JP2012214919A - Fiber, fabric and clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber which prevents the occurence of yellow discoloration and red discoloration in the fiber while maintaining characteristics of a polyamide fiber such as dye-affinity, and also has superior deodorant effect; a fabric; and clothing.SOLUTION: The fiber contains a polyamide resin, an acidic compound and titanium oxide. The polyamide resin is at least one resin selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12. The acidic compound is a styrene-maleic anhydride copolymer or an acid anhydride. The fiber contains 0.15-3 pts. wt. of the acidic compound and 2.5-10 pts. wt. of titanium oxide with respect to 100 pts. wt. of the polyamide resin.

Description

The present invention relates to a fiber, fabric, and garment that suppresses the occurrence of yellowing and redness of the fiber and has an excellent deodorizing effect while maintaining the properties such as dyeability of the polyamide fiber.

Fibers made of polyamide resin (hereinafter also referred to as polyamide fibers) have excellent chemical and mechanical properties and are widely used as fibers for clothing and industrial materials. Such a polyamide fiber is an excellent fiber in that the polyamide resin constituting the fiber has an amino group at the molecular chain terminal and has good dyeability with an acid dye.

However, this amino group is active against acidic substances. For example, when it reacts with an acidic gas such as nitrogen dioxide gas in the air, a polyamide fiber or a fabric made of such a fiber is colored and yellowed. In some cases, the commercial value of the polyamide fiber product is significantly impaired. Specifically, there has been a problem that the polyamide fiber is yellowed by exhaust gas from a prime mover such as an automobile or exhaust gas from a petroleum heater such as a fan heater.

For this reason, various yellowing prevention methods have conventionally been proposed for polyamide fibers. For example, Patent Document 1 discloses an anion for the purpose of preventing yellowing of polyamide fibers packed and protected in paper. A method for treating polyamide fibers with a solution containing a compound having a system active group and acetic acid is disclosed. Patent Document 1 claims that by using such a method, an excellent yellowing prevention effect can be obtained as compared with single solution treatment with dilute sulfuric acid or acetic acid. However, this method has a problem that the dyeing property in the dyeing process is impaired unless the anionic active agent used in the treatment is removed by alkali scouring or the like.

Patent Document 2 proposes a method in which a polyamide fiber is treated with a solution containing an acylating agent, and an amino group is blocked with a covalent bond.
However, this method is excellent in yellowing resistance, but there is a problem that the yellowing resistance is insufficient in an aqueous medium unless a large amount of acid anhydride is used. Furthermore, it is difficult to block the amino group to such an extent that the dyeability is not affected, and the color developability of the polyamide fiber is also lowered.

With the improvement of living environment in recent years, interest in daily life odors has been increasing in order to ensure further comfort in living space, such as clothing field, life related field, sanitary material field, interior field, industrial material field. Many products with deodorant function and antibacterial function are on the market.
In particular, in the field of clothing products, various deodorization processing techniques have been developed since these are actually worn on the body, and development for other uses including interior products is also steadily being promoted.
One of the bad odors that should be taken into account when providing a deodorizing function is the smell of excrement. As an excrement odor, there is an ammonia odor that is decomposed into bacteria by urine and emits an odor, and it has been strongly demanded to remove the ammonia odor to further enhance the comfort of living space.
In addition, clothing and the like using a large amount of polyamide fiber have been required to impart deodorizing properties against bad odors such as ammonia odor.

Japanese Patent Publication No.55-47150 JP-A-4-272270

In view of the above situation, the present invention is a fiber, fabric, and garment that suppresses the occurrence of yellowing and redness of the fiber and has an excellent deodorizing effect while maintaining the properties such as dyeability of the polyamide fiber. The purpose is to provide.

The present invention is a fiber containing a polyamide resin, an acidic compound and titanium oxide, and the polyamide resin is at least one resin selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12. The acidic compound is a styrene-maleic anhydride copolymer or an acid anhydride, and 0.15 to 3 parts by weight of the acidic compound and 2.2 of titanium oxide with respect to 100 parts by weight of the polyamide resin. It is a fiber containing 5 to 10 parts by weight. The present invention is described in detail below.

As a result of intensive studies, the present inventor has added a predetermined amount of an acidic compound and titanium oxide to a fiber containing a specific polyamide resin, thereby causing yellowing or redness of the fiber during distribution process or use. It was found that the properties such as dyeability and the like possessed by the polyamide fiber can be maintained. Furthermore, the inventors have found that it is possible to greatly improve the deodorizing property against bad odor such as ammonia odor, and have completed the present invention.

The fiber of the present invention contains a polyamide resin made of at least one resin selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12.
The fiber containing the polyamide resin has excellent chemical and mechanical properties and high dyeability.

The at least one resin selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12 is not particularly limited, but may be a single composition, that is, a homopolymer. Other copolymerization components may be copolymerized so long as they are not impaired, for example, 50 mol% or less, preferably 10 mol% or less in all monomers.

The fiber of the present invention contains an acidic compound, and the acidic compound is a styrene-maleic anhydride copolymer or an acid anhydride.
In the present invention, by using such an acidic compound, the yellowing resistance of the fiber can be greatly improved.

When a styrene-maleic anhydride copolymer is used as the acidic compound, the effect of preventing yellowing is likely to be sustained even after repeated washing, particularly when the sweat component remains in the fiber and receives sunlight. Greatly suppresses discoloration in the environment.

The styrene-maleic anhydride copolymer has a segment derived from styrene and a segment derived from maleic anhydride, but the segment derived from styrene and the segment derived from maleic anhydride The ratio of the segment derived from styrene to 1 is preferably 1/3 to 1 and more preferably 1 to 1 based on maleic anhydride.

The preferable lower limit of the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is 1000, and the preferable upper limit is 50000. If it is less than 1000, the fiber surface may bleed out, and if it exceeds 50000, fuzzy yarn may be easily generated in the fiber.

Examples of the acid anhydride include phthalic anhydride, maleic anhydride, acetic anhydride, benzoic anhydride, succinic anhydride, nicotinic anhydride, propionic anhydride, -n-caproic anhydride, glutaric anhydride, formic anhydride, Examples thereof include tetrahydrophthalic anhydride and trifluoroacetic anhydride. Of these, phthalic anhydride is preferable.

The minimum of content of the said acidic compound in the fiber of this invention is 0.15 weight part with respect to 100 weight part of polyamide resins, and an upper limit is 3 weight part. If the amount is less than 0.15 parts by weight, the effect of suppressing yellowing and redness cannot be obtained. Or drop. The preferred lower limit of the content of the acidic compound is 0.2 parts by weight, the more preferred lower limit is 0.3 parts by weight, the preferred upper limit of the content of the acidic compound is 2 parts by weight, and the more preferred upper limit is 1.5 parts by weight. Part.

When the styrene-maleic anhydride copolymer is used as the acidic compound, a preferable lower limit of the content of the styrene-maleic anhydride copolymer in the fiber of the present invention is 0.000 parts by weight with respect to 100 parts by weight of the polyamide resin. 3 parts by weight, the preferred upper limit is 2.5 parts by weight. If the amount is less than 0.3 parts by weight, the effect of suppressing yellowing or redness may not be obtained. If the amount exceeds 2.5 parts by weight, the physical properties of the fiber itself may be reduced, or yarn breakage may occur during spinning. May occur and the spinnability may decrease. The minimum with more preferable content of the said styrene-maleic anhydride copolymer is 0.5 weight part, and a more preferable upper limit is 2 weight part.

When the acid anhydride is used as the acidic compound, the preferable lower limit of the content of the acid anhydride in the fiber of the present invention is 0.3 parts by weight with respect to 100 parts by weight of the polyamide resin, and the preferable upper limit is 2 parts by weight. It is. If the amount is less than 0.3 parts by weight, the effect of suppressing yellowing or redness may not be obtained. If the amount exceeds 2 parts by weight, the physical properties of the fiber itself may deteriorate, or yarn breakage may occur during spinning. As a result, spinnability may deteriorate. The minimum with more preferable content of the said acid anhydride is 0.5 weight part, and a more preferable upper limit is 1.8 weight part.

The fiber of the present invention contains titanium oxide.
By containing the above titanium oxide, it is possible to decompose organic substances by the oxidation-reduction action of titanium oxide, and in particular, to impart a deodorizing property against ammonia odor caused by sweat or urine. As a result, the fiber of the present invention can be suitably used for clothing that is in direct contact with the body such as clothing. Furthermore, the titanium oxide can realize excellent deodorizing properties even when compared with general inorganic fillers.
Moreover, the white color requested | required for underwear and sportswear can be obtained by containing a titanium oxide. Furthermore, a light-colored fiber can be obtained by adding a separate pigment based on the white color.
In addition, by containing titanium oxide, the feeling of stickiness when wet can be reduced, and a smooth texture can be obtained.

As the titanium oxide, any of rutile type titanium oxide, anatase type titanium oxide and brookite type titanium oxide is preferably used, and rutile type titanium oxide is particularly preferable.
The rutile-type titanium oxide is more susceptible to yarn breakage at the time of spinning due to breakage of the base polymer molecular chain in which the titanium oxide is dispersed, and fiber strength over time, compared to titanium oxide other than the rutile-type titanium oxide such as anatase-type titanium oxide. Defects such as deterioration hardly occur and can be used suitably.

Further, the titanium oxide is preferably subjected to a surface treatment, and examples of the surface treatment agent include metal oxides such as silica, alumina and zirconia; silane coupling agents, titanium coupling agents, organic acids, polyols. And organic substances such as silicone. Among these, titanium oxide surface-treated with at least one selected from silica, alumina and zirconia is preferable.

Although it will not specifically limit if the particle diameter of the said titanium oxide is a form which can achieve the effect of this invention, The preferable minimum of an average particle diameter is 10 nm, and a preferable upper limit is 2000 nm. When the average particle diameter of the titanium oxide is within the above range, it is possible to exhibit high deodorizing properties against bad odors such as ammonia odor. In addition, the value of the said average particle diameter can be obtained by calculating the arithmetic mean value of a maximum particle diameter from the photograph image | photographed with the electron microscope, for example.
When the average particle diameter is less than 10 nm, reaggregation tends to occur and the fibers may be fuzzy. When the average particle diameter exceeds 2000 nm, spinnability becomes unstable and yarn breakage may occur. is there.

The lower limit of the titanium oxide content in the fiber of the present invention is 2.5 parts by weight with respect to 100 parts by weight of the polyamide resin, and the upper limit is 10 parts by weight. When the amount is less than 2.5 parts by weight, the deodorizing property against bad odor such as ammonia odor is insufficient, and when the amount exceeds 10 parts by weight, the spinnability becomes unstable and yarn breakage may occur. A preferred lower limit is 3 parts by weight and a preferred upper limit is 8 parts by weight.

The fiber of the present invention preferably contains a phosphorus-based antioxidant. By containing the phosphorus-based antioxidant, it is possible to significantly improve the resistance to reddenation.
In the present invention, the phosphorus-based antioxidant refers to an antioxidant having a phosphorus atom, and is preferably an antioxidant having a P (OR) ₃ structure. Here, R is an alkyl group, an alkylene group, an aryl group, an arylene group, etc., and three Rs may be the same or different, and any two Rs are bonded to each other to form a ring structure. It may be.

Examples of the phosphorus antioxidant include tris- (nonylphenyl) -phosphite (manufactured by Ouchi Shinsei Chemical Co., Ltd., “NOCRACK TNP”), tris (2,4-di-t-butylphenyl) phosphite. ("Irgafos 168" manufactured by Ciba Japan Co., Ltd.), Tris [2-[[2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine (manufactured by Ciba Japan, “Irgafos12”), bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid (Ciba “Irgafos 38” manufactured by Japan Co., Ltd.), bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite (manufactured by Ciba Japan Co., Ltd., “Irgafo 126 "), tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite (Ciba Japan," IrgafosP-EPQ "), bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite (ADEKA, “ADEKA STAB PEP36”), distearyl pentaerythritol-di-phosphite (ADEKA, “ADEKA STAB” PEP-8 "), 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [ 1,3,2] dioxaphosphepine (manufactured by Sumitomo Chemical Co., Ltd., “Sumilyzer GP”) and the like.

The minimum with preferable content of the said phosphorus antioxidant in the fiber of this invention is 0.1 weight part with respect to 100 weight part of polyamide resins, and a preferable upper limit is 3 weight part. If the amount is less than 0.1 parts by weight, the effect of suppressing reddening may not be obtained. If the amount exceeds 3 parts by weight, bleeding from fibers tends to occur and powdering may occur. A more preferred lower limit is 0.4 parts by weight, a more preferred upper limit is 1.5 parts by weight, a still more preferred lower limit is 0.5 parts by weight, and a still more preferred upper limit is 1 part by weight.

The embodiment of the fiber of the present invention is not particularly limited, and may be composed of only the above polyamide resin, acidic compound and titanium oxide, but may be used in combination with other resins.

Moreover, the fiber of this invention may contain additives, such as a flame retardant, a ultraviolet absorber, an antistatic agent, a light stabilizer, an inorganic substance, and a higher fatty acid salt, in the range which does not impair the effect of this invention.

When the fiber of the present invention contains a resin other than the above polyamide resin, it may be formed by spinning a mixture of these resins or a conjugate fiber.
The other resin is not particularly limited, and examples thereof include polyester resins such as PET, PBT, and PTT, rayon, and acrylic.
When the other resin is used, in order to prevent discoloration and fading at the composite interface or the contact interface, the ratio similar to the ratio in which the acidic compound and the titanium oxide are added to the polyamide resin in the other resin as well. It is preferable to add at.

The conjugate fiber is not particularly limited, and examples thereof include a core-sheath conjugate fiber, a side-by-side conjugate fiber, a radial conjugate fiber, and a hollow annular conjugate fiber.
When the fiber of the present invention is the core-sheath conjugate fiber, the polyamide resin may be used for the core, the other resin may be used for the sheath, the other resin may be used for the core, and the polyamide may be used for the sheath. A resin may be used.

The shape of the core-sheath conjugate fiber is not particularly limited. For example, the cross-sectional shape when cut perpendicularly to the length direction of the fiber may be a perfect circle, or may be an ellipse or the like. Also good. Further, it may be a concentric core-sheath conjugate fiber in which a core part and a sheath part are formed concentrically, or an eccentric core-sheath conjugate fiber in which a core part and a sheath part are formed eccentrically. May be. Furthermore, it may be a partially open core-sheath conjugate fiber in which a part of the sheath is opened. In addition, a structure in which a plurality of core portions exist when cut perpendicular to the length direction of the fiber may be employed.

The form of the fiber of the present invention may be a multifilament or a monofilament.
In the case of a multifilament, the fineness of the multifilament is preferably 20 to 2400 dtex, and the fineness of the single yarn constituting the multifilament is preferably 1 to 20 dtex.
In the case of a monofilament, the fineness is preferably 1.1 to 10 decitex in consideration of convergence, durability and weaving when twisting.

The fiber of the present invention is preferably provided with a spinning oil comprising a nonpolar compound.
By applying the above spinning oil, the lubricity of the fibers is increased and the bleedout of the added acidic compound and titanium oxide is reduced.

In the present invention, a nonpolar compound is used as the spinning oil.
Examples of the spinning oil agent composed of the nonpolar compound include a silicone-based spinning oil agent and polyethylene wax. These may be used alone or in appropriate combination. In the present invention, it is preferable to use a silicone-based spinning oil.
In addition, the said spinning oil agent is provided to the fiber of this invention by a normal roller type or nozzle type oil supply method.

The preferable lower limit of the amount of the spinning oil in the fiber of the present invention is 0.1 part by weight with respect to 100 parts by weight of the fiber, and the preferable upper limit is 10 parts by weight. If the amount is less than 0.1 parts by weight, the friction between the fibers and the knitting needles increases, and the fabric may be damaged during knitting. If the amount exceeds 10 parts by weight, refining becomes difficult (the oil agent is sufficient when refining). May not fall). A more preferred lower limit is 0.3 parts by weight, and a more preferred upper limit is 8 parts by weight.

The method for producing the fiber of the present invention is not particularly limited, and for example, a conventionally known method such as a method of performing melt spinning using pellets containing the polyamide resin, acidic compound and titanium oxide can be used.
In the case of a conjugate fiber using the other resin, a polyamide resin, an acidic compound, and a pellet containing titanium oxide, and a pellet containing the other resin are put into a composite spinning apparatus, Examples thereof include a method of obtaining a conjugate fiber by melt spinning.

A fabric using the fiber of the present invention is also one aspect of the present invention.
In the present specification, the fabric includes a knitted fabric, a woven fabric, a non-woven fabric, and the like.
The fabric of the present invention may be composed only of the fiber of the present invention, but it is crossed with other fibers for the purpose of improving the requirements necessary for clothing such as the touch within the range not impairing the object of the present invention. You can knitting. Such other fibers are not particularly limited, and examples thereof include polyester, cotton, and rayon.
The clothing using the fiber of the present invention or the fabric of the present invention is also one aspect of the present invention.
Examples of the clothing of the present invention include leg wear such as socks and stockings, outerwear, underwear, gloves, arm covers, face masks, hats, mufflers, and the like.

According to the present invention, it is possible to provide fibers, fabrics and clothing that maintain the properties such as dyeability of polyamide fibers, suppress the occurrence of yellowing and redness of the fibers, and have an excellent deodorizing effect. .

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
100 parts by weight of nylon 6 (Ube Kosan Co., Ltd., “UBE nylon 1011FB”), 2.5 parts by weight of styrene-maleic anhydride copolymer (Sartomer Japan Co., Ltd., “SMA1000”), phosphorous oxidation 0.1 parts by weight of an inhibitor (manufactured by Sumitomo Chemical Co., Ltd., “Sumilyzer GP”), 0.3 part by weight of an ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), a light stabilizer (manufactured by Ciba Japan, After adding 0.3 part by weight of “Tinuvin 144” and 6 parts by weight of titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., “D-918”, average particle size: 260 nm), the resin is melt-mixed and resin is added using a pelletizer. A pellet was prepared.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Example 2)
100 parts by weight of polyamide 66 nylon (UBE Nylon 2015B), 1.5 parts by weight of styrene-maleic anhydride copolymer (Sartomer Japan, “SMA1000”), phosphorous oxidation 0.5 parts by weight of an inhibitor (manufactured by Ciba Japan, “Irgafos126”), 0.3 part by weight of an ultraviolet absorber (manufactured by Ciba Japan, “Cinuvin 234”), a light stabilizer (manufactured by Ciba Japan, After adding 0.3 part by weight of “Tinuvin 144”) and 5 parts by weight of titanium oxide (“D-918” manufactured by Sakai Chemical Industry Co., Ltd.), the mixture was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Example 3)
100 parts by weight of nylon 11 (manufactured by Arkema, “Rilsan BESNTL”), 0.5 part by weight of a styrene-maleic anhydride copolymer (manufactured by Sartomer Japan, “SMA1000”), a phosphorus-based antioxidant 1 part by weight (manufactured by ADEKA, “Adeka Stub PEP36”), 0.3 part by weight of ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), light stabilizer (manufactured by Ciba Japan, “Cinuvin 144”) After adding 0.3 part by weight and 4 parts by weight of titanium oxide (“D-918” manufactured by Sakai Chemical Industry Co., Ltd.), the mixture was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

Example 4
100 parts by weight of nylon 12 (Ube Industries, “UBESTA3014B”), polyamide resin 0.3 parts by weight of styrene-maleic anhydride copolymer (Sartomer Japan, “SMA1000”), phosphoric antioxidant 2 parts by weight (manufactured by Sumitomo Chemical Co., Ltd., “Sumilyzer GP”), 0.3 parts by weight of ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), light stabilizer (manufactured by Ciba Japan, “Cinuvin 144”) ) After adding 0.3 part by weight and 4 parts by weight of titanium oxide (“D-918” manufactured by Sakai Chemical Industry Co., Ltd.), the mixture was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Example 5)
100 parts by weight of nylon 6 (Ube Kosan Co., Ltd., “UBE nylon 1011FB”), 2.5 parts by weight of styrene-maleic anhydride copolymer (Sartomer Japan Co., Ltd., “SMA1000”), phosphorous oxidation 0.5 parts by weight of an inhibitor (manufactured by ADEKA, “Adeka Stub PEP36”), 0.3 part by weight of an ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), a light stabilizer (manufactured by Ciba Japan, Tinuvin 144 ") 0.3 parts by weight and titanium oxide (" D-918 "manufactured by Sakai Chemical Industry Co., Ltd.) 3 parts by weight were added, melted and mixed, and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Example 6)
Polyamide resin nylon 12 (Ube Industries, "UBESTA3014B") 100 parts by weight, phthalic anhydride 1.5 parts by weight, phosphorus antioxidant (Sumitomo Chemical Co., Ltd., "Sumilyzer GP") 0.5 parts by weight , 0.3 part by weight of an ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), 0.3 part by weight of a light stabilizer (manufactured by Ciba Japan, “Tinuvin 144”), and titanium oxide (Sakai Chemical) After adding 8 parts by weight of “D-918” manufactured by Kogyo Co., Ltd., it was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Example 7)
100 parts by weight of polyamide resin nylon 6 (Ube Industries, "UBE nylon 1011FB"), 1 part by weight of phthalic anhydride, phosphorus antioxidant (ADEKA, "Adeka Stub PEP36") 0.3 parts by weight, Phosphorus antioxidant (Ciba Japan, “Irgafos126”) 0.1 parts by weight, UV absorber (Ciba Japan, “Cinuvin 234”) 0.3 parts by weight, light stabilizer (Ciba Japan) After adding 0.3 part by weight of “Chinubin 144”) and 5 parts by weight of titanium oxide (“D-918” manufactured by Sakai Chemical Industry Co., Ltd.), the mixture is melt-mixed and resin pellets are obtained using a pelletizer. Produced.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Example 8)
Polyamide resin nylon 66 (Ube Industries, "UBE Nylon 2015B") 100 parts by weight, phthalic anhydride 0.5 parts by weight, phosphorus antioxidant (Sumitomo Chemical Co., "Sumilyzer GP") 0.5 Parts by weight, 0.3 part by weight of an ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), 0.3 part by weight of a light stabilizer (manufactured by Ciba Japan, “Tinuvin 144”), and titanium oxide ( After adding 4 parts by weight of “D-918” (manufactured by Sakai Chemical Industry Co., Ltd.), the mixture was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

Example 9
100 parts by weight of nylon 11 (Arkema, “Rilsan BESTNL”), 0.3 parts by weight of phthalic anhydride, 1 part by weight of a phosphorus-based antioxidant (ADEKA, “Adeka Stub PEP36”), UV absorption 0.3 parts by weight of an agent (manufactured by Ciba Japan, “Tinuvin 234”), 0.3 part by weight of a light stabilizer (manufactured by Ciba Japan, “Tinuvin 144”), and titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd.) , “D-918”) 3 parts by weight was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Example 10)
100 parts by weight of nylon 12 (Ube Industries Co., Ltd., “UBESTA3014B”), 1.5 parts by weight of phthalic anhydride, 0.3 part by weight of an ultraviolet absorber (Ciba Japan Co., Ltd., “Tinubin 234”), After adding 0.3 parts by weight of a light stabilizer (manufactured by Ciba Japan Co., Ltd., “Tinuvin 144”) and 5 parts by weight of titanium oxide (manufactured by Sakai Chemical Industry Co., Ltd., “D-918”), they were melt mixed. Resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Comparative Example 1)
100 parts by weight of nylon 6 (Ube Industries, “UBE nylon 1011FB”), 5 parts by weight of a styrene-maleic anhydride copolymer (Sartomer Japan, “SMA1000”), a phosphoric antioxidant 5 parts by weight (manufactured by ADEKA, “Adeka Stub PEP36”), 0.3 part by weight of ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), light stabilizer (manufactured by Ciba Japan, “Cinuvin 144”) After adding 0.3 part by weight and 5 parts by weight of titanium oxide (“D-918” manufactured by Sakai Chemical Industry Co., Ltd.), the mixture was melt-mixed and resin pellets were prepared using a pelletizer.
Subsequently, the obtained resin pellets were used for yarn production by a melt spinning method. Due to frequent filament breakage, the yarn could not be collected.

(Comparative Example 2)
100 parts by weight of nylon 66 (Ube Industries, “UBE Nylon 2015B”), 1 part by weight of a styrene-maleic anhydride copolymer (Sartomer Japan, “SMA1000”), a phosphorous antioxidant 0.2 parts by weight (manufactured by Sumitomo Chemical Co., Ltd., “Sumilyzer GP”), 0.3 parts by weight of UV absorber (manufactured by Ciba Japan Co., Ltd., “Tinubin 234”), light stabilizer (manufactured by Ciba Japan Co., Ltd., “Cinubin” 144 ") 0.3 parts by weight and 2 parts by weight of titanium oxide (" D-918 "manufactured by Sakai Chemical Industry Co., Ltd.) were added, melted and mixed, and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Comparative Example 3)
100 parts by weight of nylon 66 (Ube Industries, “UBE Nylon 2015B”), 1 part by weight of a phosphorus-based antioxidant (Ciba Japan, “Irgafos126”), UV absorber (Ciba Japan) Manufactured, "Tinubin 234") 0.3 parts by weight, light stabilizer (Ciba Japan, "Tinuvin 144") 0.3 parts by weight, and titanium oxide (Sakai Chemical Industry Co., Ltd., "D-918" ) After adding 5 parts by weight, it was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Comparative Example 4)
100 parts by weight of polyamide 11 nylon 11 (manufactured by Arkema, “Rilsan BESTNL”), 0.3 part by weight of styrene-maleic anhydride copolymer (manufactured by Sartomer Japan, “SMA1000”), UV absorber (Ciba -Japan Co., Ltd., "Tinubin 234") 0.3 parts by weight, light stabilizer (Ciba Japan Co., Ltd., "Tinubin 144") 0.3 parts by weight, and barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., "B -31 ") After adding 5 parts by weight, it was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Comparative Example 5)
Polyamide resin nylon 12 (Ube Industries, "UBESTA3014B") 100 parts by weight, styrene-maleic anhydride copolymer (Sartomer Japan, "SMA1000") 0.05 parts by weight, phosphorus antioxidant 0.05 parts by weight (manufactured by ADEKA, “ADEKA STAB PEP36”), 0.3 parts by weight of UV absorber (manufactured by Ciba Japan, “TINUVIN 234”), light stabilizer (manufactured by Ciba Japan, “TINUBIN 144”) “) 0.3 parts by weight and 5 parts by weight of titanium oxide (“ D-918 ”manufactured by Sakai Chemical Industry Co., Ltd.) were added, and then melt-mixed to prepare resin pellets using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Comparative Example 6)
100 parts by weight of nylon 11 (manufactured by Arkema, “Rilsan BESTNL”), 0.1 part by weight of phthalic anhydride, 0.6 parts by weight of a phosphorus-based antioxidant (ADEKA, “ADK STAB PEP36”), 0.3 parts by weight of an ultraviolet absorber (manufactured by Ciba Japan, “Tinuvin 234”), 0.3 part by weight of a light stabilizer (manufactured by Ciba Japan, “Tinuvin 144”), and titanium oxide (Sakai Chemical Industry) After adding 5 parts by weight of “D-918” manufactured by the company, it was melt-mixed and resin pellets were prepared using a pelletizer.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 130 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Subsequently, after rinsing with hot water of 50 ° C., heat setting was performed at 120 ° C. for 15 seconds.

(Comparative Example 7)
Nylon 6 (Ube Industries, “UBE Nylon 1011FB”) 100 parts by weight, UV absorber (Ciba Japan, “Tinuvin 234”) 0.3 parts by weight, light stabilizer (Ciba Japan) After adding 0.3 part by weight of “Chinubin 144” manufactured by the company and 5 parts by weight of “D-918” manufactured by Sakai Chemical Industry Co., Ltd., melt-mix and produce resin pellets using a pelletizer. did.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Subsequently, it was immersed in a 1% aqueous solution of acetic anhydride and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Comparative Example 8)
Nylon 6 (Ube Industries, “UBE Nylon 1011FB”) 100 parts by weight, UV absorber (Ciba Japan, “Tinuvin 234”) 0.3 parts by weight, light stabilizer (Ciba Japan) After adding 0.3 part by weight of “Chinubin 144”) and 5 parts by weight of titanium oxide (“D-918” manufactured by Sakai Chemical Industry Co., Ltd.), the mixture is melt-mixed and resin pellets are obtained using a pelletizer. Produced.
Next, using the obtained resin pellets, yarn was produced by a melt spinning method to obtain a raw yarn having a fineness of 120 dtex (36 filament configuration) and a diameter of about 20 μm per filament. The resulting raw yarn was knitted to produce a milling fabric.
The resulting milling dough is thoroughly washed and removed of the fiber oil, then dried and heat treated at 180 ° C. for 30 seconds. Next, it was immersed in water and treated at 40 ° C. for 10 minutes. Next, after rinsing with warm water at 50 ° C., heat setting was performed at 170 ° C. for 15 seconds.

(Evaluation)
The fabrics obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 1-2.

(1) Coatles yellowing test A dough sample of 3 cm × 10 cm was prepared and sandwiched between test papers containing 0.01% dibutylnitrophenol and further sandwiched between glass plates. Subsequently, the film was sealed with a film containing no dibutylhydroxytoluene (BHT), and a weight was placed on the film so that no gap was formed between the dough sample and the test paper, and the film was stored at 50 ± 3 ° C. for 16 hours. Thereafter, the sample was cooled to room temperature, the film and the glass plate were removed, and the degree of yellowing of the fabric was immediately measured by a gray scale (JIS L 0805). Evaluation was performed in 0.5 grade and 1 to 5 grade, and the case of grade 4 or higher was judged good.
In addition, using a fully automatic washing machine for household use (manufactured by Sharp Corporation, ES-S4A), the prepared fabric sample was “standard course”, detergent (attack (non-fluorescent)) 0.67 g / L, bath ratio 1:30. After washing without the net, it was left in a temperature-controlled room set at 40 ° C. for 12 hours.
The degree of yellowing after the washing / drying process was repeated 100 times was also measured.

(2) NOx yellowing test The degree of yellowing was measured using a colorimeter (Macbeth WHITE-EYE3000) in accordance with “Strong test” in JIS L 0855 “Testing method for fastness to dyeing with nitrogen oxides”. Then, the change (Δb ^* value) between before and after the test of the b ^* value of CIELAB color system was evaluated. It shows that yellowing is so large that (DELTA ⁾ b ^* value is large.
Δb ^* value = (b ^* value after test) − (b ^* value before test)

(3) Fan heater redness test After preparing a 5 cm × 10 cm fabric sample, place it at a distance of 90 cm from the outlet of a pump spray type petroleum fan heater (KD-25CTD manufactured by Mitsubishi Electric Corporation). After operating for a total of 24 hours, the degree of redness of the dough samples was examined. This evaluation takes into account the discoloration problem when NOx, SOx, and a high-humidity atmosphere act simultaneously. The degree of reddening is to colorimetry by using a colorimeter (Macbeth WHITE-EYE3000), was evaluated by the change in the previous test ^{a *} value of CIELAB color system and after the test (.DELTA.a ^* value). It shows that redness is so large that (DELTA) a ^* value is large.
Δa ^* value = (a ^* value after test) − (a ^* value before test)

(4) Sweat light resistance test Measured with an ultraviolet carbon arc lamp light resistance tester using an alkaline artificial sweat solution in accordance with JIS L 0888 "Method B" of "Dyeing fastness test method for light and sweat". It was.

(5) Ammonia deodorization test 28% ammonia water was added dropwise so that the concentration in a 1 L glass container was 100 ppm of ammonia. Next, 1 g of the dough sample was suspended in the glass container and sealed.
This sealed glass container was placed in a 50 ° C. constant temperature bath, and the ammonia concentration in the glass container after 2 hours was measured using a Kitagawa gas detector.
In addition, it shows that it is excellent in ammonia deodorizing property, so that a measured concentration value is small.

(6) Dyeing test
A 5 cm × 5 cm dough sample was prepared, and this was immersed in a solution containing an acidic dye at 100 ° C. for 30 minutes, and it was visually determined whether it was dyed or not dyed. In addition, as a liquid containing an acidic dye, Yellow C.I. I. 25% 3% solution, Blue C.I. I. 25% 3% solution and Red C.I. I. A 3% solution of 25 was used.
In addition, the determination was made by sensory evaluation by comparison with a control example in which the milling dough of Comparative Example 8 was immersed in a solution containing an acidic dye at 100 ° C. for 30 minutes.

According to the present invention, it is possible to provide a fiber, a fabric, and a garment that suppresses the occurrence of yellowing and redness of the fiber and has an excellent deodorizing effect while maintaining the properties such as dyeability of the polyamide fiber. be able to.

Claims (4)

A fiber containing a polyamide resin, an acidic compound and titanium oxide,
The polyamide resin is at least one resin selected from the group consisting of nylon 6, nylon 66, nylon 11 and nylon 12;
The acidic compound is a styrene-maleic anhydride copolymer or an acid anhydride,
A fiber comprising 0.15 to 3 parts by weight of the acidic compound and 2.5 to 10 parts by weight of titanium oxide with respect to 100 parts by weight of the polyamide resin. The fiber according to claim 1, further comprising a phosphorus-based antioxidant inhibitor. A fabric comprising the fiber according to claim 1 or 2. A clothing comprising the fiber according to claim 1 or 2 or the fabric according to claim 3.