JPH02216217A - Deodorizing sheath-core conjugate fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber having sufficiently high mechanical performance and excellent deodorizing function by forming a sheath part having fine pores and made of a polyester and a core part made of a thermoplastic polymer containing a deodorant. CONSTITUTION:The objective fiber consists of (A) a polyester sheath part containing fine pores having diameter of 0.001-5mum and a length/diameter ratio of <=50, distributed over the cross-section of the fiber, oriented in the direction of the fiber axis and connected at least partly to the core part and (B) a core part made of a thermoplastic polymer containing 1-50wt.% of a deodorant. The fiber stably retains the deodorant and exhibits deodorizing property having excellent durability when used as clothes, sanitary materials, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a core-sheath composite fiber having a deodorizing function. More specifically, the present invention relates to a core-sheath composite fiber that has special micropores in its sheath portion and has a highly durable deodorizing function and good mechanical properties.

(Prior art) Activated carbon is the conventional method for imparting deodorizing properties and deodorizing properties to m-fibers. A method in which a treatment agent containing a deodorizing agent is attached to the fiber surface by post-processing etc. (see, for example, Japanese Patent Publication No. 47-29984), a method in which a polymer containing an odor absorbent is made into fibers. (For example, see Japanese Utility Model Publication No. 61-37227.) etc. have been proposed.

However, activated carbon fiber 1771H itself is colored and is extremely brittle, so it cannot be used in the clothing field, where aesthetics are required, and the sanitary material field, where dust generation is extremely objectionable. On the other hand, in the post-processing method, the deodorant tends to fall off during use, and there is a problem in terms of the durability of the deodorizing function. Also,
In the method of blending an odor adsorbent, it is necessary to blend the adsorbent in a fairly large amount in order to provide a satisfactory deodorizing function. Therefore, the mechanical properties of the obtained material are insufficient. A common way to improve such mechanical properties is to use polymers that do not contain deodorants to make composite fibers, but in order to develop sufficient deodorizing function, it is necessary to It is necessary to expose the blended polymer to the outer surface of the fiber. Therefore, there is a problem in that the deodorant-containing polymer falls off from the surface of the m-thread due to mechanical friction during the spinning process, post-processing process, etc., resulting in frequent troubles.

(Object of the Invention) The present invention was made to solve the problems of the above-mentioned prior art, and its purpose is to simultaneously provide sufficient mechanical performance and an excellent deodorizing function. The object of the present invention is to provide a new deodorizing composite fiber that does not cause any trouble during spinning and post-processing processes.

(Structure of the Invention) As a result of intensive studies aimed at achieving the above object, the present inventor has found that a deodorant is present in a high concentration in the center of the fiber, and a communicating hole is formed from the fiber surface to the area where the deodorant exists. It has been discovered that the above objects can be achieved at the same time because the fibers formed with this do not contain a deodorizing agent in the surface layer of the fibers, leading to the present invention.

That is, the present invention provides a core-sheath composite IIM composed of a sheath made of polyester having micropores and a core made of a thermoplastic polymer containing 1 to 50% by weight of a deodorant, The diameter of the micropores in the part is o, ooi ~ 5
μ, the deodorant is characterized in that its length is 50 times or less the diameter, it is scattered in the cross section of the fiber, it is arranged in the direction m away from the axis, and at least a part of it is in communication with the core. This relates to a core-sheath composite fiber.

The micropores present in the sheath of the core-sheath composite fiber of the present invention have a diameter within the range of 0.001 to 5 μm,
The length must be 50 times or less than the diameter, and the fine pores must exist throughout the fiber cross section and be arranged in the m minor axis direction, and at least 181S of them must be in communication with the hollow part.

Note that the diameter of the micropore referred to herein refers to the width in the direction perpendicular to the fiber axis at the portion where the micropore opens onto the fiber surface.

When the diameter of these micropores is less than 0.001 μm, the deodorizing II ability is insufficient, and when it exceeds 5 μm, sufficient fiber strength cannot be obtained. A range of .01 to 3 μm is preferred. In addition, especially when the length of the micropore is longer than 50 times its diameter,
Even if all other conditions are satisfied, the strength and fibril resistance of lla will be low, and 30 times or less is particularly preferred.

Further, since the micropores are scattered throughout the fiber cross section and arranged in the m-fiber axis direction, and at least a portion of them communicates with the core, a sufficient deodorizing function can be obtained. If the micropores are concentrated near the coating surface in the cross section of the composite fiber or do not communicate with the core, the deodorizing properties will be insufficient no matter how many micropores the composite fiber has.

How these micropores are present in the cross section of the fiber and whether at least some of them communicate with the core can be determined by observing the cross section of the fiber about 3000 times larger.

Furthermore, if the proportion of the total cross-sectional area of the micropores in the fiber cross-section is too small, the deodorizing function will be reduced, and if it is too large, the fiber strength will be reduced. It is preferably in the range of 0.01 to 50%, particularly preferably in the range of 0.1 to 30%.

Next, the core part constituting the composite I miscellaneous material of the present invention is coated with 1 deodorizer.
It consists of a thermoplastic polymer containing ~50% by weight. The thermoplastic polymer used here does not need to be particularly limited;
It may be either a homopolymer or a copolymer. Examples of such polymers include polyethylene, polypropylene, and polystyrene.

Polybutadiene, polyisoprene, nylon-6° nylon-1)6. Examples include polyethylene terephthalate, polybutylene terephthalate, and copolymers mainly composed of these. These may be used alone or in combination of two or more.

Further, the deodorant is not particularly limited as long as it is an agent that exhibits a deodorizing effect by adsorbing odor components or reacting with odor components, and does not decompose or volatilize during fiber formation. Examples of such agents include activated alumina, silica gel, and activated clay.

Inorganic adsorbents with extremely fine pores whose main components are zeolite, activated titanium oxide, activated zinc oxide, etc., as well as fumaric acid, iron ascorbic acid compounds, metal phthalocyanine compounds, metal porphyrin compounds, flavonoid compounds, and amino acids. system compound.

Examples include organic deodorants such as tannin compounds, sugars, and purine bases. The blending amount of such a deodorant varies depending on the type of deodorant used, but is 1 to 50% by weight, preferably 5 to 50% by weight.
It needs to be 35% by weight. If the blending amount is less than 1% by weight, a sufficient deodorizing function cannot be obtained, while if it exceeds 50% by weight, the silk-spinning properties will be extremely reduced and the mechanical properties of the resulting fibers will be insufficient, so it is preferable. do not have.

Further, the conjugate fiber of the present invention does not need to be particularly limited as long as it is a core-sheath conjugate fiber, and the shapes of the core and sheath in cross section may be arbitrary. For example, the outer shape and the core may both be circular, one of the outer shape and the core may be circular and the other has an irregular shape, or both the outer shape and the core may have similar or dissimilar irregular shapes. There is no need to particularly limit the size of the external shape. Further, the number of core portions can be any number greater than or equal to one.

The ratio of the sheath part to the core part in the fiber cross section can also be within a very wide range, but if the ratio of the core part is too large, the strength of the composite fiber obtained will be insufficient.
The ratio of the core portion in the fiber cross section is preferably 50% or less. On the other hand, if the proportion of the core is too small, the deodorizing function tends to deteriorate, so it is preferable to make it 5% or more of the fiber cross-sectional area.

Various methods can be considered to produce the composite fiber of the present invention, but for example, a polyester containing a specific sulfonic acid metal salt or a polyester copolymerized with an organic sulfonic acid may be blended with a normal polyester. (hereinafter collectively referred to as modified polyester) is used as a sheath part, and a thermoplastic polymer blended with the deodorant is used as a core part, and melt-spun using a core-sheath composite spinneret, and stretched and heat treated as necessary.

Preferably, a method is employed in which predetermined micropores are formed by crimping (bulking) the obtained composite fiber directly or by knitting and weaving it and then treating it with an alkaline aqueous solution to remove at least a part of the modified polyester in the sheath. be done.

Among the modified polyesters constituting the sheath portion of the composite II cloth used herein, a polyester containing a specific sulfonic acid metal salt will be exemplified and explained. The polyesters targeted here include terephthalic acid as the main acid component and fullylene glycols having 2 to 6 carbon atoms, ie, ethylene glycol, trimethylene glycol, and tetramethylene glycol.

A polyester whose main glycol component is at least one type of glycol selected from pentamethylene glycol and hexamethylene glycol. Such polyesters may have up to 10 mole percent of their acid component replaced by other difunctional carboxylic acids. Such other carboxylic acids include, for example, difunctional aromatic carboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, β-oxyethoxybenzoic acid, p-oxybenzoic acid, sebacic acid, adipic acid, and oxalic acid. Examples include difunctional aliphatic carboxylic acids such as, and difunctional alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid. In addition, 10% of the glycol component of polyester
Less than mol% may be replaced with other glycol components,
Such glycol components include the above-mentioned glycols other than the main component and other diol compounds, such as cyclohexane-
Examples include aliphatic, alicyclic and aromatic diol compounds such as 1,4-dimetatool, neopentyl glycol, bisphenol A, and bisphenol S.

Such polyesters can be obtained by any manufacturing method. For example, to explain polyethylene terephthalate, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol are transesterified to form a glycol ester of terephthalic acid. and/or is easily produced by a first stage reaction in which a low polymer thereof is produced, followed by a second stage reaction in which the product is heated under reduced pressure and subjected to a polycondensation reaction until a desired degree of polymerization is achieved.

When melt-spinning the above-mentioned polyester as a sheath component to make a composite fiber, at least one sulfonic acid metal salt represented by the following general formula [, I] is added to the polyester at any stage until the melt-spinning is completed. It is added in an amount of 0.3 to 15 mol % based on the constituent acid components.

In the formula, Ml and M2 are metals, and Ml is particularly L.
i, alkaline earth metal, Mn1/2.

Cot/2 or Zn1/2 is preferred, and Ca1/2 and MG1/2 are particularly preferred,
M2 is particularly preferably an alkali metal or an alkaline earth metal, especially i, Na, K.

Ca1/2, Mat/2 are particularly preferred, Ml and M
2 may be the same or different. n is 1 or 2. R is a hydrogen atom or an ester-forming functional group, and the ester-forming functional group is -C0OR' (However, R
' is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group) or -GO[0(CH2)u]mOH (where 9 is an integer of 2 or more, and 9 is an integer of 1 or more).

Preferred specific examples of such sulfonic acid metal salts include 3
-Carbomethoxybenzenesulfonic acid Na-5-carboxylic acid Li, 3-carbomethoxybenzenesulfone 1-
5-carboxylic acid, 3-carpomethoxybenzenesulfone! ! Na-5-carboxylic acid Ca1/2.3-carbomethoxybenzenesulfonic acid Na-5-carboxylic acid Mg
l/2, 3-hydroxyethoxycarbonylbenzenesulfone MNa -5-carboxylic acid Mg1/2, 3-
) Lephoxyethoxycarbonylbenzenesulfonic acid N
a5-carboxylic acid Zn1/2. Sodium benzenesulfonate
-3,5-di(carboxylic acid [i), Na-3,5-di(carboxylic acid), Na-3,5-di(carboxylic acid Cal/2) benzenesulfonate
, benzenesulfonic acid Na-3,5-di(carboxylic acid M
(J1/2) etc. can be given.

The above-mentioned sulfonic acid metal salts may be used alone or in combination of two or more. It may be added at any stage before the end of the spinning process of melt-spinning polyester into composite IN; for example, it may be added into the polyester raw material, during polyester synthesis, or at the end of synthesis. It may be added later before melt spinning.

In any case, it is preferable to mix the additives in a molten state.

If the amount of the sulfonic acid metal salt added is too small,
The above-mentioned micropores are not sufficiently formed, resulting in insufficient deodorizing properties of the final composite fiber. On the other hand, if it is added too much, it will be added before the synthesis of polyester is completed.
It is difficult to obtain polyester with a sufficient degree of polymerization, and if it is added between after the completion of synthesis and before the completion of melt spinning, troubles are likely to occur during spinning. Therefore, the amount added should be in the range of 0.3 to 15 mol%, preferably 0.5 to 5 mol%, based on the acid component constituting the polyester.

Next, as the modified polyester obtained by mixing a polyester copolymerized with an organic sulfonic acid compound and a normal polyester, for example, the modified polyester exemplified in JP-A-56-20612 can be used as is.

There is no need to employ any special method to melt-spun the thus obtained modified polyester and the thermoplastic polymer containing the deodorant to form a core-sheath composite fiber, and a normal composite spinning method can be arbitrarily adopted. .

The composite l! thus obtained! Part of the modified polyester can be easily removed from the fabric by subjecting it to stretching heat treatment or false twisting as necessary, or by immersing it in an aqueous solution of an alkaline compound after making it into a fabric. can.

The alkaline compounds used here include sodium hydroxide, potassium dihydroxide, tetramethylammonium hydroxide, and sodium carbonate.

Examples include potassium carbonate. Among these, sodium hydroxide and potassium hydroxide are particularly preferred.

The II of such an aqueous solution of an alkali compound varies depending on the type of alkali compound, processing conditions, etc., but is usually 0.01.
-40% by weight is preferred, particularly preferably 0.1-30% by weight.a The treatment temperature is preferably in the range of room temperature to 100°C, and the treatment time is usually carried out in the range of 1 minute to 4 hours. Further, the amount of the modified polyester to be eluted and removed by treatment with the aqueous solution of the alkali compound should be in the range of 2 to 50% by weight based on the weight of the sheath portion of the composite fiber. By treating with an aqueous solution of an alkaline compound in this way, the fibers are scattered throughout the sheath of the cross section of the composite fiber, arranged in the fiber axis direction, and at least a portion of which is in communication with the core, and has a diameter of about 0.001~ With a length of 5 μm, micropores with a diameter of 50 times or less are formed, and exhibit excellent deodorizing properties.

Note that the composite fiber obtained by the method of the present invention may contain optional additives, such as a catalyst 2 color inhibitor, a heat resistant agent, an a-flame agent, a fluorescent whitening agent, and a matting agent, if necessary.

A coloring agent, inorganic fine particles, etc. may be included.

(Effects) The composite fiber of the present invention has a core containing a high concentration of deodorant surrounded by a sheath that does not contain a deodorant, so it has sufficient mechanical properties and can be used easily. The deodorant does not fall off even when rubbed, and exhibits excellent deodorizing performance with excellent durability. In addition, since the sheath has micropores that communicate with the core, the level of deodorizing performance is extremely high, and IJ can be used in a wide range of fields, such as clothing and sanitary materials.

(Example) Hereinafter, the present invention will be further explained in detail by giving Examples.

Example 1 Dimethyl terephthalate 100! 1 part by weight of ethylene glycol, 66 parts by weight of manganese acetate tetrahydrate, and 0.03 parts by weight of manganese acetate tetrahydrate were added to the transesterification color, and the temperature was raised from 140°C to 230°C over 14 hours in a nitrogen gas atmosphere to remove the generated methanol from the system. The transesterification reaction was carried out while distilling off.

The resulting product was then treated with 56% of orthophosphoric acid as a stabilizer.
Aqueous solution 0.03 double hanging part.

0.04 parts by weight of antimony trioxide, Na-3,5-di(carbonlli!2M(11/2)
20% ethylene glycol slurry (1.5 parts by weight) was added and transferred to a polymerization can. Then over an hour 7
The pressure was reduced from 60MH9 to 1 part pressure, and at the same time polymerization was carried out at 230°C to 285°C for 1 hour and 30 minutes for an additional 2 hours and 30 minutes, for a total of 4 hours, and the intrinsic viscosity was 0.650. A modified polyester having a softening point of 261°C was obtained.

100 parts by weight of polyethylene and deodorant Tomix〇 −
700 (manufactured by Tomita Pharmaceutical Co., Ltd.) 50 heavy weight part was thoroughly heated and mixed in a kneading machine, and the obtained blend composition was used as the core part, and the above-mentioned modified polyester was used as the sheath part, and spun using a concentric core-sheath composite spinning machine, After stretching 4 times at 100°C, it was heat-set at 160°C to form a core-sheath composite fiber.

Composite ratio (area ratio core/sheath) in the cross section of this composite fiber
was 1/3 and the $1ili configuration was 30 denier/3 filament. This composite fiber was knitted into a knitted fabric, scoured and preset by a conventional method, and then treated in a 1% caustic soda aqueous solution at a temperature of W1 so that the weight loss rate was 20% based on the weight of the sheath.

Ammonia gas having a concentration of 14,001) [11] was put into a 1,500 cc container containing 5 g of the obtained fabric, and the residual concentration of ammonia was measured after 1 hour and found to be 60 ppm. (Deodorization rate: 96%) Example 2 297 parts of dimethyl terephthalate, 265 parts of ethylene glycol, 53 parts of sodium 3.5-di(carbomethoxy)benzenesulfonate (11.1 mol based on dimethyl terephthalate) %), 0.084 parts of manganese acetate tetrahydrate and 1.22 parts of sodium acetate trihydrate were placed in a glass flask equipped with a distillation tower, and a transesterification reaction was carried out according to a conventional method. After distillation of the theoretical amount of methanol. The reaction product was placed in a polycondensation flask equipped with a rectifying column, and 0.090 parts of a 56% aqueous solution of orthophosphoric acid as a stabilizer and 0.135 parts of antimony trioxide as a polycondensation catalyst were added, and the mixture was heated at a temperature of 275°C under normal pressure. The mixture was reacted for 15 minutes under a reduced pressure of 30 rrrts H9 for 15 minutes, and then for 100 minutes under high vacuum. Final internal pressure is 0
．． The obtained copolymer had an intrinsic viscosity of 8,405 and a softening point of 200°C. After the reaction was completed, the copolymer was made into chips according to a conventional method.

15 parts of chips of this copolymer and an intrinsic viscosity of 0.64
After mixing with 85 parts of polyethylene terephthalate chips of No. 0 for 5 minutes in a Nauta mixer (manufactured by Amiside Ironworks), the mixture was heated at 110°C for 2 hours in a nitrogen stream, and then at 150°C for 7 hours.
After drying for 29 hours, a twin-screw extruder was used to
The mixture was melted and kneaded at 0°C to form chips. The intrinsic viscosity of this chip is 0.520. The softening point was 262°C.

A core-sheath composite fiber was obtained in the same manner as in Example 1 except that this polymer was used as the sheath component, but the core-sheath ratio was 115). This was knitted into a knitted fabric in the same manner as in Example 1, and subjected to alkali weight loss treatment (loss rate: 15%) to obtain a fabric. The ammonia gas deodorization rate of this fabric was 91%.

Example 3 A fabric was obtained in the same manner as in Example 1, except that the amount of the deodorant added to the polyethylene was changed as shown in Table 1.

Table 1 shows the deodorizing properties of this fabric.

Table 1 Comparative Example 1 The ammonia gas deodorization rate when the knitted fabric obtained in Example 1 was not subjected to alkali treatment was measured in the same manner as in Example 1, and was found to be 25%.

Comparative Example 2 297 parts of dimethyl terephthalate, 2 parts of ethylene glycol
65 parts of manganese acetate tetrahydrate and 0.084 parts of manganese acetate tetrahydrate were placed in a glass flask equipped with a rectification tower, and transesterification was carried out according to a conventional method. After the theoretical amount of methanol had been distilled off, the reaction product was placed in a glass flask equipped with a rectification tower. Add 56% of orthophosphoric acid to the condensation flask.
0.090 part of aqueous solution and 0.135 part of antimony trioxide were added, and the reaction was allowed to proceed at a temperature of 215°C for 20 minutes under normal pressure and for 15 minutes under reduced pressure of 30MH9. After adding 7.5 parts of a sodium alkyl sulfonate mixture having an average carbon number of 14, the pressure inside the system was gradually reduced, and the reaction was allowed to proceed for 80 minutes with stirring. The final internal pressure is 0.32
rNRHs, and the intrinsic viscosity of the obtained polymer is 0.
It was 622. After the reaction was completed, chips were formed according to a conventional method.

A multifilament of 30 denier/3 filaments was obtained by spinning and drawing in the same manner as in Example 1 except that this polymer was used as the sheath component. This multifilament was made into a knitted fabric, and after scouring and presetting, it was treated with a 0.5% caustic soda aqueous solution at boiling temperature for 180 minutes to obtain a fabric with an alkali weight loss rate of 15% (based on the weight of the sheath). . The ammonia gas deodorization rate of this fabric was 95%.

In addition, when the surface of a single fiber subjected to alkali weight loss treatment was observed using an electron microscope at a magnification of 3000 times, the micropores were striped and elongated.
Most of the diameters were 100 times or more the diameter of the pores.

After the dyed fabric was worn 200 times, microscopic observation revealed that fibrils were formed.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing a preferred example of the deodorizing composite fiber of the present invention. 1 Sheath part having micropores 2 Core part containing deodorant 3 Micropores 4 Micropores communicating to the core part

Claims (1)

[Claims] A core-sheath composite fiber consisting of a sheath made of polyester having micropores and a core made of a thermoplastic polymer containing 1 to 50% by weight of a deodorant, the fiber having micropores in the sheath. have a diameter of 0.001 to 5 μm, a length of not more than 50 times the diameter, are scattered in the cross section of the fiber, are arranged in the fiber axis direction, and at least a part of them communicates with the core. A deodorizing core-sheath composite fiber.