JPS63135512A - Deodorizing polyolefin yarn - Google Patents

Abstract

PURPOSE:To obtain the titled yarn capable of being subjected to melt spinning, causing neither coloring nor change of color with time, yet having deodorizing function, by blending a spinnable polyolefin resin with specific inorganic fine powder as a deodorant. CONSTITUTION:A spinnable polyolefin resin is blended with 0.5-10wt% fine powder, having <=10mum particle diameter, of ferrous sulfate having <=20wt% sum of water of crystallization and free water, or aluminum sulfate, potash alum, sodium alum or zinc sulfate having <=5wt% sum of water of crystallization and free water as a deodorant and subjected to melt spinning to give the aimed yarn. Preferably master batch pellets containing the inorganic fine powder in high concentration is produced, the master batch is blended with a polyolefin resin for spinning in a given ratio and the blend is spun.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyolefin fiber containing an inorganic fine powder having a deodorizing ability, thereby having a deodorizing ability.

(Prior Art and Problems) Removal of bad odors generated in the living environment is a major topic in pursuit of living comfort. Regarding the removal of bad odors, it is known that there are products that are effective through various mechanisms such as masking action, adsorption action, and neutralization action, and deodorizing fibers that utilize these mechanisms are used in nursing homes, severely disabled people, etc. Its uses are also being expanded, mainly in storage facilities. However, if a deodorizer is applied, sprinkled, or dipped into paper, cloth, cotton, etc., there is a risk that the deodorizing effect will be impaired due to its own shedding, diffusion, or elution due to mechanical action from the outside. There is.

Polyolefin fibers such as polypropylene fibers and polyethylene fibers are used for paper, wet-laid non-woven fabrics, fishing rods, and other materials in the fishing industry due to their thermoplasticity, flexibility, high strength, and water resistance, and there is a demand for fibers that have a sustained deodorizing effect. There is.

On the other hand, deodorizing agents are broadly classified into those based on adsorption and those based on chemical reaction. Reactive deodorizers are quick and powerful against specific malodor sources.

It is known that ferrous sulfate removes ammonia and that the reaction product of ferrous sulfate and ammonia is capable of removing hydrogen sulfide.

(Japanese Patent Publication No. 30-6698, Japanese Patent Publication No. 51-50889) Recent research has shown that ferrous sulfate exhibits deodorizing ability through a similar mechanism even when blended with polyolefin polymers. It is being however,
Divalent iron compounds tend to become progressively oxidized under normal conditions, producing iron rust odors and iron rust colored stains and imparting colored stains to those with which they come into contact.

A method of using L-ascorbic acid in combination with the purpose of stabilizing a divalent iron compound is also known, but L-ascorbic acid generally tends to decompose at the melt-spinning temperature of polyolefin resin and impair spinnability. Thick.

(Objective of the Invention) An object of the present invention is to provide a polyolefin fiber that can be melt-spun and has a deodorizing function without discoloration over time.

The inventors of the present invention have conducted intensive research to achieve the above two objectives.
Fine powder of ferrous sulfate with a total amount of water of crystallization and free water of 20% by weight or less, or aluminum sulfate, potassium alum, sodium alum, or sulfuric acid with a total amount of 5% or less by weight of these in a spinnable polyolefin resin. By adding and mixing fine zinc powder as an inorganic fine powder deodorizing agent with a particle size of 10 μm or less, it can be melt-spun, does not color or discolor over time, has a deodorizing function, and also fulfills the original function as a fiber. The present invention was completed based on the discovery that polyolefin fibers having the following properties can be obtained.

The total amount of crystal water and free water used in the present invention is 20% by weight.
The following fine powder of ferrous sulfate and less than 5% by weight of aluminum sulfate, potassium alum, sodium alum, or zinc sulfate are substances that cannot be said to have good miscibility with resins, so the desired admixtures can be concentrated at high concentrations. It is preferable to prepare a master punch containing a resin, mix the masterbatch with a spinning resin at a predetermined ratio, and spin the mixture.

(Structure of the Invention) The present invention provides fine powder of ferrous sulfate having a total amount of water of crystallization and free water of 20% by weight or less, or a powder of ferrous sulfate having a total amount of 5% by weight or less of water of crystallization and free water, as a deodorizing agent for spinnable polyolefin resin raw materials. Concerning polyolefin fibers having a deodorizing function obtained by adding 0.5 to 10% by weight of fine powders of aluminum sulfate, potassium alum, sodium alum, or zinc sulfate as inorganic fine powders with a particle size of 10 μm or less and melt-spinning them. It is.

Ferrous sulfate can be obtained as a heptahydrate salt by a conventional manufacturing method, and is commercially available in this form. When ferrous sulfate heptahydrate is mixed with a spinnable polyolefin resin and heated to the melting temperature of the resin, part of the crystallized water is liberated and vaporized and foams, impairing spinnability.

On the other hand, when heptahydrate is heat-treated at about 120℃,
It loses most of its crystal water and becomes monohydrate. Ferrous sulfate monohydrate does not lose crystal water under normal melt spinning conditions and does not vaporize and foam during spinning. Ferrous sulfate heptahydrate is easily oxidized, has hygroscopic properties, and has extremely poor miscibility with hydrophobic resins, but monohydrate has greater resistance to oxidation and moisture absorption, and has good mixed phase properties. .

Ferrous sulfate is hydrophilic, so in addition to crystallization water, ferrous sulfate usually contains
It adsorbs so-called free water. Ferrous sulfate at 300℃, 1
Since it is recognized that all the water is removed by heating for about an hour, the weight loss rate in the treatment at 300° C. for 1 hour is defined as the total amount of crystal water and free water. When the total moisture content of water of crystallization and free water expressed in this way is 20% by weight or less, preferably 15% by weight or less, most of the ferrous sulfate exists as monohydrate, and some of the ferrous sulfate exists as monohydrate. It is considered to be mixed with salt and can be advantageously used for the purpose of the present invention.

The ferrous sulfate used in the present invention needs to be a fine powder. It is sufficient if the particle size is 10 μm or less, preferably 8 μm or less. The smaller the particle size, the fewer problems occur during spinning, and the larger the specific surface area, the greater the deodorizing ability.

The most stable form of aluminum sulfate is the 18-hydrate, that of potassium alum and sodium alum is the 12-hydrate, and that of zinc sulfate is the 7-hydrate. Commercially available products adsorb some free water in addition to crystallization water, and when these are added to spinnable polyolefin resin raw materials and melt-spun, these water vaporizes and foams, inhibiting spinnability. Also,
The deodorizer itself also causes undesirable phenomena such as re-dissolution and aggregation.

On the other hand, there are aluminum sulfate and its double salts which do not contain water of crystallization and are commercially available under the names of anhydrous aluminum sulfate or burnt alum.

When these anhydrous salts are stored under normal conditions, they tend to absorb moisture from the atmosphere. It is conceivable that the absorbed water is in the state of free water or partially crystallized water. As mentioned above, their total amount can be measured as the loss on heating at 300°C, but if this amount is less than 5% by weight of the salt used, phenomena such as vaporization foaming and aggregation will occur under normal melt spinning conditions. It is recognized that fibers suitable for the purposes of the present invention can be obtained without any modification.

It is necessary to use these anhydrous aluminum sulfate or calcined alum with a particle size of 10 μm or less, preferably 8 μm or less. In order to obtain a fine powder with a small particle size, it may be crushed and classified by air.

The spinnable polyolefin resin raw material used in the present invention includes, for example, polyethylene and polypropylene, but is not particularly limited as long as it can be melt-spun.

These are supplied to a spinning machine in the form of pellets, powder, beads, granules, etc., and are spun by applying heat and pressure. For spinning, a master pasotiber yarn containing the above resin raw material and a fine powder of ferrous sulfate monohydrate, anhydrous aluminum sulfate, calcined potassium alum, calcined sodium alum, or anhydrous zinc sulfate with a particle size of 10 μm or less is prepared at a high concentration. B. It is preferable to feed the master punch pellet and the resin to a spinning machine.

The content of these inorganic fine powder deodorizers is 0.0% relative to the resin.
If the content is 5 to 10% by weight, fibers can be obtained that have deodorizing properties in addition to their functions as fibers.

On the other hand, the above deodorizing agent is used at a high concentration, for example, 10 to 10
It is also possible to prepare a masterbatch containing 0% by weight.

When manufacturing the master patch, in order to ensure good dispersion of the deodorizer in the resin composition, the molecular weight is set in advance to 1. ．． 5
By kneading with a low molecular weight resin in the range of 00 to 60,000, coating the surface of the deodorant fine powder particles with the low molecular weight resin, mixing with a spinning resin, and pelletizing with an extruder for pellet forming. You can create a master punch pellet.

At this time, it is preferable to contain a resin having a molecular weight of 1,500 to 60,000 in an amount of 115 to 10 times the weight of the deodorant fine powder particles.

The low molecular weight resin used for particle surface coating and the resin for spinning do not need to be the same type of resin as long as they have sufficient compatibility, and resins with slightly different compositions can be used. The reason for using low-molecular-weight resins is that they have good fluidity and can be thoroughly kneaded, but if the molecular weight is too small, the viscosity will be too low, and the deodorant fine powder particles will have a higher specific gravity than the resin. Mixing becomes even more difficult.

When spinning the resin, it is also possible to add commonly used additives such as matting agents, colorants, and ultraviolet absorbers.

(Effect of the invention) Ferrous sulfate reacts with ammonia, and ferrous sulfate reacts with ammonia.
As already mentioned, the reaction product of iron and ammonia reacts with hydrogen sulfide, and ammonium sulfate and its double salt also react with ammonia to remove its odor. Polyolefin fibers having deodorizing performance are obtained by adding fine powders of ferrous sulfate, aluminum sulfate and their double salts, or zinc sulfate, each having a low moisture content, to a spinnable polyolefin resin and melt-spinning the mixture.

In the present invention, it is thought that the particles that actually exhibit the deodorizing effect are limited to particles exposed on the fiber surface and particles located near the surface and covered with a thin fiber skin layer.

Among them, those exposed on the surface are eluted by washing with water, but particles covered with a thin fiber skin layer are not eluted by washing, but are thought to react with malodorous component gases diffused in the fibers and deodorize them. In addition, the particles under such a thin fiber skin layer have a long-lasting effect, although their immediate deodorizing ability is inferior to particles exposed on the fiber surface, and they are resistant to oxidative deactivation caused by oxygen in the air. is also expected to be large.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 Commercially available ferrous sulfate heptahydrate was vacuum dried at 120° C. for 2 hours to obtain a powder with a total water content of crystal water and free water of 13.9 h. This powder was further finely pulverized using an ACM-10 type pulperizer (manufactured by Sokuyo Tekko Co., Ltd.), and air-classified using a micron separator MS-1 type manufactured by Honkawa Micron Co., Ltd. to obtain an average particle size of 3.2 μm. A fine powder with a maximum particle size of 63 μm was obtained. To 40 parts by weight of the above fine powder, add an average molecular weight of 50 parts by weight.
00, 19 parts by weight of low molecular weight polyethylene wax with a density of 0.93 g/cm' and tetrakis [methylene-3-(
1 part by weight of 3',5'-butyl-4'-hydroxyphenylzolopione-1 methane was added, and the mixture was melt-kneaded at 120°C using three rolls to obtain a wax-coated product. This wax coated product has a density of 0.923 jq
/cm3. Melt flow index 7g 710 minutes, 2
140 parts by weight of low-density porous IJ ethylene powder passing through a 0 mesh was added, mixed in a tumbler type blender, and then extruded using a singles free extruder at a reduced pressure of 350 Torr and a molten resin temperature of 130°C to form ferrous sulfate of 20 parts by weight. weight%
A polyethylene master patch pellet containing the following was prepared.

9 parts by weight of low-density polyethylene with a density of 0.9397 cm and a melt flow index of 5,971.0 to 1 part by weight of the master punch pellet thus produced;
4 parts by weight and 23 parts by weight were each blended and melt-spun using a 50-hole spinneret at a spinning temperature of 280°C. After temporarily winding the spun weeping yarn, it was heated at 85°C, 2 times at a magnification of 4.
Stretched at 0 and 130°C.

A drawn yarn bundle having a total denier of 300 deniers and a single yarn denier of 6 deniers was obtained by heat treatment at a relaxation rate of 8%.

The ferrous sulfate contents of this drawn yarn are 2%, 4%, and 67%, respectively.
It is Chi.

The spinning and drawing conditions were good with no yarn breakage.

9.7 t capacity containing ammonia concentration 90 ppm
2 g of the drawn yarn was put into a closed container, and the gas concentration was measured after 4 hours. As a result, the ammonia removal rates by the drawn yarn were 78%, 93%, and 95%, respectively.

Comparative Example 1 In place of the ferrous sulfate in Example 1, the total moisture content of crystal water and free water was 10.6%, but ferrous sulfate with an average particle size of 7 μm and a maximum particle size of 15 μm was used, and Example A master patch pellet having a ferrous sulfate content of 20% was prepared according to method 1. Using this master punch pellet, melt spinning was performed in the same manner as in Example 1.

During spinning, yarn breakage occurred frequently and winding could not be performed.

Example 2 Commercially available anhydrous aluminum sulfate (300°C ignition loss) 3
3 parts by weight was pulverized using the same apparatus as used in Example 1 to obtain a fine powder with an average particle size of 3.0 μm and a maximum particle size of 61 μm. To 40 parts by weight of this fine powder, an average molecular weight of about 50
00. 30 parts by weight of low molecular weight polyethylene wax with a density of 0.93 ji/cm3 was added, and 1
The mixture was melt-kneaded at 20°C to obtain a wax-coated product. To this wax-coated product, 180 parts by weight of low-density polyethylene powder having a density of 0.923, melt flow index of 7, and passing through 20 meshes was added, mixed in a tumbler-type blender, and then mixed using a single-screw extruder. A polyethylene master patch pellet containing 16% by weight of anhydrous aluminum sulfate was produced by extruding the molten resin at a temperature of 140°C.

One part by weight of the master patch pellet thus produced had a density of 0.939/1yn3 and a melt flow index of 4. ! 4 parts by weight and 2 parts by weight of 9/10 minute low density polyethylene were blended together under the same conditions as in Example 2 to obtain a drawn yarn bundle with a total denier of 300 denier and a single filament denier of 6 denier.

The aluminum sulfate content of this drawn yarn is 3.
Section 2, number 53.

The spinning and drawing conditions were good with no yarn breakage.

The ammonia concentration was measured under the same conditions as in Example 1, and the ammonia removal rates were 84% and 9, respectively.
It was 0chi.

Comparative Example 2 In place of the anhydrous aluminum sulfate used in Example 2, 30
An attempt was made to produce a master punch in the same manner as in Example 2 using a commercially available dehydrated aluminum sulfate powder with an ignition loss of 26% by weight at 0°C and a pass through 100 mesh of 75% or more, but during the wax kneading process, the particles Agglomeration and foaming caused poor dispersion, and it was not possible to obtain a uniformly dispersed coated product.

Furthermore, using this coated product, polyethylene masterbanotibele) was applied under the same conditions as in Example 2.
, Poly +) 1 part of ethylene master punch wavelet, 2 parts of melt flow indene and 5 parts of low density polyethylene were blended and melt spinning was performed under the same conditions as in Example 1, but there were many yarn breakages and winding was difficult. .

Example 3 Commercially available burnt potash alum (ignition loss at 300°C: 0.8% by weight) with an average particle size of 57 μm and a maximum particle size of 105 μm was air classified to produce fine particles with an average particle size of 3.5 μm and a maximum particle size of 70 μm. I got it. A wax-coated product was obtained according to the method of Example 1 using the burnt potassium alum fine particles. Density 0.9 0 9/1yn for 30 parts by weight of this wax coated product
3. Add 70 parts by weight of polypropylene powder with a melt flow index of 5, 5 g/l for 0 minutes and 20 meshes, mix in a tumbler type blender, then extrude using a single screw extruder at a molten resin temperature of 250°C. ,
A polypropylene masterbatch pellet containing 20% more burnt potassium alum by weight was produced.

Density 0.90 g/m to 1 part by weight of the burnt potassium alum/polypropylene master punch pellets obtained above,
9 parts by weight of polypropylene with a melt flow index of 4, 9/10 minutes was blended and melt-spun at 280°C under the same conditions as in Example 1. Stretched at 85°C to give a total denier of 300 denier and a single yarn denier of 6 denier. A thread was obtained.

Comparative Examples 3 and 4 Density 0.90ji/cm in 1 part by weight of burnt potassium alum/polypropylene master punch pellet of Example 3
, 50 parts by weight of polypropylene (Comparative Example 3) and 07 parts by weight (Comparative Example 4) with a melt flow index of 4 and 9/10 minutes were blended, and using the same conditions as Example 1, a total denier of 300 denier and a single yarn was prepared. Melt spinning was performed with the aim of obtaining a yarn bundle with a denier of 6 denier.

Example 4 Sodium alum crystals (12
water salt) was prepared, pre-dehydrated at 110°C, and then heated to 300°C.
It was fired in an electric furnace to produce anhydrous fired sodium alum.

This was roughly crushed with a hammer and then crushed with a ball mill. The powder was ground using a ball mill and classified using an air classifier to obtain fine particles with an average particle size of 2.5 μm and a maximum particle size of 5.8 μm. The calcined thorium alum fine particles were heated under the same conditions as in Example 3.
A polyethylene master bathoret containing 6% of weight was produced.

Density 0.9 to 3 g/cm per part by weight of sodium alum/polyethylene masterpanochiperenoto obtained above
, 3 parts by weight of low-density polyethylene with a melt flow index of 4 g/l 0 minutes was blended, and the mixture was melt-spun and stretched under the same conditions as in Example 2 to give a total denier of 300.
A drawn yarn bundle having a single yarn denier of 6 denier was obtained.

Example 5 Commercially available anhydrous zinc sulfate powder (ignition loss at 300°C: 1.5% by weight) was further ground into fine powder using a costomizer (manufactured by Nara Kikai Seisakusho Co., Ltd.), and air classified to obtain an average particle size. Diameter 2
A fine powder with a diameter of 3 μm and a maximum of 75 μm was obtained. A polyethylene master pellet containing 20% by weight of this fine powder was produced under the same conditions as in Example 1.

2.5 parts by weight of low-density polyethylene with a density of 0.93 i/1yn3 and melt 70-indenox 4 g/10 minutes was blended with 1 part by weight of the zinc sulfate/polyethylene master panochiheresoto obtained above. Melt spinning and drawing were carried out under the same conditions to obtain a drawn yarn bundle with a total denier of 300 deniers and a single filament denier of 6 deniers.

Comparative Example 5.6 1 part by weight of zinc sulfate/polyethylene master punch belene of Example 5 has a density of 0.93777 cm5 and a melt flow index of 4 g710 minutes of low-density polyethylene 7
0 parts by weight (Comparative Example 5) and 0.3 parts by weight (Comparative Example 6) were blended, and using the same conditions as in Example 1, a drawn yarn with a total denier of 300 denier and a single yarn denier of 6 denier was obtained. It was melt-spun for this purpose.

Table 1 summarizes the fiber compositions of Example 3.4.5 and Comparative Example 3.4.5.6, the spinning conditions, and the ammonia removal rates of the produced weeping yarns.

In Examples 3.4.5, good yarns were obtained with few yarn breakages during spinning and drawing. Moreover, the deodorizing performance was also sufficient. In Comparative Example 3.5, the conditions during spinning and stretching were good, but the ammonia removal function was insufficient. On the other hand, in Comparative Examples 4 and 6, many yarn breakages occurred during spinning and drawing, making them unsuitable for continuous production.

Claims (1)

[Claims] Ferrous sulfate, which is a fine powder with a particle size of 10 μm or less, and whose total amount of crystal water and free water is 20% by weight or less, or sulfuric acid whose total amount is 5% by weight or less, is added to the spinnable polyolefin resin. A deodorizing polyolefin fiber characterized by being melt-spun to contain 0.5 to 10% by weight of aluminum, potassium alum, sodium alum, or zinc sulfate.