JP2905629B2 - Deodorant and deodorant fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to diapers, carpets,
The present invention relates to a synthetic fiber having excellent deodorizing performance and deodorizing performance, which is suitable for use in curtains, hospital sheets, and other applications that dislike bad odor. In more detail, the decay of vegetables, etc., against basic gases such as ammonia, which is the main odor of meat, which is said to be the four major odors in the world, and trimethylamine, which is the main odor of fish, etc. Effective against acidic gases such as hydrogen sulfide, which is the main component of putrefactive odors such as methyl mercaptan, egg and milk, and has excellent deodorizing performance against a wide range of malodorous components. About fibers.

[0002]

2. Description of the Related Art Among synthetic fibers, polyester fibers, polyamide fibers and the like are indispensable as garment materials because of their excellent dimensional stability, chemical resistance, strength and durability. However, depending on the intended use, it has been desired to further provide a special function. For example, in applications that dislike bad odors, such as hospital sheets, diapers, carpets, and nonwoven fabrics for sanitary materials, there has been a demand for a fiber product that retains the performance of reducing the odor that causes the odor as much as possible. Conventional needles, natural needles, extracts from broad-leaved trees or extracts from green tea, etc. are attached to the surface of textile products by post-processing methods, etc., but the durability is insufficient. There were certain drawbacks. In particular, there has been a problem that the deodorizing performance is extremely reduced when, for example, repeated washing is performed or when a textile is dyed.

[0003] As a deodorant type kneaded into a resin for the purpose of improving durability, there is a compound in which a divalent ion compound of iron and L-ascorbic acid are compounded. For this reason, there has been a problem that heat resistance is insufficient, or a malodorous substance becomes decolorized after being deodorized when it becomes a fiber product, so that the fiber material can be used only for a specific application. Under such circumstances, the present inventors have conducted intensive studies to solve this problem, and as a result, have arrived at the present invention.

[0004]

That is, the object of the present invention is to provide a deodorant with a fiber in order to fundamentally solve the above-mentioned disadvantages of the conventional post-processing method of attaching a deodorant to the surface of the fiber. When used as a fiber contained inside, it is an effective fiber that has durability such as washing durability, is effective in deodorizing a wide range of malodor components, and does not cause defects such as discoloration of textile products. In order to do so, what kind of material should be used and what kind of configuration and conditions should be used, and the present invention has sought out this point.

In the synthetic fiber of the present invention, the thermoplastic polymer contains a phosphate type layered compound containing an antibacterial metal ion having an average particle size of 5 μm or less in an amount of 0.1 to 10 μm.
15% by weight, a fiber mixed with a thermoplastic polymer having a melting point of 120 ° C. or more, wherein the metal ion having antibacterial properties is silver and / or copper, and the stabilizer is added to the phosphate type layered compound particles. Wherein the stabilizer is an alkali metal and / or ammonia and / or an amine, and the total of the metal ions and the stabilizer is added in an amount of 2 mol or less per 1 mol of the basic unit of the phosphate compound. Characterized in that it is a phosphate type layered compound.

Hereinafter, the fiber of the present invention and a method for producing the same will be described in detail. The fine powder of the phosphate type layered compound used in the present invention preferably has an average particle diameter of 5 μm or less. If the particle size exceeds 5 microns, filter clogging and fluff breakage are likely to occur during melt spinning, making it difficult to use. In particular, when application to various clothing materials, bedding products, and the like is considered, a fine denier yarn having a single fiber denier of about 1 denier is also required. Therefore, the phosphate type layered compound used in the present invention preferably has an average particle size of 5 μm or less, more preferably 1 μm or less.

As a phosphate type layered compound as a substrate, for example, zirconium phosphate Zr (HPO ↓ 4) ↓ 2
・ NH ↓ 2O, titanium phosphate Ti (HPO ↓ 4) ↓ 2 ・ n
H ↓ 2O, aluminum tripolyphosphate AlH ↓ 2P ↓ 3
O ↓ 10 · nH ↓ 2O can be used. What is important is that the ion-exchangeable proton portion of the phosphate type layered compound as a base material is one of metal ions having antibacterial properties.
It is to use one that has been ion-exchanged with one or more species.

Preferred examples of metal ions having antibacterial properties include Ag, Cu, Zn, Fe, Cr, Ni, Sn, and Hg.
Is mentioned. Particularly, ions of Ag, Cu and Zn are preferable. Most preferably, Ag is suitable in view of the fact that it is preferable that the antibacterial property is high and that the fiber is not colored on the market. The above-mentioned metals having antibacterial properties can be used alone or in combination.

The phosphate type layered compound used in the present invention is, for example, a compound having atoms such as zirconium, titanium and aluminum bonded to adjacent atoms such as zirconium, titanium and aluminum to have a planar spread. Above and below the plane, PO 3 (OH) groups are bonded to atoms such as zirconium, titanium, and aluminum through the oxygen atom, and the OH group of the PO 3 (OH) group is opposite to the plane ( (External as viewed from the plane). Then, a plurality of atomic groups having such a planar spread are stacked to form a layered compound used in the present invention. The H proton (H ↑ +) of the OH group can be exchanged with various cations. The cation is the above-mentioned metal ion having antibacterial properties, and its ion exchange amount (bond amount) is 2 mol at a maximum with respect to 1 mol of the basic unit of the phosphate type layered compound. If the amount exceeds 2 moles, an excessive amount of metal ions does not form an effective ionic bond with the phosphate type layered compound, which is not preferable in practical use.

[0010] The greater the bonding amount of metal ions, the more deodorizing performance is exhibited. However, if it is necessary to maintain the cost and performance at an appropriate level, the bonding amount of metal ions is appropriately adjusted to 2 mol Max. You may change it in the range. Also,
It is also possible to use silver, copper and zinc ions in combination, and in this case also, the total amount of metal ions is 2 mol or less relative to the phosphate type layered compound. Also, silver, copper,
Metal ions other than zinc, such as sodium, potassium,
The presence of calcium or other metal ions does not hinder the bactericidal effect, so that these ions can remain or coexist at all.

Although silver ions are mentioned as an example of the most suitable metal ions, silver ions are easily oxidized in the presence of oxygen and become silver oxide, so that they may have a white to gray color. In the case of textile products, discoloration of white fabric to gray is often not desirable from the viewpoint of appearance. Therefore, it is effective to add a stabilizer compound to the phosphate type layered compound of the present invention in order to avoid discoloration trouble. For example, it is preferable to use a basic compound or a basic atom such as an alkali metal and / or ammonia and / or an amine. When the stabilizer compound is used, the total amount of the metal ion bond and the total amount of the stabilizer compound is 2 mol or less per mol of the basic unit of the phosphate type layered compound.
Even if the amount exceeds 2 moles, the excess compound has no merit because it is dropped without durability.

Since the phosphate type layered compound of the present invention has an antibacterial property, it has a deodorizing effect of preventing the propagation of microorganisms to cause decay and the generation of sweaty odor in the fiber, and has the following major characteristics. It also has a deodorizing effect. In addition, it has been found that sufficient deodorizing performance can be maintained even when contained and dispersed in a thermoplastic resin. It has been found that a good deodorizing effect is exhibited also with respect to basic gases such as ammonia and trimethylamine, and also to acidic gases such as hydrogen sulfide and methyl mercaptan.

The mechanism by which the phosphate-type layered compound fine particles of the present invention have deodorizing performance is not known at present, but a certain kind of amphoteric basic gas and acidic gas between the phosphate layers. It is thought that the acetic acid-forming reaction of the compound causes the deodorizing effect, and at the same time, the physical adsorption effect of the gas by the layered structure is also exerted. An even bigger feature is
Containing and dispersing the layered compound in a thermoplastic polymer,
It was confirmed that a fiber form obtained by using the fiber had sufficient deodorizing performance. Normally, when a deodorant is added to a resin, the deodorizing performance tends to be impaired and the effect tends to be reduced. In particular, the deodorizing performance of acidic gases such as hydrogen sulfide is generally significantly reduced. However, when the layered compound of the present invention is internally added, the deodorizing performance is not greatly reduced. The reason for this is not yet clear.

Further, the layered compound of the present invention is kneaded into, for example, polyethylene terephthalate polymer and made into a fiber, and the deodorizing performance is maintained without substantially decreasing even after a high temperature dyeing treatment at 130 ° C. in a post-processing step. I knew it was there. Further, after the fiber deodorizes a gas such as ammonia and then washed, the lamellar compound exhibiting the deodorizing performance and the acetic acid body of the deodorized gas molecule are broken when washed, and the deodorized gas component is washed off when the fiber is washed. It can be seen that the deodorant performance is regenerated in a form that is almost perfect again, and by repeating the washing operation, it is possible to use semi-permanently as a fiber with deodorant performance with virtually no life. all right.

Further, even after the non-woven fabric of the final component is prepared by incorporating the layered compound used in the present invention into the heat-fusible component polymer of the heat-fusible conjugate fiber of the binder component used in the nonwoven fabric, It was confirmed that excellent deodorizing performance was exhibited.

The amount of the layered compound of the present invention added to the thermoplastic polymer is preferably 0.1 to 15% by weight. More preferably, the content is 0.5 to 15% by weight. 0.1
%, It is difficult to say that the fiber has sufficient deodorizing performance. If the added amount exceeds 15%, the deodorizing performance is sufficient, but the processability at the time of forming fibers becomes extremely poor, which is not preferable. In particular, during spinning, single yarn breakage and yarn breakage due to generation of dirt around the nozzle hole frequently occur, and the stretchability is remarkably reduced, resulting in frequent fluff and yarn breakage. Furthermore,
The yarn path wear of the equipment during the yarn running during the process is severely generated, which is not preferable.

FIG. 1 shows a measurement example of the deodorizing performance. In the case of ammonia, the ammonia sensor 1 (Toa Denpa Co., Ltd. A
E-235) and ion meter 3 (I made by Toa Denpa Co., Ltd.)
M-IE) and the recorder 4 are connected, and the change with time of the ammonia gas concentration in the container 5 is read. 500 pp in container 5
m with a predetermined amount of ammonia gas with a syringe,
Thereafter, the measurement sample 2 was set, and the ammonia concentration in the container was measured after standing for 2 hours. In the case of hydrogen sulfide, sodium bisulfide, distilled water, concH
A predetermined amount of Cl was added, a fixed amount of hydrogen sulfide gas was generated, the measurement sample was suspended in a container, stored at 25 ° C., and the head space in the flask was measured after standing for 24 hours using a Kitagawa gas detector tube. .

In the present invention, it goes without saying that the same effect can be expected for both long fibers and short fibers. The fiber of the present invention refers to a fiber constituting a woven fabric, a knitted fabric, a nonwoven fabric or a processed product thereof, and a fiber other than the fiber, for example, cotton, hemp,
Natural fibers such as wool, general polyester, nylon,
It may be a mixed fiber, a mixed fiber, or a cross-knitted fabric such as a synthetic fiber such as acrylic and a semi-synthetic fiber such as acetate and rayon. In this case, the content of the fiber of the present invention is preferably 30% or more in view of the deodorizing effect, and more preferably 5%.
0% or more.

The fiber of the present invention can be formed into a shape similar to a pentagon or hexagon by high-order processing such as false twist crimping, or can be formed into a three-lobe, T-shaped, Leaf shape, 5
It can take a multi-leaf shape such as a leaf shape, a six-leaf shape, a seven-leaf shape, an eight-leaf shape, or various cross-sectional shapes, and its effects are sufficiently exhibited.

The thermoplastic polymer constituting the present invention includes various polymers, and among them, polyolefin, polyester and polyamide are preferable. The polyester referred to in the present invention is a polyester containing polyethylene terephthalate or polybutylene terephthalate as a main component, terephthalic acid, isophthalic acid,
Naphthalene 2,6-dicarboxylic acid, phthalic acid, α, β-
(4-carboxyphenoxy) ethane, aromatic dicarboxylic acids such as 4,4'-dicarboxydiphenyl, 5-sodium sulfoisophthalic acid or aliphatic dicarboxylic acids such as adipic acid and sebacic acid, or esters thereof, and ethylene A fiber-forming polyester synthesized from a diol compound such as glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol, or polytetramethylene glycol, and a structural unit thereof. Of at least 80 mol%, especially 9
A polyester in which 0 mol% or more is a polyethylene terephthalate unit or a polybutylene terephthalate unit is preferable, and the melting point is desirably 200 ° C. or higher. If the melting point is low, the use as a fiber material for clothing and the like is somewhat limited due to insufficient heat resistance and the like, which is not preferable. Further, the polyester may contain a small amount of additives, for example, a matting agent such as titanium oxide, an antioxidant, a fluorescent whitening agent, a stabilizer or an ultraviolet absorber.

The polyamide is a polyamide containing nylon 6, nylon 66, nylon 610, nylon 46 or meta-xylene diamine nylon as a main component.
A copolymerized polyamide containing a small amount of the third component may be used, but the melting point is preferably maintained at 200 ° C. or higher. Examples of the polyolefin include polyethylene and polypropylene.

Next, a production example of the deodorant fiber of the present invention will be described. For example, in the case of polyethylene terephthalate fiber, a predetermined amount of the layered compound of the present invention is dispersed in ethylene glycol which is a monomer, and the primary compound is firstly dispersed by a vibration mill or a ball mill. After the particles are uniformly dispersed to an average of 5 microns or less, the layered compound fine powder dispersed ethylene glycol is reacted with terephthalic acid under known conditions, and then polymerized.
After that, there is a method of fiberizing. In this case, the polymerization rate is slow, or a trouble in which the molecular weight does not increase to a predetermined degree of polymerization sometimes occurs, or the layered compound fine powder is easily thermally aggregated in the esterification step or the polymerization step, and the spinning,
Problems such as yarn breakage in the drawing process occur. A safer method is a method in which a polyethylene terephthalate polymer and a layered compound fine particle finely pulverized to an average of 5 μm or less are kneaded in a predetermined amount by a twin-screw kneading extruder or the like, and repelletized into a fiber. In this case, a master polymer having a high content of the layered compound fine particles is prepared,
The fiber may be diluted to a predetermined amount by a polymer blend method during spinning.

[0023]

The fiber of the present invention has a deodorizing performance which is maintained by incorporating fine particles of a phosphate type layered compound having excellent deodorizing performance into the fiber. Moreover, the fiber of the present invention retains the deodorant performance with extremely long durability, and the deodorant performance does not decrease even if frequent washing is performed.
For example, even when used in fields such as hospital sheets and diapers that require a high degree of washing resistance, it is possible to sufficiently exhibit deodorizing performance.

[0024]

The present invention will be described below in detail with reference to examples. Washing conditions were determined by the following test methods. <Washing test method> Performed according to JIS L0217-103 method. A synthetic detergent for clothing is added and dissolved at a rate of 2 g in 1 liter of water at a liquid temperature of 40 ° C. to prepare a washing liquid. A sample and, if necessary, a load cloth are added to the washing liquid so that the bath ratio becomes 1:30, and the operation is started. After treating for 5 minutes, the operation was stopped, the sample and the load cloth were dehydrated with a dehydrator, and then the washing liquid was replaced with fresh water at room temperature, rinsed for 2 minutes at the same bath ratio, and then dehydrated. Rinse for a minute and air dry. The above operation was repeated 10 times to obtain a measurement sample after 10 times.

Example 1 A layered compound based on aluminum tripolyphosphate having an average particle diameter of 0.3 μm was used as a base material, and the base material had 1.5 moles of protons and silver ions and 0.5 moles of sodium ions. The exchanged fine particles were kneaded with a high-density polyethylene resin using a twin-screw kneading extruder manufactured by Nippon Steel Works, Ltd. to obtain a pellet containing 10 wt% of the fine powder in the high-density polyethylene resin.

Next, the pellets containing 10% by weight of the fine powder and ordinary high-density polyethylene pellets are blended at a ratio of 1: 1. The high-density polyethylene component containing 5% by weight of the fine particles is substantially sheathed, and [η] 0.67 polyethylene terephthalate as a core, core / sheath = 50 /
Core-sheath composite spinning was performed at a 50 weight ratio. Spinning head temperature 2
It was extruded at 90 ° C. and wound at 1000 m / min. The spun yarn is stretched 4.2 times at 75 ° C. in a water bath, then contracted by 8% at 90 ° C. in a water bath, and has a fineness of 2.0 dr and a strength of 3.5 g.
/ D, a fiber having an elongation of 43% was obtained. After mechanical crimping was applied to the obtained drawn yarn, it was cut to a fiber length of 51 mm to prepare cotton. Thereafter, using the obtained cotton, a web of 40 g / m @ 2 was prepared using a miniature card.
A hot air treatment at 50 ° C. was performed to perform a heat bonding treatment to prepare a nonwoven fabric, and the deodorizing performance was measured.

10 g of a measurement sample was placed in an atmosphere maintained at a concentration of 500 ppm ammonia in a 2 liter container,
Two hours later, the ammonia concentration in the container was measured, and the deodorizing rate was calculated. The deodorizing rate of the initial performance was 95%, and the performance of the tubular knitted fabric after washing 10 times according to the JIS standard was confirmed to be the ammonia deodorizing rate of 95% or more. Also, the sample whose ammonia deodorization rate was measured once was washed, and the operation for measuring the ammonia deodorization performance again was repeated 5 times. The sixth deodorization rate was 90% or more. It was confirmed that the same performance as the initial performance was exhibited again. In the same manner, the measurement was performed on hydrogen sulfide, and 10 g of a measurement sample was placed in a hydrogen sulfide atmosphere maintained at 100 ppm in a 2 liter container.
After 24 hours, the concentration of hydrogen sulfide in the container was measured, and the deodorizing rate was determined. The deodorizing rate of the initial performance was 85%, and the performance of the tubular knitted fabric after washing 10 times in accordance with JIS standard was confirmed to be a hydrogen sulfide deodorizing rate of 85% or more. In addition, the measurement of hydrogen sulfide for the sixth time after the repeated operation (measurement → washing) was repeated five times in the same manner as in the ammonia measurement. As a result, the deodorizing performance of 80% or more was confirmed as in the initial performance.

Comparative Example 1 A nonwoven fabric was formed by the same method as in Example 1 except that the sheath component did not contain the layered compound of the present invention at all, and the deodorizing performance was measured. 10 g of the measurement sample was placed in an atmosphere maintained at a concentration of 500 ppm ammonia in a 2-liter container, and the concentration of ammonia in the container after 2 hours was measured to calculate the deodorizing rate. Initial performance,
The performance of the tubular knitted fabric after washing JIS standard 10 times was also insufficient with an ammonia deodorization rate of 35%. Further, after the sample whose ammonia deodorization rate was measured once was washed and the operation of measuring the ammonia deodorization performance again was repeated five times, the sixth deodorization rate was 35%. Was. Hydrogen sulfide was similarly carried out, 10 g of a measurement sample was placed in a hydrogen sulfide atmosphere kept at 100 ppm in a 2 liter container, the hydrogen sulfide concentration in the container was measured 24 hours later, and the deodorization rate was determined. . Initial performance is also JIS standard 10
The performance of the tubular knitted fabric after repeated washing was also insufficient with a hydrogen sulfide deodorization rate of 25%. The measurement of hydrogen sulfide for the sixth time after the repeated operation (measurement → washing) was repeated five times in the same manner as in the measurement of ammonia. As a result, the deodorization rate was 25% as in the initial performance.

Examples 2 to 4 The same as Example 1 except that the content of the layered compound in the sheath component was changed to the conditions shown in Table 1 by changing the blending ratio during spinning. And the deodorizing performance was evaluated.

[0030]

[Table 1]

It was confirmed that the fiberization process was good and the deodorizing performance was sufficient.

EXAMPLE 5 A layered compound based on aluminum tripolyphosphate having an average particle diameter of 0.3 μm was used as a base material. The base material was ion-exchanged with 1.5 moles of protons and silver ions and 0.5 moles of sodium ions. The obtained fine particles were kneaded with a polyethylene terephthalate resin by using a twin screw kneading extruder manufactured by Japan Steel Works, Ltd. to obtain a pellet containing 3 wt% of the fine particles in the polyethylene terephthalate resin. Next, the pellets were supplied to an extruder, and the obtained spinning raw yarn obtained by spinning at a spinning temperature of 300 ° C. and a spinning speed of 1000 in / min using a die having 24 spinning holes with a hole diameter of 0.2 mm was drawn under ordinary conditions. Then 75
A multifilament of 24 denier filaments was obtained. A knitted fabric was prepared, and the deodorizing performance before and after washing 10 times was measured. Table 2 shows the results.

Example 6 Nylon 6 was used as the resin to be used.
A pellet was obtained in the same manner as in Example 5, except for using. Next, the pellets were fed to an extruder, and a pore size of 0.2
spinning temperature of 2 mm with a spinneret having 24 holes
A drawn yarn of 75 denier and 24 filaments was obtained at 60 ° C. by a direct spinning drawing method. Next, a knitted fabric was prepared, and the deodorizing performance was measured.

[0034]

[Table 2]

Comparative Example 2 The same phosphate layered compound as in Example 1 was kneaded with a high-density polyethylene resin using a twin-screw kneading extruder manufactured by Japan Steel Works, Ltd. Then, a pellet containing 20 wt% of the fine powder was obtained. Next, when the spinning was carried out in the same manner as in Example 1 except that the pellet containing 20 wt% of the fine powder was used as a sheath component as it was, single yarn breakage and breakage during spinning frequently occurred. The stretchability was also poor.

Comparative Example 3 A taffeta woven fabric was prepared using polyethylene terephthalate 75 denier 24 filament drawn yarn. The same phosphate-type layered compound as in Example 1 and a urethane resin were mixed, and the mixture was coated on a taffeta fabric so that the layered compound was 2% by weight. The texture of the woven fabric became slightly hard and the texture was poor. As a result of measuring the ammonia deodorizing performance, the initial performance was 95.0%, which was sufficient, but after 10 washes, the coated layered compound dropped off sharply, and the performance was reduced to 35%, resulting in a reduced performance. did.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus for measuring deodorizing performance.

[Explanation of symbols]

 1: Ammonia sensor 2: Measurement sample 3: Ion meter 4: Recorder 5: Container

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int.Cl. ⁶ , DB name) D01F 1/10

Claims (1)

(57) [Claims] 1. A phosphate type layered compound having an average particle size of 5 μm or less and containing an antibacterial metal ion is mixed with a thermoplastic polymer having a melting point of 120 ° C. or more at 0.1 to 15% by weight. What fiber der that is, have the antibacterial
The metal ion to be formed is silver and / or copper, and phosphate
A layered compound particle containing a stabilizer,
The agent is an alkali metal and / or ammonia and / or
And the total of the metal ion and the stabilizer is phosphoric acid.
2 mol or less is added to 1 mol of the basic unit of the salt compound.
Fiber characterized layered compound der Rukoto phosphates-type has.