JP6931037B2 - Deodorant fiber - Google Patents

Description

The present invention relates to deodorant fibers, and particularly to deodorant fibers that still have deodorant properties even after being washed with water a plurality of times, and deodorant mother particles used in the deodorant fibers.

In recent years, when selecting spun products by consumers, emphasis has been placed on comfort in use, such as moisture absorption and quick drying, heat storage and heat retention, refreshing tactile sensation, and antibacterial deodorization, whereas many functional fibers are on the market. It is being developed by demand. The need for clothing related to outdoor sports is increasing, and the removal of offensive odors remaining on clothing through sports activities is an extremely important part of consumer appeal. In addition, it is one of the demands of consumers to eliminate the body odor emitted from the human body by the function added to the spun product.

According to the existing technology of deodorant fiber, the deodorizing effect is achieved by adsorbing the odor on the surface of the fiber to which the activated carbon material such as bamboo charcoal or coconut charcoal is added.

The principle of deodorization by deodorant material is that although the adsorption effect is achieved by the porous material, the adsorption capacity by this porous material is limited. It is desirable to use it to neutralize the odor and then wash it with water to restore the deodorant material to its original function.

Regarding such deodorant fibers, according to CN102822411A (Cited Document 1), which is a Chinese patent gazette, when polyester fibers are immersed in an aqueous hydroxy acid solution and further heat-treated, they have both durability against washing with water and a deodorizing effect. Was disclosed.

As a method similar to this, according to CN103334456A (Reference 2), which is a Chinese patent publication, the woven fabric is immersed in an aqueous solution of titanium dioxide, irradiated with UV, and then further heat-treated to give the woven fabric the photocatalytic properties of titanium dioxide. It was disclosed that the effects such as antibacterial and deodorant were achieved.

Further, according to CN1756870A (Cited Document 3), which is a Chinese patent gazette, deodorant fine particles having a particle size of 0.1 to 1.5 μm are attached to fibers with a binder resin, and then heat-treated, dried and washed with water. Was disclosed. However, it has been disclosed that the use of a binder deteriorates the feel of the woven fabric and reduces the deodorizing effect after washing with water, which is a post-processing treatment.

According to CN1029787727A (Cited Document 4), which is a Chinese patent gazette, it is possible to improve the antibacterial effect by post-processing a fiber woven fabric made by spinning mother particles produced by using an antibacterial agent with an antibacterial agent. Disclosed.

CN102822411A CN103343456A CN1756870A CN1029787727A

In order to solve the above-mentioned problems of the existing technology, one object of the present invention is to disperse the deodorant powder modified by a modifier capable of improving the dispersibility of the deodorant powder in the fiber in the resin. It is to provide the technology to make it. This modified deodorant powder is an inorganic powder having excellent thermal stability, and is at least one selected from oxides of Al, Ti, Zn, Si, Fe, and Zr, and composite oxides thereof. And contains an inorganic powder having a particle size of 1 μm or less.

When the total weight of the modified deodorant powder of the present invention is 100 wt%, the modified deodorant powder contains 0.1 to 20 wt% of a silane coupling agent or a phthalate ester-based modifier, and is preferable. Contains 1-10 wt% 3-acryloxypropyltrimethoxysilane or stearoyl titanate.

Another object of the present invention is deodorization containing 50 to 95 wt% of a thermoplastic resin (polymer resin), 1 to 30 wt% of modified deodorant powder, and 0.01 to 5 wt% of an antioxidant. It is to provide the mother particle. Since the modified deodorant powder is uniformly dispersed in the resin, the bondability to the resin can be improved, and the increase value of the pressure loss when the deodorant mother particles pass through the filter is 0.5 bar. It can be said that it has a good deodorizing effect because it is less than / g and the deodorizing effect of the deodorizing fiber obtained by spinning can be maintained at 70% or more before and after washing with water.

The antioxidant of the present invention may be a hindered phenol-based or phosphite ester-based antioxidant, and is bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. It is preferable to have.

Another object of the present invention is to have a deodorizing effect even when a low-concentration deodorant is used, that is, a deodorizing substance capable of removing 70% or more of an odorous gas when deodorized for 2 hours. To provide fiber.
When the deodorant fiber of the present invention is washed with water, the deodorizing effect before and after washing with water is good.

The deodorant powder of the present invention is an inorganic powder having excellent thermal stability, and at least one selected from oxides of Al, Ti, Zn, Si, Fe, Zr and composite oxides thereof should be used. The particle size of this inorganic powder is 1 μm or less. Further, the surface of the inorganic powder is modified with a modifier such as a silane coupling agent or a phthalate ester. The amount of the modifier used is 0.1 to 20 wt%, preferably 1 to 10 wt%, based on 100 wt% of the modified inorganic powder (modified inorganic powder).

Examples of the silane coupling agent of the present invention include vinyl silicochlorochloro, vinyltrimethoxysilane, vinyltriethoxysilane, ethyltri (β-mesoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ. -(2-Aziridine) Aminopropyltrimethoxysilane, γ-epoxypropyroxypropyltrimethoxysilane, γ-epoxypropyroxypropyltrimethyldiethoxysilane, γ-epoxypropyroxypropyltriethoxysilane, γ-methylpropenylpropylmethyldimethoxy Silane, γ-methylpropenylpropyltrimethoxysilane, γ-methylpropenylpropylmethyldiethoxysilane, γ-methylpropenylpropyltriethoxysilane, N-β (aziridine) γ-aminopropylmethyldimethoxysilane, N-β (aziridine) γ-Aminopropyltrimethoxysilane, N-β (aziridine) γ-aminopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl -Γ-Aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, di- (3- [triethoxysilyl] -propyl) -tetrasulfide (TESPT) or di- (3-) [Triethoxysilyl] -propyl) -disulfide can be used, and 3-acryloxypropyltrimethoxysilane is preferably used.

As the titanium acid ester of the present invention, those selected from isostearyl titanate, stearoyl titanate, oleyl titanate and pyrophosphate titanate can be used, and stearyl titanate is preferably used.

As a procedure for modifying the deodorant powder of the present invention, first, the deodorant powder is put into a stirring tank using a fence type blade as a stirring blade, stirred at a rotation speed of 250 rpm, and after the modification. Weigh the modifier 3-acryloxypropyltrimethoxysilane so that 100 wt% of the deodorant powder (modified deodorant powder) occupies 1 to 10 wt%, and the modifier: isopropyl in terms of volume ratio. The modifier was diluted and dissolved with an isopropyl alcohol solvent so that alcohol = 1: 6, and the obtained diluted solution was gradually added dropwise to the deodorant powder at a dropping rate of 1 ml / min, and the mixture was stirred by a stirring tank. The speed was adjusted to 1000 rpm. After completion of the dropping, the temperature of the stirring tank was raised to 120 ° C., and the mixture was stirred for 2 hours to volatilize isopropyl alcohol to obtain a modified deodorant powder.

In the method for preparing the deodorant mother particles of the present invention, first, the modified deodorant powder is composed of 1 to 30 wt% of the modified deodorant powder and the polyester powder or the polyester granules as raw materials, and the intrinsic viscosity (IV) is 0. 50 to 95 wt% of thermoplastic polymer, which is 2 to 2.0, preferably 0.8, and 0.01 to 5 wt% of antioxidant are uniformly mixed to form a powder mixture, and then a twin-screw screw extrusion is performed. By kneading under the conditions of a kneading temperature of 180 to 280 ° C. and a kneading speed of 250 rpm using a machine, the thermoplastic polymer (resin) is in a molten state, and at that time, the modifier with the deodorant powder has. Since the end group has very high compatibility with the resin, the deodorant powder can be uniformly dispersed in the resin, and after water cooling and drying, it is pelletized, and further, 4 to 6 at a temperature of 140 ° C. The deodorant mother particles of the present invention were obtained by drying for a long time.

More specifically, since the surface of the deodorant powder composed of the inorganic material of the present invention is modified, the dispersibility in the resin can be improved, and the deodorant powder is more completely dispersed in the resin. We were able to. Therefore, in the spinning process using the deodorant mother particles of the present invention, the increase in pressure loss when passing through the filter is small, and good spinning can be performed over a long period of time.

As the antioxidant of the present invention, one selected from a hindered phenolic antioxidant or a phosphite ester antioxidant can be used.

Examples of the phosphite ester-based antioxidant include dimethyl 3,5-di t-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di t-butyl-4-hydroxybenzylphosphonate, 3,5-. Dipropyl g-t-butyl-4-hydroxybenzylphosphonate, dibutyl 3,5-g t-butyl-4-hydroxybenzylphosphonate, diamill 3,5-dit-butyl-4-hydroxybenzylphosphonate 3,5 -G-t-butyl-4-hydroxybenzylphosphonate dihexyl, 3,5-G-t-butyl-4-hydroxybenzylphosphonate dipentyl, 3,5-G-t-butyl-4-hydroxybenzylphosphonate dioctyl, bis ( 2,6-G t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate diethyl manganese, bis (3,5-di-) t-butyl-4-hydroxybenzyl) phosphonate diethylmagneside, bis (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate diethylcalcium, bis (3,5-di-t-butyl-4-hydroxy) Those selected from diethylzincide benzyl) phosphonate can be used, preferably bis (2,6-di t-butyl-4-methylphenyl) pentaerythritol diphosphite.

The deodorant fiber of the present invention is obtained by melt-spinning the deodorant mother particles after drying. The fiber structure of the deodorant fiber has a core portion made of polyester and a sheath portion made of deodorant mother particles, and the core-sheath ratio (core / sheath) is 40/60 to 60/40. A core-sheath type structure made of composite spinning having a (volume ratio) can be used. Since the deodorant is distributed in the outer layer of this fiber structure, it can efficiently react with the offensive odor gas.

The method for producing the deodorant fiber of the present invention first comprises composite spinning using the deodorant mother particles of the present invention as a raw material under the conditions of a spinning temperature of 230 to 290 ° C. and a spinning winding speed of 1000 to 3000 m / min. The deodorant fiber of the present invention is a processed yarn (DTY) having a diameter of 10 to 30 μm and a fiber fineness of 1 to 10 dpf by producing a semi-stretched deodorant yarn (POY) having a core-sheath structure and performing false twisting. Was produced.

In the deodorant fiber of the present invention, a core-sheath type structure is adopted as the fiber structure, and the fiber sheath portion is coated with deodorant powder, so that the deodorant effect of the deodorant fiber is high even after washing with water 10 times. Can be maintained. Therefore, the deodorant fiber of the present invention can be widely used in textile-related industries such as underwear, household decorations, and spun products for outdoor sports.

Hereinafter, some examples (Examples 1 to 4) will be illustrated to explain the production of modified deodorant powder and the processing into deodorant mother particles and deodorant fibers, and a comparative example as a control will also be given. Thereby, the object, effect and principle of the present invention will be described.

The modified deodorant powder and deodorant fiber produced in each Example and Comparative Example were evaluated for their physical properties according to the method described below.
1. 1. Test on increase in pressure loss: Dilute the deodorant mother particles with PET resin so that the final concentration of the deodorant mother particles is 8%, and use a filtration pressure increase tester (LabTech, model number: LTF34-GP). The increase value of the pressure loss of the deodorant mother particles when passed through a filter having a mesh of 15 μm was measured. The lower the increase value of the pressure loss, the higher the dispersibility of the deodorant powder in the polyester resin. On the other hand, the higher the increase value of the pressure loss, the lower the dispersibility of the deodorant powder in the polyester resin.
2. Deodorization test: Based on ISO 17299, a knitted fabric with a size of 10 cm x 10 cm (without distinguishing between the front and back surfaces) was prepared and left to stand in an environment of 20 ° C. RH 65% for 24 hours, and the concentration was different in 3 LTDlar-bag. A gas (ammonia gas 100 ppm or acetic acid gas 30 ppm) was filled, and the concentration of the gas in the bag after 120 minutes had passed was detected by a detector tube, and the rate of decrease in the gas concentration was calculated.

[Example 1]
<Modification for deodorant powder>
With reference to the compounding component A1 in Table 1, the deodorant powders Al ₂ O ₃ , ZnO, and SiO ₂ are charged into the stirring tank, and the stirring is performed at a rotation speed of 250 rpm by a stirrer using a fence type blade as the stirring blade. Then, the modifier 3-acryloxypropyltrimethoxysilane is weighed so as to occupy 1 wt% in 100 wt% of the modified deodorant powder, and the modifier: isopropyl alcohol = 1: 6 by volume ratio. The modifier was diluted and dissolved with isopropyl alcohol so as to be obtained, and the obtained diluted solution was gradually added dropwise to the deodorizing powder at a dropping rate of 1 ml / min, and the stirring speed by the stirring tank was adjusted to 1000 rpm. .. After completion of the dropping, the temperature of the stirring tank was raised to 120 ° C., and the mixture was stirred for 2 hours to volatilize isopropyl alcohol to produce a modified deodorant powder (modified deodorant powder A1).
<Production of deodorant mother particles>
Refer to the raw material components in Table 2, PET resin 79.5 wt%, modified deodorant powder A1 20 wt%, and bis (2,6-g t-butyl-4-methylphenyl) pentaerythritol diphosphite (2,6-G t-butyl-4-methylphenyl). Hereinafter, melt granulation was carried out using a twin-screw screw extruder using 0.5 wt% (hereinafter abbreviated as “antioxidant RPEP36”) as a raw material.
<Manufacturing deodorant fiber>
Spinning is performed under the conditions of a spinning temperature of 280 ° C. and a spinning speed of 2500 m / min, and the core portion is composed of dried polyester granules and the sheath portion is composed of dried deodorant mother particles, and the core-sheath ratio is 50. A partially drawn yarn (POY) of 75D / 72F, which is / 50, was obtained, further processed into a processed yarn (DTY), knitted and woven on a knitted fabric, and dyed and washed with water.
The increase value of the pressure loss of the obtained deodorant mother particles when passing through the filter was measured, and the results are shown in Table 2. Further, spinning is performed using the deodorant mother particles, further weaving is performed on the knitted fabric, dyeing is performed, the deodorizing effect is measured, and the results are shown in Tables 3 and 4. In addition, after washing the knitted fabric with water 10 times, a test for deodorant effect was performed, and the results are shown in Table 5. As a result, the deodorant effect could still be maintained at the initial level, in other words, the deodorant effect before and after washing with water was almost unchanged.

[Example 2]
In Example 1, the modified deodorant powder (modified deodorant powder A2) was used in the same manner as in Example 1 except that the amount of the modifier added was changed to 5 wt% (see compounding component A2 in Table 1). I made it.
Then, referring to the raw material components in Table 2, PET resin 79.5 wt%, modified deodorant powder A2 20 wt%, and antioxidant RCPEP36 0.5 wt% are used as raw materials and melted by a twin-screw screw extruder. Granulation was performed to produce deodorant mother particles.
The increase value of the pressure loss of the obtained deodorant mother particles when passing through the filter was measured, and the results are shown in Table 2. Spinning was performed using the deodorant mother particles, and after weaving the knitted fabric, dyeing was performed and the deodorizing effect was measured. The results are shown in Tables 3 and 4. After washing the knitted fabric with water 10 times, a test on the deodorizing effect was performed, and the results are shown in Table 5. As a result, the deodorant effect could still be maintained at the initial level, in other words, the deodorant effect before and after washing with water was almost unchanged.

[Example 3]
In Example 1, the modified deodorant powder (modified deodorant powder A3) was used in the same manner as in Example 1 except that the amount of the modifier added was changed to 10 wt% (see compounding component A3 in Table 1). I made it.
Then, referring to the raw material components in Table 2, PET resin 79.5 wt%, modified deodorant powder A3 20 wt%, and antioxidant RCPEP36 0.5 wt% are used as raw materials and melted by a twin-screw screw extruder. Granulation was performed to produce deodorant mother particles.
The increase value of the pressure loss of the obtained deodorant mother particles when passing through the filter was measured, and the results are shown in Table 2. Spinning was performed using the deodorant mother particles, and after weaving the knitted fabric, dyeing was performed and the deodorizing effect was measured. The results are shown in Tables 3 and 4. After washing the knitted fabric with water 10 times, a test on the deodorizing effect was performed, and the results are shown in Table 5. As a result, the deodorant effect could still be maintained at the initial level, in other words, the deodorant effect before and after washing with water was almost unchanged.

[Example 4]
In Example 1, the modified deodorant powder (modified deodorant powder) was the same as in Example 1 except that the modifier was changed to stearoyl titanate having an addition amount of 1 wt% (see compounding component A4 in Table 1). A4) was manufactured.
Then, referring to the raw material components in Table 2, PET resin 79.5 wt%, modified deodorant powder A4 20 wt%, and antioxidant RCPEP36 0.5 wt% are used as raw materials and melted by a twin-screw screw extruder. Granulation was performed to produce deodorant mother particles.
The increase value of the pressure loss of the obtained deodorant mother particles when passing through the filter was measured, and the results are shown in Table 2. Spinning was performed using the deodorant mother particles, and the fabric was further woven into a knitted fabric. After dyeing, a test on the deodorizing effect was performed, and the results are shown in Tables 3 and 4. After washing the knitted fabric with water 10 times, a test on the deodorizing effect was performed, and the results are shown in Table 5. As a result, the deodorant effect could still be maintained at the initial level, in other words, the deodorant effect before and after washing with water was almost unchanged.

[Comparative Example 1]
As a deodorant powder, an unmodified powder was prepared (see compounding component A5 in Table 1).
Then, referring to the raw material components in Table 2, PET resin 79.5 wt%, deodorant powder A5 20 wt%, and antioxidant RCPEP36 0.5 wt% are used as raw materials, and melt granulation is performed by a twin-screw screw extruder. This was done to produce deodorant mother particles.
The increase value of the pressure loss of the obtained deodorant mother particles when passing through the filter was measured, and the results are shown in Table 2. Spinning was performed using the deodorant mother particles, and after weaving the knitted fabric, dyeing was performed and a test on the deodorizing effect was performed. The results are shown in Tables 3 and 4. After washing the knitted fabric with water 10 times, the deodorant effect test was conducted again, and the results are shown in Table 5. As a result, the deodorizing effect could still be maintained at the initial level, in other words, the deodorizing effect before and after washing with water was almost the same, but the deodorizing effect was lower than in Examples 1 to 4. ..

As can be seen from the above test results, the deodorant powder modified with 3-acryloxypropyltrimethoxysilane, which is the modifier of Examples 1 to 3, and stearoyl titanate, which is the modifier of Example 4. Each of the deodorant powders modified by The increase value of the pressure loss at that time was measured, and as shown in Table 2, all of them were 0.5 bar / g or less, which means that the dispersibility of the deodorant powder in the polyester resin was very good. It means that.
The deodorant powder of Comparative Example 1 was kneaded and granulated with the resin and the dispersant as it was without being modified, and the obtained deodorant mother particles were dried, and then the pressure at the time of passing through the filter by the filtration pressure increase tester. When the increase value of the loss was measured, it was a value of 2.4 bar / g (see Table 2). Since this value exceeds 0.5 bar / g, it means that the dispersibility of the deodorant powder in the polyester resin was poor.
According to the above comparison results, the dispersibility of the deodorant powder that has been modified with the modifier in the polyester resin is improved, and the blocking phenomenon of the powder is reduced, so that the pressure loss is increased. It is considered that the spinning process of suppressing and producing deodorant fibers can proceed more smoothly.
After removing water by drying the deodorant mother particles obtained in Examples 1 to 4, a core-sheath type composite yarn in which the core portion and the sheath portion were each composed of polyester and deodorant mother particles was produced. Then, after winding into a roll, it was processed into a processed yarn, further woven into a knitted fabric, dyed, and then the related effect was evaluated. As a result, the deodorizing effect of spinning obtained using the modified deodorizing powder is higher than the deodorizing effect of the unmodified deodorizing powder (see Table 3), and even 10 times. The same tendency is shown even if it is washed with water (see Table 4).
In both Examples 1 to 4 and Comparative Example 1, no significant change was observed in the deodorizing effect of spinning before and after washing with water. This is because the deodorant powder itself is not incorporated into the knitted fabric by the impregnation process or coating process, which is post processing via a binder, but is directly bonded to the resin and incorporated into the fiber body. This is probably because there was no significant change in the deodorant effect before and after washing with water (see Table 5).

Claims (8)

A deodorant fiber obtained by melt-spinning deodorant mother particles, wherein the total weight of the deodorant mother particles is 100 wt%.
a) 50 to 95 wt% of a thermoplastic polymer composed of polyester powder or polyester granules and having an intrinsic viscosity of 0.2 to 2.0.
b) One or more powders selected from aluminum, titanium, zinc, silicon, iron, zirconium oxides and composite oxides thereof, and the surface thereof is modified with 3-acryloxypropyltrimethoxysilane. The amount of 3-acryloxypropyltrimethoxysilane used is 1 to 10 wt% with respect to 100 wt% of the total amount of the modified deodorant powder, and the modified deodorant powder contains a powder having a particle size of 1 μm or less. Odor powder 1 to 30 wt%,
c) Antioxidant 0.01-5 wt%,
Containing and
According to ISO17299, when the deodorant fiber is left in an atmosphere having an ammonia gas concentration of 100 ppm or an acetic acid gas concentration of 30 ppm for 2 hours, the concentration of ammonia gas or acetic acid gas decreases by 70% or more, and the deodorant fiber is used. A deodorant fiber characterized in that the concentration of ammonia gas or acetic acid gas decreases by 70% or more even when the product washed 10 times is left in an atmosphere having an ammonia gas concentration of 100 ppm or acetic acid gas of 30 ppm for 2 hours. The deodorant fiber according to claim 1, wherein the increase value of the pressure loss of the deodorant mother particles when passing through the filter is 0.5 bar / g or less. The deodorant fiber according to claim 1 or 2, wherein the deodorant fiber has a fiber fineness of 1 to 10 dpf. The deodorant fiber has a core-sheath structure, the core is made of polyester, the sheath is made of the deodorant mother particles, and the core-sheath ratio is 40:60 to 60:40. The deodorant fiber according to claim 3, which is characteristic. The deodorant fiber according to claim 3, wherein the deodorant fiber has a diameter of 10 to 30 μm. The deodorant fiber according to claim 1, wherein the thermoplastic polymer has an intrinsic viscosity of 0.8. The deodorant fiber according to claim 1, wherein the antioxidant is a hindered phenol-based antioxidant or a phosphite ester-based antioxidant. The deodorant fiber according to claim 1, wherein the antioxidant is bis (2,6-di - t-butyl-4-methylphenyl) pentaerythritol diphosphite.