JP3301709B2 - Fiber with excellent deodorant performance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber which has a good feeling similar to natural fibers, a good luster, a good hygroscopicity and a superior deodorizing performance and, as one component, ethylene-vinyl alcohol. The present invention relates to a conjugate fiber using a system copolymer.

[0002]

2. Description of the Related Art Polyester fibers are hydrophobic and therefore have a disadvantage that the fibers themselves are inferior in hygroscopicity and water absorption. Various proposals have been made to improve such disadvantages. As one of them, the present inventors have proposed a composite fiber of a polyester and an ethylene-vinyl alcohol-based copolymer (Japanese Patent Application No. 2-27826). However, the ethylene-vinyl alcohol copolymer is a polymer which is easily crosslinked and gelled by heating, and is a polymer which is difficult to handle. On the other hand, there have been attempts to add various functionalities by adding inorganic fine particles to fibers, and various proposals have been made. Among them, Japanese Patent Application Laid-Open No. 4-174711 discloses a fiber comprising an ethylene-vinyl alcohol-based copolymer, in which fine crystalline particles are added to the polymer to impart far-infrared characteristics. ing.

[0003] However, the fiber described in Japanese Patent Application Laid-Open No. 4-174711 is low in spinning temperature because it is a single fiber of an ethylene-vinyl alcohol copolymer. Gels due to crosslinking are less likely to be generated. In compounding with a fiber-forming thermoplastic polymer having a melting point exceeding 200 ° C., an ethylene-vinyl alcohol-based copolymer is liable to generate a gel by self-crosslinking,
Complex spinning at spinning temperatures close to 300 ° C. was accompanied by difficulty. In particular, when composite spinning is carried out by including fine particles in the copolymer, the fine particles act as an initiator for self-crosslinking of the copolymer or a nozzle fouling, which causes gel generation and poor fiberization processability, Composite spinning was not possible. Therefore, the above-mentioned proposal of the present inventors (Japanese Patent Application No.
No. 27826) could only contain fine particles in the polyester.

[0004]

The inventors of the present invention have studied the factors of self-crosslinking, gelation and nozzle fouling of ethylene-vinyl alcohol copolymer due to heat.
A method for preventing this was found, and it was possible to suppress the gelation of the ethylene-vinyl alcohol-based copolymer and to include a specific agent for imparting functionality to the copolymer, thereby enabling other polymers to be contained. -In particular, it has enabled composite spinning with a fiber-forming thermoplastic polymer having a high melting point.

[0005]

According to the present invention, there is provided an ethylene-vinyl alcohol copolymer (A) having an ethylene content of 25 to 70 mol% and a saponification degree of 95% or more, and a melting point of 20%.
A deodorizing performance comprising a composite fiber comprising a fiber-forming thermoplastic polymer (B) at 0 ° C. or higher, wherein (A) the polymer contains an antioxidant and a deodorant. Excellent fiber.

The polymer constituting the composite fiber of the present invention
As for (A), the one having a high degree of saponification of 95% or more and an ethylene content of 25 to 75 mol% is optimal. When the content of ethylene in the polymer (A) increases, that is, when the content of vinyl alcohol decreases, properties such as hydrophilicity are naturally lowered due to a decrease in hydroxyl groups, and a natural fiber-like feeling can be obtained. become unable.
Conversely, when the ethylene content is increased, that is, when the vinyl alcohol content is increased, the melt moldability is reduced, and in some cases, yarn breakage and single yarn breakage occur frequently during composite spinning. From such a viewpoint, the ethylene content in the polymer (A) is preferably from 28 to 55 mol%.

The polymer (A) is produced by saponifying an ethylene-vinyl acetate copolymer with caustic soda, and it is important that the degree of saponification is 95% or more as described above. When the saponification degree is low, the crystallinity of the polymer (A) is low, which causes not only a decrease in the strength of the conjugate fiber, and also a decrease in the strength of the fiber product, but also a decrease in the polymer.
(A) is likely to soften, and there is a high possibility that a problem will occur in the processing step.

Next, the polymer (B) will be described. The polymer (B) is a fiber-forming thermoplastic polymer having a melting point of 200 ° C. or higher, and examples thereof include polyester and polyamide. The polyamide is a polyamide mainly composed of nylon 6, nylon 66, and nylon 12, and may be a polyamide containing a small amount of the third component.

As the polyester, terephthalic acid, isophthalic acid, naphthalene 2,6-dicarboxylic acid, phthalic acid, α, β- (4-carboxyphenoxy) ethane,
Aromatic dicarboxylic acids such as 4,4-dicarboxydiphenyl and 5-sodium sulfoisophthalic acid; adipic acid;
Aliphatic dicarboxylic acids such as sebacic acid or esters thereof, ethylene glycol, diethylene glycol,
1,4-butanediol, 1,6-hexanediol,
Polyesters composed of diol compounds such as neopentyl glycol, cyclohexane 1,4-dimethanol, polyethylene glycol and polytetramethylene glycol can be mentioned. %, Especially 90 mol% or more is a polyester having ethylene terephthalate units or butylene terephthalate units.

In the present invention, in melt-spinning a composite fiber composed of the polymer (A) and the polymer (B), the generation of gel due to self-crosslinking due to the heating of the polymer (A) is suppressed. It has a great feature in that it contains an antioxidant and also contains a deodorant to impart functionality. The antioxidant to be contained in the polymer (A) is a hydroxytertiary butylphenyl compound, in which the hydroxy group is located at the ortho position to the butyl group (hereinafter referred to as a phenolic compound). ) Is preferable, and it is preferable to add 0.08% by weight or more based on the polymer (A). The phenolic compound is generally used as an antioxidant,
Many kinds of antioxidants are known in addition to the phenolic compound, but the phenolic compound, particularly the compound containing a nitrogen atom, is a polymer (A) having a stability at the time of spinning, particularly a gelation inhibitor. It has a remarkable effect in terms of Generally, when inorganic fine particles are added, depending on the type of the fine particles, thermal decomposition of the polymer (A) or gelation may be promoted. The effect of promotion can be greatly suppressed. Despite the large amount of deodorants described below,
Excellent spinnability is provided by the action of the phenolic compound. Phenol-based compound polymer
As described above, the amount added to (A) is preferably 0.08% by weight or more, but if it is less than 0.08% by weight, the effect of improving spinnability is not exhibited. The upper limit of the amount of the antioxidant added is not particularly limited, but is preferably 5% by weight or less, and particularly preferably in the range of 0.1 to 3% by weight.

The phenolic compounds suitably used in the present invention include compounds represented by the following chemical formula (1).

Embedded image In the formula, M represents an organic group, R represents an alkyl group, and n represents an integer of 1 to 3. However, when n is 2 or more, R may be the same or different. Specific compounds include the following compounds.

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The deodorant used in combination with the above-mentioned antioxidant is a component which adsorbs odor components or reacts with odor components to exhibit a deodorizing effect, and is a substance which is hardly decomposed or volatilized during fiber formation. There is no particular limitation. Specific examples of such a deodorant include activated alumina, silica gel, activated clay, zeolite, and an adsorbent having inorganic ultrafine pores mainly composed of active zinc oxide, fumaric acid,
Organic deodorants such as iron ascorbic acid compounds, metal phthalocyanine compounds, metal porphyrin compounds, flavonoid compounds, amino acid compounds, tannin compounds, and saccharides can be mentioned.
A deodorant which reacts with (A) and easily gels is not preferred. Among them, various odor components such as acidic odor components such as lower fatty acids such as formic acid, acetic acid, propionic acid and valeric acid, basic odor components such as nitrogen-containing compounds, sulfur-containing compounds and neutral odor components such as aldehydes can be effectively used. It is preferable to use a deodorant consisting of a phosphate of a tetravalent metal, a hydroxide of a divalent metal and a photocatalyst which can be removed.

Hereinafter, this deodorant will be described. The photocatalyst that constitutes the deodorant refers to a photocatalyst that generates active radicals by irradiation with light such as ultraviolet rays, oxidizes and decomposes many harmful substances and malodorous substances, and functions as a photooxidation catalyst. Therefore, the photocatalyst often belongs to the category of the oxidizing photocatalyst. When such a photocatalyst is used, the odor can be deodorized using catalytic decomposition instead of a mere adsorption action, so that the deodorizing or deodorizing effect can be maintained for a long time. Further, this photocatalyst not only decomposes harmful substances and malodorous substances, but also has a bactericidal action, an antibacterial action and the like.

As the photocatalyst, various optical semiconductors can be used regardless of whether they are inorganic or organic. In many cases, the photocatalyst is an inorganic optical semiconductor. As the photocatalyst, for example, a sulfide semiconductor (Cd
S, ZnS, In ₂ S ₃ , PbS, Cu ₂ S, Mo
S ₃ , WS ₂ , Sb ₃ S ₃ , Bi ₃ S ₃ , ZnCdS ₂
Etc.), metal chalcogenite (CdSe, In ₂ Se ₃ ,
WSe ₃ , HgSe, PbSe, CdSe, etc.), oxide semiconductors (TiO ₂ , ZnO, WO ₃ , CdO, In ₂ O)
₃ , Ag ₂ O, MnO ₂ , Cu ₂ O, Fe ₂ O ₃ , V ₂
O _5, SnO _2, etc.) and the like, as a semiconductor other than an oxide and sulfide, GaAs, Si, Se, CdP _3,
Zn ₂ P _{3 and the} like are also included. These photocatalysts can be used alone or in combination of two or more.

Among these photocatalysts, sulfide semiconductors such as CdS and ZnS, TiO ₂ , ZnO, SnO ₂ and WO ₃
Oxide semiconductors such as TiO ₂ and ZnO are particularly preferable. The crystal structure of the optical semiconductor constituting the photocatalyst is not particularly limited. For example, TiO ₂ may be any of anatase type, brookite type, rutile type, amorphous type and the like. Particularly preferred TiO ₂ is an anatase type.

The photocatalyst can be used in the form of a sol or a gel, or may be used in the form of a powder. When the photocatalyst is used in the form of powder, the average particle size of the photocatalyst can be selected within a range that does not impair the photoactivity and deodorization efficiency.
Preferably it is 0.05-1 μm. If the particle size exceeds 5 μm, for example, filter clogging and fluff breakage are likely to occur during melt spinning. If it is too small, secondary aggregation is likely to occur, which may cause problems such as filter clogging.

The amount of the photocatalyst used can be selected from a wide range which does not impair the catalytic activity, for example, 0.1 to 25% by weight, preferably 0.3 to 20% by weight, based on the whole fiber.
It is more preferably in the range of 0.5 to 15% by weight, and generally in the range of 0.5 to 10% by weight in many cases.

Next, a phosphate of a tetravalent metal and a hydroxide of a divalent metal constituting the deodorant will be described. As long as the tetravalent metal forming the phosphate is a tetravalent metal, the group in the periodic table is not particularly limited, and the tetravalent metal includes a group 4 element of the periodic table, for example, a group 4A element (titanium, zirconium, Hafnium, thorium, etc.) and 4B group elements (germanium, tin, lead, etc.). Among these metals, metals belonging to Group 4A elements of the periodic table, such as titanium, zirconium, hafnium, and Group 4B elements, such as tin, are preferable, and titanium and zirconium are particularly preferable.

The phosphoric acid constituting the phosphate includes various phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, and the like.
Triphosphate, tetraphosphate and the like. Phosphoric acid is often orthophosphoric acid, metaphosphoric acid or pyrophosphoric acid. Phosphates also include hydrogen phosphates such as ortho hydrogen phosphate. In this specification, phosphoric acid means orthophosphoric acid unless otherwise specified.

These tetravalent metal phosphates are generally insoluble or poorly soluble in water. Further, the phosphate may be a crystalline salt, but is preferably an amorphous salt. These tetravalent metal phosphates can be used alone or in combination of two or more.

The divalent metal forming the hydroxide may be a divalent metal irrespective of the group of the periodic table. The divalent metal includes, for example, a Group 1B element of the periodic table such as copper, magnesium,
Periodic table 2A for calcium, strontium, barium, etc.
Periodic table of group 2B elements such as zinc, cadmium, etc. Periodic table 8 of group 6A elements such as chromium and molybdenum, group 7A elements such as manganese, iron, ruthenium, cobalt, rhodium, nickel and palladium Group elements and the like. These divalent metal hydroxides may be used alone or in combination of two or more.

Preferred divalent metals include transition metals, for example, Group 1B elements such as copper, Group 2B elements such as zinc, Group 7A elements such as manganese, and Periodic Table 8 such as iron, cobalt and nickel. Group elements. Preferably copper,
Zinc, iron, cobalt and nickel.

These divalent metal hydroxides are usually insoluble or poorly soluble in a weakly acidic to weakly alkaline region (pH 4 to 10). The hydroxide may be crystalline, but is often amorphous.

The ratio between the phosphate of the tetravalent metal and the hydroxide of the divalent metal can be selected within a range that does not impair the catalytic activity, the ability to adsorb to odor components and the ability to deodorize. Atomic ratio (divalent metal / tetravalent metal) = 0.1-1
0, preferably 0.2 to 7, more preferably 0.2 to
5 range. When a plurality of phosphates and / or hydroxides are used in combination, the metal atomic ratio based on the total amount of each metal may be within the above range. Further, a composition composed of a phosphate of a tetravalent metal and a hydroxide of a divalent metal may be compounded by coprecipitation or the like like a mixed gel. In particular, when a deodorant composed of a combination of a phosphate of a tetravalent metal and a hydroxide of a divalent metal and the above-described photocatalyst are used in combination by mixing or coprecipitation, a high catalytic activity is obtained. Thus, various compounds such as odor components can be efficiently removed over a long period of time.

The total amount of the phosphate of the tetravalent metal and the hydroxide of the divalent metal can be appropriately selected similarly to the amount of the photocatalyst.
For example, it is preferably in the range of 0.1 to 25% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight based on the whole fiber. In addition, the amount of the photocatalyst is 1 to 1000 with respect to 100 parts by weight of the total amount of the above-mentioned phosphate and hydroxide.
Parts by weight, preferably 10 to 750 parts by weight, more preferably 20 to
The range of -500 parts by weight is preferred.

The above-mentioned phosphates of tetravalent metals and hydroxides of divalent metals may be combined with silicon dioxide which is useful for increasing the specific surface area and increasing the adsorption capacity. As silicon dioxide, an inorganic polymer which itself has a high molecular weight,
A composite compound of silicon dioxide and a tetravalent metal phosphate may, for example, be mentioned. Further, silicon dioxide may be hydrated silicon dioxide. Such silicon dioxide may be crystalline, but is preferably amorphous. The content of silicon dioxide can be selected within a range that does not decrease the catalytic activity or adsorption performance of the photocatalyst. For example, the content of silicon / (tetravalent) in terms of metal atom ratio with respect to the total amount of the above-mentioned phosphate and hydroxide is described. Metal and divalent metal) = 0.2 to 10, preferably 0.5
-8, more preferably 1-7.

The above-mentioned deodorant is preferably an amorphous substance, particularly a coprecipitated substance formed by coprecipitation. The amorphous deodorant produced by co-precipitation is usually from 10 to 1000 m ² /
g, preferably 30 to 1000 m ² / g, more preferably 50 to 1000 m ² / g. Therefore, the fiber containing such a deodorant functions as a deodorant fiber having a high deodorant property,
It also has antibacterial performance.

The deodorant can be obtained by various conventional methods. For example, by mixing a tetravalent metal phosphate, a hydroxide of a divalent metal, and a photocatalyst with another deodorant (such as silicon dioxide) as necessary, a deodorant can be easily obtained. . At the time of the mixing, the respective powdery components obtained by pulverization or the like may be mixed.

The adjustment of the photocatalyst is carried out according to a conventional method, for example, a method of forming a water-insoluble precipitate from an aqueous solution containing a metal ion corresponding to the photocatalyst, a method of adjusting from a metal alkoxide, a gas phase method of oxidizing at a high temperature, and the like. be able to.

In producing the photocatalyst, a compound containing a component corresponding to the catalyst can be used. This will be described using titanium oxide as an example. TiC as such a component
titanium halide such as l ₄ , TiF ₄ , TiBr ₄ , T
i (SO ₄ ) ₂ , sulfates such as TiOSO ₄ , (CH
₃ O) ₄ Ti, (C ₂ H ₅ O) ₄ Ti, [CH ₃ (CH
₂ ) O] ₄ Ti, [(CH ₃ ) ₂ CHO] ₄ Ti, [C
H ₃ (CH ₂ ) ₃ O] ₄ Ti, [(CH ₃ ) ₂ CHCH
C _1-6 alkoxy titanium such as ₂ O] ₄ Ti can be used. Alternatively, a titanium oxide sol or the like that has been adjusted in advance may be used.

As the deodorant, a solution containing a tetravalent metal ion, a divalent metal ion and a component corresponding to a photocatalyst, or an aqueous solution containing two or more metal ions among these metal ions can be used. Can be also obtained by a method of producing a mixed precipitate of water-insoluble substances. The mixed precipitate obtained by this method is usually in a gel state, and becomes a mixture having an amorphous structure by drying. In this method, it is preferable that the component corresponding to the photocatalyst is adjusted to an appropriate crystal structure in advance and added to the aqueous solution.

Various aqueous metal compounds are used for adjusting the aqueous solution containing tetravalent metal ions and divalent metal ions. Examples of such a water-soluble metal compound of a divalent metal or a tetravalent metal include various metal salts and metal alkoxides. As the metal salt, a normal metal salt (normal salt)
In addition, metal salts in the form of acid salts, oxy salts, and other double salts and complex salts may be used. The metal salt is p
Even if H is a compound that is insoluble near neutrality, it may be a compound that dissolves in an acidic solution. Of these metals,
In many cases, inorganic acid salts, particularly strong acid salts such as sulfates and nitrates, are used. In addition, an oxymetal salt is often used as a titanium compound or a zirconium compound among tetravalent metal compounds.

In order to produce a phosphate of a tetravalent metal and a hydroxide of a divalent metal, a hydroxide of a divalent metal is produced in the presence of a phosphate of a tetravalent metal and a divalent metal ion. Just do it. For example, (i) a phosphate of a tetravalent metal may be formed in an aqueous solution in which a tetravalent metal ion and a divalent metal ion coexist, and then a hydroxide of a divalent metal may be formed; After a phosphate of a tetravalent metal is previously generated in an aqueous solution containing no divalent metal ion, an aqueous solution containing a divalent metal ion may be added to generate a hydroxide of the divalent metal.

The photocatalyst may be added to the reaction system for producing the phosphate of the tetravalent metal and the hydroxide of the divalent metal, for example, in the form of powder, and the phosphate and / or the tetravalent metal may be added.
Alternatively, after a hydroxide of a divalent metal is generated, it may be added to a reaction system or a generated precipitate.

Further, the photocatalyst may be formed simultaneously with the formation of the phosphate of the tetravalent metal and / or the hydroxide of the divalent metal. For the production of the photocatalyst, the above methods (i) and (ii) can be used. For example, when producing titanium oxide, a titanium halide such as titanium chloride, an inorganic acid salt (sulfate such as titanium sulfate) or an alkoxide is added to the reaction system as required, and the pH of the reaction system is adjusted to neutral or alkaline. It can be generated by adjusting to.

When preparing a composition containing silicon dioxide, silicon dioxide and / or silicate ion species may be added in at least one step of the precipitate formation reaction, and the photocatalyst component and the like may be added. Silicon dioxide may be mixed with the resulting precipitate containing the silicon dioxide. When silicon dioxide is formed together with the formation of the precipitate, an alkaline silicate solution (eg, sodium silicate, potassium silicate, etc.) can be used instead of alkali.
When a silicate ion species is used, a hydrous silicon dioxide can be generated by adjusting the pH to a neutral range of 4 to 12 together with the generation of a hydroxide of a divalent metal.

The precipitate thus obtained may be purified by a conventional method, if necessary. For example, the reaction solution containing the precipitate such as the mixed precipitate is filtered, washed with a washing solvent such as warm water or water, to remove impurities such as metal salt anion species, and purified by drying. A deodorant can be obtained. The filtration can be performed under normal temperature, normal pressure, reduced pressure, or increased pressure using a filter paper, a filter cloth, or the like, and may be performed using a centrifugal separation method, a vacuum filtration method, or the like. In cleaning, an inclined cleaning method or the like may be used. The drying operation may be performed by a conventional method, for example, air drying, and may be performed at a temperature lower than the decomposition temperature of the deodorant, for example, about 4 ° C.
The heat treatment may be performed at a heating temperature of not higher than 00 ° C, preferably not higher than 200 ° C.

As a method of adding the deodorant to the polymer (A), a master batch is prepared by adding a deodorant to the polymer (A), and the master batch is used. There is a method in which a deodorant is added at an arbitrary stage until the polymer (A) is spun (for example, at a stage of preparing a polymer pellet, at a stage of melt spinning, etc.). Among these methods, there are a method in which a deodorant is added to a raw material slurry of the polymer (A), a method in which a deodorant is added immediately after the prepolymer is produced and the prepolymer is further subjected to polycondensation, A method of adding a deodorant immediately after the polymerization of (A) and while it is still in a liquid state may be employed. However, since the deodorant has a very high catalytic activity, depending on the type of the polymer, Care must be taken as the reaction may proceed. Considering the process, the master-batch method described above is preferable.

The above-mentioned deodorants can be used alone or
More than one species may be used in combination. The amount of the deodorant varies depending on the type of the deodorant, but if the amount is too small, the deodorizing performance becomes insufficient.On the other hand, if the amount is too large, the stability of the spinning process is reduced, and the mechanical properties of the obtained fiber are reduced. The strength also tends to decrease. For this reason, 0.5 to the polymer (A)
The range is preferably from 15 to 15% by weight, particularly preferably from 1.0 to 10% by weight.

The composite form of the polymer (A) and the polymer (B) is not particularly limited, and may be any composite form capable of deodorizing performance. Therefore, it is preferable that 30% or more, particularly 60% or more of the fiber cross-sectional circumference is made of the polymer (A). Specifically, a core-sheath type composite fiber in which the polymer (A) forms the sheath and the polymer (B) forms the core, the polymer (A) and the polymer (B) are laminated side by side. Composite fiber, polymer
Examples thereof include a multilayer-bonded conjugate fiber in which (A) and a polymer (B) are alternately multilayer-bonded, and a non-uniform mixed conjugate fiber in which the composite form is random between single fibers. Among these, from the viewpoint of the deodorizing effect, examination type composite fibers, multi-layer bonded type composite fibers, and heterogeneous mixed fibers having a large fiber cross-sectional circumference of the polymer (A) are preferable.

In the case of a core-sheath type composite fiber, it can be used as it is as a textile product for clothing and living purposes, but it is used as a false twisted yarn for woven or knitted fabric, or as a raw yarn structure yarn by air entanglement. It is also possible to

In the case of the multi-layer laminated conjugate fiber and the random conjugate fiber, they can be used as a fiber product as they are, but it is difficult to form a fibrous product by splitting fibrils by a physical / chemical method. It is preferable since it has excellent deodorizing effect. As a physical division means,
False twisting, air processing, water current processing, etc. can be mentioned,
Examples of the chemical resolving means include a treatment with an aqueous alkali solution or a stirring treatment with hot water when the polymer (B) is a polyester, and a treatment with benzyl alcohol or benzoic acid when the polymer (B) is a polyamide. The fiber fineness after split fibrillation is preferably in the range of 0.1 to 2.0 denier.

The cross-sectional shape of the composite fiber of the present invention is not particularly limited, and may be any of a round cross section, an irregular cross section, a solid fiber, and a hollow fiber. The composite ratio of the polymer (A) and the polymer (B) is (A) :( B) = 20: 80.
~ 80: 20 (weight ratio), especially 30: 70 ~ 70: 3
It is preferably 0. 80% by weight of polymer (A)
When the ratio is more than 1, the proportion of the polymer (B) in the fiber is reduced, the fiber properties are inferior, and the drawn fluff and the yarn breakage are liable to occur. On the other hand, if it is less than 20% by weight, a good feeling similar to natural fibers cannot be maintained, and the deodorizing performance is also poor.

The polymer (A) has a melting point of 150-1.
It is a polymer at around 80 ° C. In hot water, the phenomenon of melting point drop actually occurs, and it becomes easy to soften. Therefore, since a fiber-forming thermoplastic polymer having a melting point of 200 ° C. or more is used as the polymer (B), especially when the exposed area of the polymer (A) is large in the composite shape of the fiber cross section, especially the core-sheath type composite fiber In the case of (1), sticking occurs between the single fibers depending on the dyeing conditions. In order to adjust the hardness of the feeling due to the sticking phenomenon to a certain extent, it is preferable that the polymer (A) is acetalized with monoaldehyde, dialdehyde, or an acetalized product thereof to impart hot water resistance.

The fiber obtained in the present invention is a synthetic fiber, but has a feeling similar to that of a natural fiber, a moisture absorption property, a re-contamination property, a coloring property and a glossiness, and is excellent in deodorizing property. It is a fiber that can maintain the deodorizing performance for a period. Therefore, a woven or knitted fabric, a nonwoven fabric, or the like is prepared from such fibers and processed into a final fiber product. Further, 100% of the fiber may be used, or a part thereof may be mixed with another fiber.

[0046]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The physical properties in the examples were measured and measured by the following methods.
This is the calculated value. (1) Intrinsic viscosity (g / dl) of polyester: Measured at 30 ° C. using a mixed solution of phenol / tetrachloroethane by weight. (2) Relative viscosity of polyamide Measured at 30 ° C. using orthochlorophenol.

(3) Evaluation of deodorant performance a. Initial performance Under normal incandescent fluorescent light irradiation (500 lux), 15 cm
Sample 3 in a Tedlar bag (3 liters in volume)
g was sealed, and then air containing a predetermined concentration of odor component was injected into the Tedlar bag using a syringe so that the total gas volume was 3 liters. The injected gas is ammonia 40 ppm, hydrogen sulfide 15 ppm, acetic acid 40 ppm
Met. After a specified time after injecting the gas, the gas in the Tedlar bag was sampled with a microsyringe, and the gas concentrations of hydrogen sulfide and acetic acid were measured by gas chromatography (GC-7A manufactured by Shimadzu Corporation), and the odor component was measured. The removal rate was calculated by the following equation. Ammonia was measured directly using a gas detector tube (manufactured by Kitagawa Corporation, ammonia type), and the gas concentration in the Tedlar bag was calculated to calculate the odor component removal rate. In the same manner, measurement under light shielding was also performed. Removal rate (%) = [(C ₀ −C) / C ₀ ] × 100 C ₀ : initial gas concentration C: gas concentration after 1 hour b. Repeated deodorization performance Under normal incandescent fluorescent light irradiation (500 lux), 15 cm
Sample 3 in a Tedlar bag (3 liters in volume)
g was sealed, and then air containing a predetermined concentration of odor component was injected into the Tedlar bag using a syringe so that the total gas volume was 3 liters. The injected gas was acetic acid 4
It was 0 ppm. One hour after the gas was injected, the gas concentration was measured by gas chromatography, and air containing 40 ppm of acetic acid was injected into the Tedlar bag.
Measurement of gas concentration and injection of acetic acid were repeated every hour. c. Washing Durability Using a sample which was washed 50 times, the deodorization of ammonia was evaluated by the method of a.

(4) Evaluation of antibacterial performance A bacterial solution of Escherichia coli was dropped on the sample, and cultured at 35 ° C. × 18 hours under light irradiation (30 cm under 30 W two fluorescent lamps) or light shielding, and the viable cell count was measured. A standard nylon cloth was used as a control cloth. (5) Hand The hand was evaluated by five panelists and evaluated according to the following criteria. Evaluation criteria ◎: Four or more persons evaluated it as good. ：: Three persons evaluated it as good. B: One or two persons evaluated it as good. ×: All the members were evaluated as poor.

<< Adjustment of Deodorant >> A deodorant [Cu (II) -Ti (IV) -SiO ₂ -TiO ₂ ] was prepared by the following method. Copper sulfate crystals (CuSO ₄ · 5H ₂ O, Wako Pure Chemical Industries, Ltd. special grade) was dissolved in 43.9g distilled water 1 liter of an aqueous solution obtained in the titanium sulfate solution (about 30% strength by weight, Wako Pure Chemical (A reagent manufactured by the company) was added. This mixed solution contains 0.175 mol of Cu (II) and 0.0
It contained 75 moles. The pH of the mixed solution was about 1. About 110 g of a 15% by weight phosphoric acid solution was added dropwise while stirring the mixed solution at room temperature, and a white precipitate was formed. The mixed solution in which the precipitate was generated was stirred as it was overnight. While stirring the solution containing the precipitate (solution A) and 471 g of an aqueous solution containing sodium silicate (solution B) in separate beakers, the solution was dropped parallel to a vessel containing 500 ml of distilled water. As a result, Cu (II) -Ti
(IV) mixtures precipitate pale containing -SiO ₂ was produced. The dripping amounts of the A liquid and the B liquid were adjusted so that the pH at the time of mixing the A liquid and the B liquid was always about 7. Solution B is prepared by diluting sodium silicate (manufactured by Wako Pure Chemical Industries, Ltd.) to 30% by weight with distilled water (containing 0.86 mol as SiO ₂ ) and adding 30 ml of a 15% by weight aqueous sodium hydroxide solution. Was adjusted accordingly.

The mixed solution of the solution A and the solution B is added
After stirring for an hour, the blue-white mixed precipitate was filtered by suction, washed sufficiently with warm deionized water, and then dried at 40 ° C.
The dried product is ground in a mortar to 120 μm or less, and Cu (II)-
To give a pale powder containing Ti (IV) -SiO _2. Titanium oxide powder (Ishihara Sangyo Co., Ltd.)
(MC-90), 20 parts by weight, and pulverized by a jet mill to prepare a deodorant.

Example 1 10% by weight of the above deodorant and 10% by weight of Irganox 10 were added to an ethylene vinyl alcohol polymer having a saponification degree of 99%, a vinyl alcohol component of 56 mol% and a melt index of 6.0.
98 (registered trademark: Ciba-Geigy Corporation) was added at 0.3% by weight, melt-mixed at 260 ° C. for 20 minutes, extruded while kneading with an extruder, filtered through a 250 mesh wire mesh, and used for master batch. A pellet was made. 1 part by weight of the pellets was mixed with 1 part by weight of an ethylene vinyl alcohol copolymer having a saponification degree of 99%, a vinyl alcohol component of 56 mol% and a melt index of 6.0 to prepare a polymer ( Polymer A). On the other hand, polymer
Polyethylene terephthalate having an intrinsic viscosity of 0.68 as B
And melt extruded with separate extruders so that the polymer A becomes the sheath and the polymer B becomes the core.
= 50: 50 (weight ratio), and then metered by a gear pump, and then fed into a spinning pack, and
It was discharged at 0 ° C. and wound up at a speed of 1000 m / min. Then, the film was stretched at a magnification of 2.9 by a roller heater at 75 ° C.
It was heat-set with a plate heater at 130 ° C. to obtain a drawn yarn of 75 denier / 24 filaments. A tubular knitted fabric was prepared using the drawn yarn and subjected to relaxation, washing, drying, and presetting, and each performance was evaluated. Table 1 shows the results.

Examples 2 to 5 In Example 2, a drawn yarn was obtained in the same manner as in Example 1 except that the composite structure of the yarn was a side-by-side cross-sectional structure.
The obtained drawn yarn was subjected to false twist processing to form a tubular knitted fabric, and subjected to relaxation, washing, drying, and final setting, and each performance was evaluated. In Example 3, a tubular knitted fabric was prepared in the same manner as in Example 1 except that the composite structure of the yarn was a vertically split type composite fiber cross-section (11-layer alternating lamination type), and each performance was evaluated. . Further, in Example 4, a tubular knitted fabric was prepared in the same manner as in Example 1 except that the composite structure of the yarn was a vertically split type composite fiber cross section (five-layer alternate lamination type), and each performance was evaluated. did. Further, in Example 5, the composite structure of the yarn was
And Polymer B were passed through a static mixer (4 elements) to form a tubular knitted fabric in the same manner as in Example 1 except that a random mix type structure was formed, and each performance was evaluated. Table 1 shows the evaluation results.

Examples 6 and 7 In Example 1, except that the composite ratio was A: B = 33: 67 (weight ratio) (Example 6), the composite ratio was A: B = 6.
A tubular knitted fabric was prepared in the same manner except that the weight ratio was 7:33 (Example 7). Table 1 shows the performance evaluation results.

Examples 8 to 10 In Example 1, nylon 6 (manufactured by Ube Industries, 1013K, relative viscosity 1.18) was used instead of polyethylene terephthalate, and Cyanox 1 was used as an antioxidant.
790 (registered trademark: manufactured by American Cyanaside Co.) (Example 8), except that polybutylene terephthalate (intrinsic viscosity 0.83) was used (Example 9). A cylindrical knitted fabric was prepared in the same manner as in Example 10 except that polyethylene terephthalate (intrinsic viscosity: 0.60) containing 0.7 mol% was used. Table 1 shows the performance evaluation results.

Comparative Example 1 A drawn yarn was prepared in the same manner as in Example 1 except that Irganox 1098, which is an antioxidant, was not added to Polymer A. Could not be obtained.

Comparative Example 2 A drawn yarn was produced in the same manner as in Example 1 except that no deodorant was added to Polymer A, and a tubular knitted fabric was produced. Although a slight deodorizing effect was observed due to the presence of the polymer A, the fiber obtained in Example 1 was of course inapplicable. However, the spinning processability was good due to the presence of the oxidative spinning agent.

Reference Example 1 In Example 1, the limiting viscosity was changed to 0.
A drawn yarn and a tubular knitted fabric were prepared in the same manner except that polyethylene terephthalate No. 68 was used. The deodorizing effect was the same as that of the fiber obtained in Example 1, but the hand was cool and was far from natural fiber. Table 1 shows each performance evaluation.

Reference Example 2 A drawn yarn and a tubular knitted fabric were prepared in the same manner as in Example 1 except that a deodorant was added to Polymer B. Since the deodorant was contained in the core portion of the core-sheath type composite fiber, the deodorizing effect was just a step away, but the texture as the fiber was a good texture similar to natural fibers. Table 1 shows each performance evaluation.
Although no antioxidant was added to Polymer A,
Since the deodorant was added to Polymer B, breakage of single yarn was observed in the spinning step, but there was no major problem with the obtained fiber.

[0059]

[Table 1]

[0060]

According to the present invention, by adding a deodorant and an antioxidant to an ethylene vinyl alcohol copolymer, a fiber free of thread breakage and fluff can be obtained. By adding a deodorant in the vinyl alcohol-based copolymer and exposing the ethylene vinyl alcohol-based copolymer to a large amount on the fiber surface, the deodorizing effect is high and a wind similar to natural fibers is obtained. It is possible to obtain a composite fiber.

Continuation of the front page (72) Inventor Junhiro Nakagawa 1621 Sazu, Kurashiki-shi, Okayama Prefecture Kuraray Co., Ltd. Examiner Yumiko Kawaguchi (56) References JP-A-8-284011 (JP, A) JP-A-5-222614 (JP, A) JP-A-3-234815 (JP, A) JP-A-3-119178 (JP, A) JP-A-3-69611 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) D01F 8/10 D01F 1/10

Claims (8)

(57) [Claims] 1. An ethylene-vinyl alcohol copolymer (A) having an ethylene content of 25 to 70 mol% and a saponification degree of 95% or more, and a fiber-forming thermoplastic polymer having a melting point of 200 ° C. or more. (B) a composite fiber comprising (A)
A fiber having excellent deodorizing performance, characterized in that an antioxidant and a deodorant are contained in a polymer. 2. The fiber according to claim 1, wherein the deodorant comprises a phosphate of a tetravalent metal, a hydroxide of a divalent metal and a photocatalyst. 3. The fiber having excellent deodorizing performance according to claim 1, wherein the fiber has a core-sheath type composite form comprising (A) a polymer as a sheath and (B) a polymer as a core. 4. The fiber excellent in deodorizing performance according to claim 1, wherein the fiber is a split-type laminated composite form in which (A) a polymer and (B) a polymer are laminated alternately. 5. The fiber excellent in deodorizing performance according to claim 1, wherein the polymer (A) and the polymer (B) form random composite forms different from each other among the single fibers. . 6. The fiber according to claim 4 or 5, which has a single fiber fineness of 0.1 to 2.0 denier obtained by splitting the fiber by false twisting and / or air processing, and has excellent deodorizing performance. Fiber. 7. The single fiber fineness obtained by subjecting the fiber according to claim 4 or 5 to a splitting treatment by reducing the alkali has a fineness of 0.1 to 0.1.
2.0 denier fiber with excellent deodorant performance. 8. A single fiber fineness obtained by subjecting the fiber according to claim 4 or 5 to splitting treatment by hydroentanglement, to have a fineness of 0.1 to 2.
0 denier fiber with excellent deodorant performance.