optical brighteners, stabilizers, or ultraviolet absorbers.

Polyamide is a polyamide whose main component is nylon 6, nylon 66, or methaquinene diamine nylon, and may also be a copolyamide containing a small amount of a third component, but the melting point must be maintained at 150'C or higher. is preferred.

It goes without saying that the same effect can be expected in the present invention with both long fibers and short fibers.

The invention! Fiber refers to fibers that make up woven, knitted, non-woven fabrics, or processed products thereof, but includes fibers other than these, such as natural fibers such as cotton, linen, and wool, and synthetic fibers such as general polyester, nylon, and acrylic. Fibers, blended fibers such as semi-synthetic fibers such as acetate and rayon,
It may be of mixed knitting or weaving. In this case, the content ratio of the fiber of the present invention is preferably 30% or more in terms of deodorizing effect,
More preferably, it is 50% or more.

The fibers of the present invention can be obtained by high-order processing such as pre-combustion crimping.
It can be shaped like an angular or hexagonal shell, or it can be made into multi-lobed shapes such as trilobal, T-shaped, four-lobed, five-lobed, six-lobed, seven-lobed, eight-lobed, etc. due to the irregular cross-section nozzle during spinning. It can take various shapes and cross-sectional shapes, and its effects are fully expressed.

Next, a manufacturing example of the deodorant fiber of the present invention will be explained. For example, in the case of polyethylene terephthalate fiber, a predetermined amount of the inorganic fine powder of the present invention is dispersed in ethylene glycol, which is a monomer, and the inorganic fine powder is uniformly dispersed using a vibration mill or a ball mill to an average of 5 microns or less. There is a method of reacting powdered ethylene glycol with terephthalic acid under known conditions, polymerizing it, and then forming it into fibers. In this case, troubles such as the polymerization rate slowing down or the molecular weight not increasing to a predetermined degree of polymerization sometimes occur, or the inorganic fine powder may thermally agglomerate during the esterification or polymerization process, or during the spinning or drawing process. Problems such as thread breakage may occur. A safer method is to knead a predetermined amount of polyethylene tereftate polymer and inorganic fine particles finely pulverized to an average size of 5 microns or less using a twin-screw kneading extruder or the like, re-pelletize the resulting product, and then make fibers. In this case, a master polymer containing a high content of inorganic fine particles may be prepared and then diluted to a predetermined amount using a polymer blending method during spinning to form fibers.

(Effects of the Invention) The fibers of the present invention maintain deodorizing performance by incorporating zinc-based inorganic fine powder having excellent deodorizing performance into the fibers. In addition, the fibers of the present invention retain deodorizing performance for a very long time and do not deteriorate even after frequent washing, so they can be used, for example, in hospital sheets and diapers that require high washing resistance. Even when used in fields such as the above, it is possible to sufficiently exhibit deodorizing performance.

(Example) The present invention will be specifically explained below with reference to Examples.

The washing conditions were determined by the following test method.

Washing test method> Conducted according to JIS LO217-103 method. Liquid aL 2 g of synthetic laundry detergent was added and dissolved in water 112 at 40° C. to obtain a washing liquid. This washing liquid has a bath ratio of 1
Load the sample and load cloth as necessary so that the ratio is 30 to 30, and start the operation. After processing for 5 minutes, stop operation,
Dehydrate the sample and load cloth using a dehydrator, then replace the washing liquid with fresh water at room temperature, rinse for 2 minutes at the same bath ratio, dehydrate, rinse again for 2 minutes, and air dry.

The above operation was repeated 10 times, and a measurement sample was obtained after 10 times.

Example 1 A fine powder of zinc silicate having an amorphous structure with a weight ratio of zinc oxide and silicon dioxide of 1:3 and an average particle size of 5 microns or less was prepared using a twin-screw kneading extruder manufactured by Japan Steel Works, Ltd. and knead with polyethylene terephthalate resin, and add 1 part of the above inorganic fine powder to the polyethylene terephthalate resin.
A pellet containing 0 wt% was obtained.

Next, the above pellets containing 10 wt% of inorganic fine powder and ordinary polyethylene terephthalate pellets were blended at a ratio of 1:4, and fiberization was performed to obtain fibers containing 2 wt% of inorganic fine powder with deodorizing performance. Obtained. Spinning temperature 29
Spinning was performed at 0° C. and a winding speed of 1000 m/min, and then drawing was performed using a roller plate method to obtain a multifilament of 75 denier and 24 filaments.

Both spinnability and stretchability were good and there were no problems. Thereafter, a tubular knitted fabric was prepared using a conventional method, and after relaxing, washing, drying, and presetting treatments, the deodorizing performance was measured.

A measurement sample log was placed in an atmosphere maintained at a sooppm ammonia concentration in a 2-liter container, and the ammonia concentration in the container was measured after 2 hours to calculate the deodorization rate. In addition to the initial performance, the performance of the JIS Standard 1 Ko knitted fabric was confirmed to have an ammonia deodorization rate of 90% or more. In addition, after repeating the procedure of washing the sample whose ammonia deodorization rate was measured and measuring the ammonia deodorization performance again in the same manner five times, the deodorization rate at the sixth time was 90% or more. It was confirmed that the same performance as the initial performance was expressed again.

In the same way, hydrogen sulfide was tested, and a measurement sample Log was placed in a 2-liter container containing hydrogen sulfide at 10,100 pp. After 24 hours, the hydrogen sulfide concentration in the container was measured, and the deodorization rate was determined. I asked for it. Initial performance is also JIS
Performance of hydrogen sulfide deodorization rate of 80% or more was confirmed from Standard 1 Ko.

In addition, when hydrogen sulfide was measured for the sixth time after repeating the operation five times (measurement → washing) in the same manner as the ammonia measurement, it was confirmed that the deodorizing performance was 80% or more, which was the same as the initial performance.

Comparative Example 1 Fine zinc oxide powder with a crystalline structure and an average particle size of 5 microns or less and fine powder with a crystalline structure and an average particle size of 5 microns or less were mixed at a weight ratio of 1:3, and the powder was prepared by Japan Steel Works, Ltd. The mixture was kneaded with a polyethylene terephthalate resin using a twin-screw kneading extruder manufactured by Co., Ltd. to obtain a pellet containing 1Qvt% of the above inorganic fine powder in the polyethylene terephthalate resin.

Next, the above pellet containing 1 ht% of inorganic fine powder and ordinary polyethylene terephthalate pellets were blended at a ratio of 1:4, and fiberization was performed to obtain fibers containing 2 wt% of inorganic fine powder with deodorizing performance. Ta. Spinning temperature 290
C. and a winding speed of 1000 m/min, and then drawing was carried out using a roller plate method to obtain a multifilament of 75 denier and 24 filaments. Both spinnability and stretchability were good and there were no problems. Thereafter, a tubular knitted fabric was prepared using a conventional method, and after relaxing, washing with water, drying, and presetting treatment, the deodorizing performance was measured.

A measurement sample log was placed in an atmosphere maintained at an ammonia concentration of 500 pPm in a 2-liter container, and the ammonia concentration in the container was measured after 2 hours to calculate the deodorization rate. The initial performance and other performance of the JIS standard 1 first knitted fabric was also insufficient with an ammonia deodorization rate of 35%. Furthermore, after repeating the procedure 5 times in which the sample whose ammonia deodorization rate was measured was washed and the ammonia deodorization performance was measured again in the same manner, the deodorization rate at the 6th time was 35%.

In the same way, hydrogen sulfide was tested, and a measurement sample log was placed in a hydrogen sulfide atmosphere containing 100 pp1 in a 2-liter container, and the hydrogen sulfide concentration in the container was measured after 24 hours to determine the deodorization rate. Ta. Initial performance is also 1. MSS standard 1 hydrogen deodorization rate was 25%, which was insufficient performance. In addition, when hydrogen sulfide was measured for the sixth time after repeating the operation (measurement-washing) five times in the same way as the ammonia measurement, the deodorization rate was 25%, which was the same as the initial performance.

Examples 2 to 4 Examples were carried out under the conditions shown in Table 1. The same amorphous zinc silicate as in Example 1 was used, but the content in the fiber was changed. The content change is amorphous zinc silicate fine powder 10wt%
The experiment was carried out by changing the blending ratio of the contained pellets and ordinary polyethylene terephthalate pellets. Other conditions are
The procedure was carried out in the same manner as in Example 1, and it was confirmed that both had good fiberization process properties and sufficient deodorizing performance.

Example 5.6 Polymers used under the conditions shown in Table 1 were nylon 6 in Example 5 and polybutylene terephthalate in Example 6. In Example 5, a drawn yarn of 75 denier and 24 filaments was obtained using a spinning direct drawing method at a spinning yield of 260°C. In Example 6, the spinning temperature was 260°C and the winding speed was 1.
Spinning was carried out at 200 m/min, and then drawing was carried out using a roller plate method to obtain a drawn yarn of 24 filaments of 75 denier. All of them had good fiberization process properties and good deodorizing performance.

Example 78 The mixing ratio of zinc oxide and silicon dioxide in amorphous zinc silicate was changed, and Example 7 had a ratio of zinc oxide to silicon dioxide of 1:1.
I, Example 8 was carried out at a ratio of 3:1, and the other conditions were the same as in Example 1. It had good fiberization process properties and sufficient deodorizing performance.

Comparative Example 2 Fine powder of amorphous zinc silicate having a weight ratio of zinc oxide and silicon dioxide of 1:3 with an average particle size of 5 microns or less was fed into a twin-screw kneading extruder manufactured by Japan Steel Works, Ltd. and knead with polyethylene terephthalate resin, and add 1 part of the above inorganic fine powder to the polyethylene terephthalate resin.
A pellet containing 0 wt% was obtained.

Next, the above pellets containing 1 ost% of inorganic fine powder and ordinary polyethylene terephthalate pellets were blended at a ratio of 1 to 199, and fiberization was performed to obtain fibers containing Q, 05 wt% of inorganic fine powder with deodorizing performance. Obtained. Spinning was carried out at a spinning temperature of 290° C. and a winding speed of 1000 m/+in, and then drawing was carried out using a roller plate method to obtain a multifilament of 75 denier and 24 filaments. Both spinnability and stretchability were good and there were no problems. Thereafter, a tubular knitted fabric was prepared using a conventional method, and after relaxing, washing, drying, and presetting treatments, the deodorizing performance was measured.

Comparative Example 3 A fine powder of zinc silicate having an amorphous structure with a weight ratio of zinc oxide and silicon dioxide of 1:3 and an average particle size of 5 microns or less was processed using a two-wheeled kneading extruder manufactured by Japan Steel Works, Ltd. The above inorganic fine powder is mixed with polyethylene terephthalate [fat] and kneaded with polyethylene terephthalate resin.
A pellet containing 5 wt% was obtained.

Next, using the pellets containing 15 wt% of the above inorganic fine powder,
When spinning was carried out, single yarn breakage and yarn breakage occurred frequently during spinning. Moreover, the stretchability was also poor.

Comparative Example 4.5 The mixing ratio of zinc oxide and silicon dioxide in amorphous zinc silicate was 15:85 in Comparative Example 4 and 85:15 in Comparative Example 5, and the pond conditions were the same as in Example 1. .

- The deodorizing performance was at a lower level than in Example 1.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an example of a deodorizing property 111i measuring device. Sensor measurement data (71!l odor vertebrae structure) Ion meter recorder container

Claims (1)

[Claims] Substantially amorphous inorganic fine particles of zinc silicate with an average particle size of 5 microns or less and a mostly amorphous structure with a ratio of zinc oxide and silicon dioxide of 1:5 to 5:1 have a melting point of 150°C or higher. 0.1 to 1 in the thermoplastic polymer of
A synthetic fiber having deodorizing performance characterized by being present in an amount of 0% by weight.