JPH05132821A - Fragrant sheath-core type conjugated filament yarn and its production - Google Patents

Abstract

PURPOSE:To obtain the subject filament yarn with sustained fragrance by melt spinning for sheath-core type conjugate yarn made up of a polymer composition containing a specified amount of essential oil as the core component and a polyester as the sheath component, followed by addition of a specific sulfonic acid compound and then treatment with an aqueous solution of alkali compound. CONSTITUTION:In carrying out melt spinning for sheath-core type conjugate yarn made up of a polymer composition containing 0.1-5wt.% of essential oil as the core component and a polyester produced by reaction of an acid component predominant in terephthalic acid and a diol component predominant in a 2-6C alkylene glycol as sheath component, 0.3-15mol%, based on the acid component, of a sulfonic acid compound of the formula (Y is H or ester-forming functional group; M<1> and M<2> are each metal; (n) is 1-2) is added to the molten polymer at any stage until completion of the melt spinning, and 10-50wt.% of the sheath part is then eluted from the resulting conjugated filament yarn to form fine pores dispersed in the remaining sheath part, oriented along the fiber axis, and (partly) penetrating to the core part, thus obtaining the objective filament yarn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a core-sheath type composite long fiber having a durable scent. More specifically, by using it for outer clothing such as blouses and underwear, as well as bedding, interior, etc., a new scent that can enjoy the "forest bathing effect", "cooling effect" etc. for an extremely long period of time The present invention relates to a core-sheath type composite filament and a method for producing the same.

[0002]

2. Description of the Related Art Polyester fiber is widely used as a fiber for clothing and industry due to its characteristics. Polyethylene terephthalate fibers, which have the characteristics of being particularly resistant to wrinkling, easy to wear immediately after washing, excellent in strength, and easy to diversify the texture, have become the mainstream of synthetic fibers as fibers for clothing. ..

On the other hand, the quality of life has become higher or interest in scents has increased. For example, "forest bath" due to the scent of cypress.
Due to the growing interest in emotional security such as effects, there has been an increasing demand for giving fragrance to these synthetic fibers.

However, this fragrance substance easily disappears, and it was difficult to maintain its effect for a long period of time. Therefore, there are various methods to obtain the "forest bathing" effect in your home by applying the natural essential oil component substances that are scattered and drifting in the forest to indoor installation items such as outerwear, bedding, interiors, or interior materials for houses. Proposed. For example, a method of adsorbing or adhering the essential oil to the final fiber product by post-processing has been proposed, but the essential oil tends to fall off by washing with water or washing, and the rate of reduction of the essential oil due to volatilization is fast, resulting in poor aroma persistence. It was a thing.

Recently, Japanese Patent Laid-Open No. 61-201012 discloses a fiber obtained by kneading several kinds of natural essential oils or an essential oil mixed with components separated therefrom into the core of a hollow core-sheath type composite fiber. JP-A-62-85010 discloses a hollow multi-core core-sheath type composite fiber, and JP-A-3-76815 discloses a core-sheath having a composition prepared by kneading a specific polymer with essential oil. Type composite fibers have been proposed. However, all of these conjugate fibers are intended for short fibers, and since the essential oil is volatilized from the cut surface and the aroma effect is exhibited, it is considered that the long fibers are used as they are. There is a drawback that the effect cannot be obtained.

Further, Japanese Patent Laid-Open No. 1-280068 discloses that
There has been proposed a method for obtaining an aromatic conjugate fiber in which a fragrance is exhausted to the core of a composite fiber whose core is partially exposed on the fiber surface. According to such a method, long fibers can be obtained as the aromatic fiber, and it is possible to simultaneously achieve the expression of the feeling unique to the long fiber woven or knitted fabric and the imparting of aromaticity. However, in order to exhaust the fragrance to the core, it is necessary to perform treatment at high temperature and high pressure for a long time, which not only reduces productivity but also
The exhaust amount was also insufficient and the durability (persistence of fragrance) was also insufficient.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and its purpose is to provide a fragrance that can enjoy an aroma effect for a very long period even though it is a long fiber. It is to provide a core-sheath type composite continuous fiber having the following and a method for producing the same.

[0008]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, the essential oil hardly penetrates through the polyester. Therefore, the essential oil is contained in the core and the polyester is arranged in the sheath. Along with that, by forming fine pores penetrating to the core portion in the sheath portion, it was found that a long fiber having a scent that is excellent in durability of the aroma effect and that can easily control the volatilization rate of the essential oil component is obtained. The invention has been reached.

That is, the present invention is: A core-sheath type composite filament having a polymer composition containing 0.1 to 5% by weight of an essential oil as a core and a polyester as a sheath, wherein the sheath of the composite filament has a cross-section of a fiber. 1. A core-sheath type composite long fiber having a scent characterized by having fine pores scattered and arranged in the fiber axis direction and at least a part of which penetrates to the core. A polymer composition containing 0.1 to 5% by weight of essential oil is used as a core, and an acid component mainly containing terephthalic acid and a carbon number of 2 to 6 are used.
In the melt-spinning of the core-sheath type composite continuous fiber with the polyester obtained by reacting the alkylene glycol as a main component with the diol component as a sheath, the following general formula (I)

[0010]

[Chemical 3]

(In the formula, Y represents a hydrogen atom or an ester-forming functional group, M ¹ and M ² represent a metal, and n represents 1 or 2.)
At least one of the sulfonic acid compounds represented by the formula (3) is added in an amount of 0.3 to 15 mol% with respect to the acid component of the polyester, and the obtained composite long fibers are treated with an aqueous solution of an alkali compound. 10 to 50 of its sheath
A scent characterized by being dispersed in the sheath portion of the composite long fiber by being leached out by weight% and arranged in the fiber axial direction, and at least a part of which forms fine pores penetrating to the core portion. A method for producing a core-sheath type composite continuous fiber having:

The aromatic component used in the present invention is an essential oil,
Especially natural essential oils such as cypress oil, peppermint oil, eucalyptus oil,
It is important to use Hiba oil or camphor oil, but the components contained in these essential oils may be separated and purified for use, or synthetic essential oils may be used.

These essential oils are usually used in the leaves, rhizomes and leaves of plants.
It is obtained by steam distillation from bark, fruits, buds, resins, etc., and contains terpenoids as the main component. This terpenoid is extremely difficult to permeate the polyester layer used in the sheath part, so as described in detail later, by controlling the amount of micropores penetrating to the core part in the sheath part, the evaporation rate of the essential oil component is controlled. Can be controlled easily.

The amount of the essential oil blended with the polymer constituting the core is required to be 0.1 to 5% by weight, preferably 0.5 to 2% by weight. If less than 0.1% by weight,
It is not preferable because the essential oil component is less likely to be volatilized into the air and a sufficient aroma effect such as a forest bath effect cannot be obtained.
On the other hand, if it exceeds 5% by weight, the solubility and dispersibility in the core polymer is deteriorated, and stable melt spinning cannot be performed, and the obtained fiber has too much volatilization amount of the essential oil component into the air. It is not preferable because it causes discomfort.

Although the polymer constituting the core is not particularly limited, the essential oil used in the present invention is generally inferior in heat resistance and is easily evaporated or decomposed by heat, so that it has a low melting point (softening point). It is desirable to use a combination, and examples thereof include various high-density / medium-density / low-density polyethylenes, ethylene-based polymers such as ethylene / vinyl acetate copolymers, and mixtures thereof.

The polymer constituting the sheath portion of the composite long fiber of the present invention is made of polyester from the viewpoint that the essential oil component is difficult to diffuse and permeate through the polymer and excellent mechanical properties and texture are obtained. In addition, in order to allow the essential oil component added and blended to the core portion to pass through the sheath portion and vaporize to the outside air without deteriorating the mechanical properties of the fiber, the sheath portion has a fiber cross-section. It is necessary that the fine holes are scattered and arranged in the fiber axis direction, and at least a part thereof penetrates to the core portion.

The method of forming such fine pores in the polyester sheath is not particularly limited, but a specific amount of the following general formula (I) is particularly preferable during the synthesis of polyester.

[0018]

[Chemical 4]

(In the formula, Y represents a hydrogen atom or an ester-forming functional group, M ¹ and M ² represent a metal, and n represents 1 or 2.)
A method is preferred in which the modified polyester obtained by adding the compound represented by the formula (3) is melt-spun as a sheath component, and the obtained core-sheath type composite long fibers are treated with an alkaline aqueous solution to remove a part of the modified polyester. The micropores formed in the sheath portion of the composite fiber thus obtained have a diameter of 0.01 to 2
Even though the length is in the range of μm and the length is 20 times longer than the diameter, the essential oil can pass through sufficiently,
The fibrillation of the sheath is unlikely to occur and the mechanical properties of the fiber are not deteriorated.

The polyester used in the present invention is mainly a polyester having terephthalic acid as a main acid component and ethylene glycol, trimethylene glycol, or tetramethylene glycol as a main glycol component. Further, it may be a polyester in which a part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and / or a polyester in which a part of the glycol component is replaced with another diol component.

The sulfonic acid compound to be blended with the polyester is represented by the following general formula (I),

[0022]

[Chemical 5]

In the formula, M ¹ and M ² are metals, and as M ¹ , alkali metal, alkaline earth metal, Mn 1/2,
Co1 / 2 or Zn1 / 2 is preferable, and Li and N are especially preferable.
a, K, Ca1 / 2 and Mg1 / 2 are particularly preferable, and as M ² , alkali metal or alkaline earth metal is particularly preferable, and Li, Na, K, Ca1 / 2 and Mg1 / 2 are particularly preferable. 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 ″ ′ ″.
(However, R '''is a hydrogen atom, an alkyl group or a phenyl group having 1 to 4 carbon atoms) or _{-CO- [O (CH 2) q} ] -
_p OH (however, q is an integer of 2 or more, p is an integer of 1 or more)
Etc. are preferred.

A preferred specific example of such a sulfonic acid compound is 3-carbomethoxybenzenesulfonic acid N.
a-5-Carboxylic acid Na, 3-carbomethoxy benzene sulfonic acid Na-5-carboxylic acid K, 3-carbomethoxy benzene sulfonic acid K-5-carboxylic acid K, 3-
Hydroxyethoxycarbonyl / benzenesulfonic acid N
a-5-carboxylic acid Na, 3-carboxy benzene sulfonic acid Na-5-carboxylic acid Na, 3-hydroxyethoxy carbonyl benzene sulfonic acid Na-5-carboxylic acid Mg1 / 2, benzene sulfonic acid Na-3,5 -Na dicarboxylic acid, Na benzene sulfonic acid Na-3,5-dicarboxylic acid Mg1 / 2 and the like can be mentioned.

The above sulfonic acid compounds may be used alone or in combination of two or more, and the compounding amount thereof is 0.3 to 15 mol% with respect to the acid component of the polyester.
Is preferred. If it is less than 0.3%, it is difficult to form fine pores penetrating to the core portion, while if it exceeds 15 mol%, the diameter of the fine pores becomes large, or the number of fine pores becomes too large, resulting in fiber dynamics. Characteristics tend to be insufficient.

The addition time may be any stage before the spinning step of melt-spinning the polyester into the composite fiber is completed.
It may be added during the synthesis of the polyester or after the completion of the synthesis and before the melt spinning. In any case, it is preferable that they are mixed in a molten state after addition.

In order to remove a part of the modified polyester from the composite fiber thus obtained, it may be subjected to stretching heat treatment, false twisting or the like, if necessary, or may be dipped in an aqueous solution of an alkali compound after being made into a cloth. Well, especially when dyeing, it is desirable to carry out after the step. This makes it possible to reduce the amount of the essential oil component eluted in the dyeing solution during dyeing.

Examples of the alkaline 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 preferable.

The concentration of the aqueous solution of the alkaline compound is
Depending on the type of alkaline compound, treatment conditions, etc.,
Usually, the range of 0.01 to 40% by weight is preferable, and particularly, the range of 0.
The range of 1 to 30% by weight is preferable. Processing temperature is room temperature ~ 1
The temperature is preferably in the range of 00 ° C., and the treatment time is usually 1 minute to 4 hours. Further, the amount of the modified polyester to be eluted and removed by the treatment of the aqueous solution of the alkaline compound is
It should be in the range of 10 to 50% by weight, preferably 15 to 30% by weight, based on the weight of the sheath component fibers. By thus treating with an aqueous solution of an alkali compound, the sheath fibers of the composite fibers are scattered in the fiber cross-section, arranged in the fiber axis direction, and at least a part of them penetrates to the core portion and has a diameter of about 0.01. Fine pores having a diameter of up to 2 μm and a length of 20 times or less of the diameter are formed, and an essential oil component volatilizing effect is exhibited.

When the above-mentioned elution amount is increased, the amount of the through holes is increased and the volatilization rate of the essential oil component is increased, while the duration of the aroma effect is shortened. On the other hand, if the amount of elution is decreased, the amount of through holes is decreased and the volatilization rate of the essential oil component is decreased, while the duration of the aroma effect is prolonged. Therefore, the degree and duration of the fragrance effect can be arbitrarily set by appropriately selecting the elution amount according to the type or application of the essential oil used.

The composite continuous fiber of the present invention may have any additives such as a catalyst, if necessary, for both its sheath and core.
An anti-coloring agent, a heat-resistant agent, a flame retardant, a fluorescent whitening agent, a matting agent, a coloring agent, inorganic fine particles and the like may be added.

Next, the composite ratio of the core part and the sheath part constituting the composite continuous fiber of the present invention is preferably in the range of 70/30 to 30/70 by weight. If the core ratio exceeds 70%,
The polyester component is insufficient, and the performance and texture of the polyester are reduced, while the ratio of the core component is 3
If it is less than 0%, the amount of essential oil retained is small, which is not desirable. Particularly preferred range is 60/40 to 40/6
It is 0.

[0033]

As described above, the core-sheath type composite continuous fiber having the scent of the present invention has a specific fine particle penetrating to the core portion, although the sheath portion is made of polyester which is difficult to permeate the essential oil component. Since it has pores, it is a long fiber and can simultaneously achieve a good fragrance effect and its excellent durability. Moreover, since the sheath portion is a long fiber composed of polyester, a fabric excellent in drapeability, waist and tension, which is peculiar to a long fiber, can be obtained, unlike conventional aromatic fibers.

Furthermore, according to the production method of the present invention, the ratio of the through-holes can be easily changed, so that the degree of the fragrance effect and the duration thereof can be easily adjusted depending on the type of essential oil used or the intended use of the obtained fiber. Can be set to.

Therefore, when the scented composite long fibers of the present invention are applied to products in the fields of outer garments such as blouses and blousons, inner garments such as underwear and underwear, interiors, vehicle interiors, etc. It is possible to enjoy the combined effect and the aroma effect at the same time.

[0036]

The present invention will be described in more detail with reference to the following examples. The scent effect was measured according to the following method.
Place 100g of sample in a box of 1m ³
After standing at 0 ° C. for 3 hours, the strength of the scent was evaluated on a 5-point scale. ++: The scent is too dark ++: The scent is slightly dark ◯: Preferable −: Slight fragrance −−: Almost no fragrance This evaluation was performed by 10 testers, and the average value was calculated.

[0037]

Example 1 A modified polyester as a sheath component was synthesized as follows. That is, dimethyl terephthalate 197
Part, ethylene glycol 124 parts, sodium benzenesulfonate-3,5-dicarboxylic acid Mg1 / 2 1.2
And 0.118 part of calcium acetate monohydrate were placed in a glass flask equipped with a rectification column for transesterification, and then 0.112 parts of trimethyl phosphate as a stabilizer and 0.079 part of antimony trioxide as a polycondensation catalyst were added. 20 minutes under normal pressure at 280 ℃, under reduced pressure of 30mmHg 1
After reacting for 5 minutes, it was reacted under high vacuum for 80 minutes. The final internal pressure was 0.38 mmHg, and the modified polyester obtained had an intrinsic viscosity of 0.600 and a softening point of 258 ° C.

Ethylene / vinyl acetate copolymer containing 20 wt% of cypress extract essential oil (copolymerization weight ratio 84: 1
6) 250 parts by weight of 5 parts by weight and 95 parts by weight of high density polyethylene having a melt index of 20 are chip blended.
Melted at ℃ to the core part, and the modified polyethylene terephthalate above was melted at 290 ° C. and fed to the core-sheath type composite spinning device so as to be placed in the sheath part, and 0.63 g / min. At the rate of 0.63 g / min. / Hole, composite was discharged from a circular spinning hole with a diameter of 0.2 mm in a core-sheath type (composite ratio 50
/ 50). The number of discharge holes was 24. 1 spun yarn
It was wound at a speed of 500 m / min, and then stretched 2.4 times in the usual way to obtain a multifilament of 76 denier / 24 filament.

The obtained multifilament was formed into a plain weave and scouring and drying was carried out by a conventional method. The sample thus obtained was dyed by a conventional method at 130 ° C. for 20 minutes and then dried, and further 30 g / L kept in a boiling state (100 ° C.).
Was immersed in the aqueous solution of caustic soda and the treatment time was changed to 5 to 120 minutes to carry out the weight reduction treatment.

The results are shown in Table 1. In the table, the observation of the fiber cross section is the result of observing the cut surface with an electron microscope after cutting the fiber after cooling in liquid nitrogen.

[0041]

[Table 1]

From the above table, when the alkali weight loss rate is less than 10% (No. 1), since the micropores do not penetrate through the sheath, the essential oil component of the core is not volatilized to the outside and the aromaticity is maintained. It turns out that it is hardly recognized.

When the alkali weight loss rate exceeds 50% (Nos. 8 to 10), a part of the sheath portion is broken and the core portion is exposed, so that the scent is too strong and rather unpleasant. It is given (7 or more people are uncomfortable), and its fragrance has a short duration and almost no scent within 1 month. Moreover, it is understood that the mechanical properties of the polyester in the sheath part are also deteriorated, so that the strength of the fabric is deteriorated, and only the drape property, the feel of the waist and the stretch are inferior.

On the other hand, the fiber (N
o. In Nos. 2 to 7), it was observed that fine holes penetrating the sheath were formed. In Nos. 3 to 5, it was determined that eight or more persons had a preferable scent. Also, when the fiber was remeasured one year later, the level of fragrance was at a desirable level.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location // D06M 101: 20 101: 32 (72) Inventor Kazunori Orii 1 Minamihonmachi, Chuo-ku, Osaka-shi, Osaka Chome 6-7 Teijin Limited

Claims (3)

[Claims] 1. A core-sheath type composite filament comprising a polymer composition containing 0.1 to 5% by weight of an essential oil as a core and a polyester as a sheath. A core-sheath type composite long fiber having a scent characterized by having fine pores which are scattered in the fiber cross-section and are arranged in the fiber axial direction and at least a part of which penetrates to the core. 2. The polyester constituting the sheath is represented by the following general formula (I): (In the formula, Y is a hydrogen atom or an ester-forming functional group, M ¹
And M ² are metals, and n is 1 or 2. The core-sheath type composite continuous fiber according to claim 1, which is a polyester obtained by adding 0.3 to 15 mol% of at least one of the sulfonic acid compounds represented by the formula (3) to the acid component of the polyester. 3. A polymer composition containing 0.1 to 5% by weight of an essential oil as a core, and an acid component mainly containing terephthalic acid and a diol component mainly containing alkylene glycol having 2 to 6 carbon atoms. When melt-spinning a core-sheath type composite continuous fiber with a polyester obtained by reaction as a sheath, the following general formula (I): (In the formula, Y is a hydrogen atom or an ester-forming functional group, M ¹
And M ² are metals, and n is 1 or 2. At least one of the sulfonic acid compounds represented by the formula (3) is added in an amount of 0.3 to 15 mol% based on the acid component of the polyester, and the obtained composite long fibers are treated with an aqueous solution of an alkali compound to obtain the composite long fibers. By eluting 10 to 50% by weight of the sheath portion thereof, the fine filaments scattered in the sheath portion of the composite long fiber are arranged in the fiber axis direction, and at least a part of the fine pores penetrates to the core portion. A method for producing a core-sheath type composite long fiber having a scent characterized by being formed.