JP2937337B2 - Deodorant polyester fiber - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyester fiber having high strength and excellent deodorizing performance, and a method for producing the same.

(Prior art) Conventionally, as a method for imparting deodorant / deodorizing performance to fibers, a method using activated carbon fibers in combination and a method of attaching a deodorant to the fibers by post-processing or the like (Japanese Patent Publication No. 47-29984) Japanese Patent Application Laid-Open No. 61-37227 discloses a method in which a polymer containing an odor adsorbent is formed into fibers. However, each of these has drawbacks,
It was not satisfactory. That is, the activated carbon fibers cannot be used for clothing requiring aesthetics, sanitary materials that dislike dust generation, and the like, since the activated carbon fibers themselves are colored and have insufficient mechanical properties and are liable to fall off. On the other hand, in the method in which the deodorant is attached to the fiber by post-processing, the durability is insufficient because the deodorant is easily dropped off during use.
In addition, the method of blending the odor adsorbent requires a large amount of blending in order to provide good deodorant performance, and as a result,
There are problems such as difficulty in fibrillation and insufficient strength of the resulting fiber.

(Object of the Invention) An object of the present invention is to provide a deodorant polyester fiber which does not have the drawbacks of the prior art, has excellent spinning process stability, has good deodorant performance and sufficient mechanical performance, and a method for producing the same. And

(Constitution of the Invention) The present inventor has conducted intensive studies in order to achieve the above object. As a result, the fibers having micropores formed therein have good deodorant properties even if the amount of the deodorant is reduced. We have found what we can achieve and arrived at the present invention.

That is, the present invention relates to a fiber made of polyester containing 0.1 to 5% by weight of a deodorant, which is scattered in the cross section of the fiber, arranged in the fiber axis direction, and at least a part of which is located at the center of the fiber. A first aspect of the present invention is a deodorant polyester fiber characterized in that micropores communicating with the vicinity are formed, and a bifunctional carboxylic acid mainly composed of terephthalic acid or an ester-forming derivative thereof and a C2 to C2 derivative. 6 is reacted with an alkylene glycol or an ester-forming derivative thereof to synthesize a polyester, and the obtained polyester is melt-spun to form a polyester fiber. formula 0.3 to 15 mol% based on the bifunctional carboxylic acid compound, and 0.1 to 5% by weight based on polyester based on the bifunctional carboxylic acid compound.
, And the resulting polyester fiber is treated with an aqueous alkaline solution to elute 2 to 50% by weight from the fiber, and the method for producing a deodorant polyester fiber described above is a second invention. Things.

The polyester in the present invention contains terephthalic acid as a main acid component, and has an alkylene glycol having 2 to 6 carbon atoms.
That is, a polyester containing at least one glycol selected from ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol as a main glycol component. Such polyesters may have up to 10 mol% of their acid components replaced by other dicarboxylic acids. Such other carboxylic acids include, for example, aromatic dicarboxylic acids such as isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, aliphatic dicarboxylic acids such as sebacic acid, adipic acid and oxalic acid; And alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid. Further, 10 mol% or less of the glycol component of the polyester may be replaced with another glycol component. Examples of the glycol component include the above-mentioned glycols and other diol compounds other than the main component, such as cyclohexane-1,4-dimethanol, Examples thereof include aliphatic, alicyclic and aromatic diol compounds such as pentyl glycol, bisphenol A and bisphenol S. Further, a hydroxycarboxylic acid component of 10 mol% or less of the acid component may be copolymerized.
Oxyethoxybenzoic acid, p-hydroxybenzoic acid, w-hydroxycaproic acid and the like can be mentioned.

In order to produce such a polyester, any of the conventionally known methods may be adopted.For example, when a case is described in which polyethylene terephthalate is produced from a terephthalic acid component and ethylene glycol, terephthalic acid and ethylene glycol are directly esterified. A first-stage reaction wherein a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol to produce a glycol ester of terephthalic acid and / or a lower polymer thereof, Then, the product is easily produced by heating the product under reduced pressure to carry out a polycondensation reaction until a desired degree of polymerization is reached.

In the present invention, in melt-spinning the polyester into a fiber, at any stage until the melt-spinning is completed, at least one kind of the metal sulfonic acid salt compound is added to the acid component constituting the polyester in an amount of 0.3 to 0.3%. ~ 15 mol%,
It is important to add 0.1 to 5% by weight of the deodorant to the polyester.

The sulfonic acid metal salt compound used in the present invention has the following general formula It is represented by In the formula, M ¹ and M ² are metals, and M ¹ is particularly an alkali metal, an alkaline earth metal, M
n1 / 2, Co1 / 2 or Zn1 / 2 is preferred, and among them, Li, Na, K, Ca1
/ 2, particularly preferably Mg1 / 2, in particular alkali metal or alkaline earth metal is preferable as M ^2, among others Li, Na, K, Ca
1/2 and Mg1 / 2 are particularly preferred. M ¹ and M ² may be the same or different. n is 1 or 2. Y is a hydrogen atom or an ester-forming functional group, and the functional group is -COOR
(Wherein, R represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms), or -COO (CH _{2) 1 p} OH (where 1
Is preferably an integer of 2 or more, and p is an integer of 1 or more.

Preferred specific examples of such sulfonic acid metal salt compounds include 3-carbomethoxy benzene sulfonic acid Na-5.
-Carboxylic acid Na, 3-carbomethoxy-benzenesulfonic acid Na-5-carboxylic acid K, 3-carbomethoxy-benzenesulfonic acid K-5-carboxylic acid K, 3-hydroxyethoxycarbonyl-benzenesulfonic acid Na-5- carboxylic acid
Na, 3-carboxy-benzenesulfonic acid Na-5-carboxylic acid Na, 3-hydroxyethoxycarbonyl-benzenesulfonic acid Na-5-carboxylic acid Mg1 / 2, benzenesulfonic acid Na-3,5-dicarboxylic acid Na, Benzenesulfonic acid Na-3,
5-1 / 2 dicarboxylic acid Mg1 / 2 etc. can be mentioned.

The metal sulfonic acid compound may be used alone or in combination of two or more. The time of its addition
Any stage before the end of the spinning step of melt-spinning polyester into fibers may be performed, for example, adding or blending in the raw material of the polyester, adding during the synthesis of the polyester, or melt-spinning after the end of the synthesis. May be added during this period. In any case, it is preferable to mix in a molten state after the addition.

If the addition amount of the above compound is too small, the deodorizing properties of the finally obtained fiber will be insufficient, and if it is too large, the addition time will be sufficient before the synthesis of the polyester is completed. It is difficult to obtain polyester, and when the addition time is from after the completion of synthesis to before the end of melt spinning, troubles are likely to occur during spinning. For this reason, the amount of addition is 0,0 based on the acid component constituting the polyester to be added.
It should be in the range of 3 to 15 mol%, preferably in the range of 0.5 to 5 mol%.

The deodorant used in the present invention is a component that adsorbs an odor component or reacts with the odor component to exhibit a deodorizing effect, and is not particularly limited as long as it is difficult to decompose or volatilize during fiber formation. . Specific examples of such a deodorant include an adsorbent having an inorganic ultrafine pore mainly composed of activated alumina, silica gel, activated clay, zeolite, activated titanium oxide, activated zinc oxide and the like, and fumaric acid, Organic deodorants such as iron ascorbic acid compounds, metal phthalocyanine compounds, metal porphyrin compounds, flavonoid compounds, amino acid compounds, tannin compounds, saccharides and purine bases.

Such deodorants may be used alone or in combination of two or more. Like the metal sulfonic acid compound, the addition may be made at any stage before the completion of the spinning step of melt-spinning the polyester into fibers, and may be performed simultaneously or separately with the addition of the metal sulfonic acid compound.

The amount of the deodorant added depends on the type of the deodorant, but if it is too small, the deodorant performance becomes insufficient,
On the other hand, if the amount is too large, the stability of the yarn-making process tends to decrease, and the mechanical strength of the finally obtained fiber tends to decrease. For this reason, the amount added should be in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the polyester.

In the present invention, the cross-sectional shape of the fiber does not need to be particularly limited, and may be a round cross section, an irregular cross section, a solid fiber, or a hollow fiber. Above all, hollow fibers are preferable because they have high air permeability and improve the deodorizing effect.
If the hollow ratio of such a hollow fiber is too high, the hollow portion is liable to be crushed and a trouble is apt to occur during a post-processing step or during use. The hollow portion may be a single hollow portion or two or more hollow portions. The shape of the hollow portion may be arbitrary, such as circular or irregular.

To remove a part of the modified polyester from the polyester fiber thus obtained, by subjecting it to stretching heat treatment or false twisting if necessary, or by further immersing the fabric into an aqueous solution of an alkali compound after fabricating the fabric. It can be done easily.

Examples of the alkali compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate and the like. Of these, sodium hydroxide and potassium hydroxide are particularly preferred.

The concentration of the aqueous solution of the alkali compound varies depending on the type of the alkali compound, the treatment conditions, and the like, but is usually 0.01 to 0.01.
A range of 40% by weight is preferred, and a range of 0.1 to 30% by weight is particularly preferred. The treatment temperature is preferably in the range of room temperature to 100 ° C., and the treatment time is usually in the range of 1 minute to 4 hours.
The amount of the alkali compound to be eluted and removed by the treatment with the aqueous solution should be in the range of 2 to 50% by weight based on the weight of the fiber. By treating with an aqueous solution of an alkali compound in this way, the fibers are scattered in the cross section, arranged in the fiber axis direction, and at least a part thereof communicates with the vicinity of the center of the fiber (hollow portion in the case of hollow fiber). Such fine pores are easily formed and exhibit excellent deodorizing properties.

(Effect) The cause of the polyester fiber of the present invention exhibiting excellent deodorant properties even when an extremely small amount of deodorant is added is not clear, but is considered as follows.

In order for the deodorant compounded in the polyester to exhibit deodorant properties, it is necessary for the odor component to diffuse from the fiber surface to the deodorant inside the fiber, and the deodorant that exists far away from the surface Cannot perform its function effectively. On the other hand, the polyester fiber of the present invention has fine pores formed up to the center of the fiber, so that the deodorant at the center of the fiber works effectively and exhibits excellent deodorant properties.

(Effect of the Invention) The deodorant polyester fiber of the present invention has excellent mechanical strength because the amount of the deodorant may be small. Also,
Since it is blended in the fiber, it has excellent durability (abrasion resistance and chemical resistance) and can be widely used for clothing, sanitary materials and the like.

(Example) Hereinafter, an example will be described in more detail.

Examples 1 to 3, Comparative Example 1 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 0.03 parts by weight of manganese acetate tetrahydrate were charged into a transesterification vessel, and heated at 140 ° C. for 4 hours under a nitrogen gas atmosphere.
From 230 ° C. to 230 ° C., and transesterification was carried out while distilling off the generated methanol out of the system. continue,
A 56% aqueous solution of orthophosphoric acid as a stabilizer was added to the obtained product.
03 parts by weight, 0.44 parts by weight of antimony trioxide, 1.5 parts by weight of a 20% ethylene glycol slurry of Na-3,5-dibenzenecarboxylate (carboxylic acid Mg1 / 2), and Tomix A deodorant
D-700 (manufactured by Tomita Pharmaceutical) was added in the amount shown in Table 1 and transferred to the polymerization can. Then, the pressure was reduced from 760 mmHg to 1 mmHg over 1 hour, and simultaneously, the temperature was raised from 230 ° C to 285 ° C over 1 hour and 30 minutes. 2 hours at polymerization temperature 285 ° C under reduced pressure of 1mmHg or less
Polymerized for 30 minutes for a total of 4 hours, intrinsic viscosity 0.650, softening point 261 ℃
A polyester was obtained. This polymer is formed into chips by a conventional method, dried, and spun using a spinneret with a circular hole with a width of 0.05 mm and a diameter of 0.6 mm, which has a circular opening with two closed circular holes. And the ratio of outer diameter to inner diameter is 3:
One hollow fiber (hollow ratio: 11%) was obtained. The spun yarn was 333 denier / 24 filament. The spun yarn was drawn at a drawing temperature of 80 ° C. and a draw ratio of 4.5 to obtain a multifilament of 74 denier / 24 filaments. The multifilament was knitted into a knitted fabric, scoured and preset by a conventional method, and then treated at a boiling temperature in a 1% aqueous solution of sodium hydroxide so as to reduce the weight loss to 20%. 5 g of the obtained cloth was placed in a 1500 cc container, and 1400 ppm of ammonia gas was introduced, and the residual ammonia concentration after 1 hour was measured. The deodorization rate was as shown in Table 1.

Comparative Example 2 Except for adding 7 parts by weight of the deodorant Tomix AD-700, the same procedure as in Example 1 was carried out except that the intrinsic viscosity was 0.650 and the softening point was 261.
° C polyester was obtained. After spinning this polymer into chips and drying it in the same manner as in Example 1, the spinning was attempted.
Hollow fibers could not be obtained due to a large increase in pack pressure and frequent breakage.

Comparative Example 3 The multifilament of 74 denier / 24 filament obtained in Example 3 was used as a knitted fabric, and scouring and presetting were performed by a conventional method.

The deodorizing performance of the obtained fabric was measured in the same manner as in Example 1 without subjecting the fabric to a weight reduction treatment with an aqueous solution of sodium hydroxide. 1
After a time, the residual ammonia concentration was 1250 ppm, and the deodorization rate was as poor as 11%.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI D06M 5/02 D01F 6/92 306A 1/10 D06M 11/38

Claims (2)

(57) [Claims] 1. A fiber made of polyester containing 0.1 to 5% by weight of a deodorant, which is scattered in a cross section of the fiber,
A deodorant polyester fiber which is arranged in the fiber axis direction and has at least a part thereof formed with micropores communicating with the vicinity of the center of the fiber. 2. A polyester is synthesized by reacting a bifunctional carboxylic acid mainly composed of terephthalic acid or an ester-forming derivative thereof with an alkylene glycol having 2 to 6 carbon atoms or an ester-forming derivative thereof to obtain a polyester. In melt-spinning polyester into polyester fibers, the following general formula is used at any stage until the melt-spinning is completed. 0.3 to 15 mol% based on the bifunctional carboxylic acid compound, and 0.1 to 5% by weight based on polyester based on the bifunctional carboxylic acid compound.
The method for producing a deodorant polyester fiber according to claim 1, wherein the added polyester fiber is treated with an aqueous alkali solution to elute 2 to 50% by weight from the fiber.