JPH05279920A - Production of mothproofing polyester fiber - Google Patents

Abstract

PURPOSE:To incorporate a mixture solution of a mothproofing agent with an aliphatic polyester in cluster fiber while preventing the mothproofing agent from evaporating and scattering by kneading the mixture solution to the polyester polymer just before its spinning and then spinning the polyester polymer. CONSTITUTION:A low-viscosity mothproofing agent (e.g. a dialkyl phthalate) is mixed with an aliphatic polyester (e.g. an adipic acid-based polyester) to provide a mixture solution feedable with a gear pump. The resultant mixture solution is then rapidly kneaded in a polyester polymer just before its spinning with a kneader, etc., and the obtained polyester polymer is subsequently spun.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an insect-repellent polyester fiber in which an insect-repellent agent is kneaded into polyester fiber to impart insect-repellent property. The present invention relates to a method for producing insect-repellent polyester fiber by kneading into

[0002]

2. Description of the Related Art Conventionally, it has been studied to mold a resin composition prepared by mixing a thermoplastic resin with an insect repellent to produce an insect repellent fiber, film or sheet.

For example, in Japanese Unexamined Patent Publication (Kokai) No. 3-205456, a resin composition prepared by melting a thermoplastic resin with one or more agents selected from dialkyl phthalate, dialkyl adipate and dialkyl fumarate is melted. It has been shown to mold to produce pest control moldings.

Here, in the production of insect repellent fibers by using the above insect repellents such as dialkyl phthalate, dialkyl adipate and dialkyl fumarate, the insect repellents are generally added to the polymer at a high temperature by a masterbatch method. It is conceivable to disperse and then spin this to produce insect-repellent fibers.

However, it is difficult to sufficiently disperse the above insect repellent in the polymer by the masterbatch method, and the above insect repellent generally has low viscosity and is liable to volatilize. When dispersed in a polymer at high temperature, these insect repellents smoke and scatter, and it becomes impossible to add a sufficient amount of insect repellent to the fiber, or these insect repellents are spun during spinning. There are problems such as evaporation and generation of air bubbles in the fiber, which lowers the strength of the fiber.

Particularly, in the case of polyester fibers having a high melt molding temperature of 280 to 300 ° C., when the insect repellent is dispersed in the polyester polymer at a high temperature as described above,
There is a problem in that the insect repellent increases the amount of fumes and it is not possible to obtain an insect repellent polyester fiber containing a sufficient amount of the insect repellent.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems in producing insect-repellent fibers by kneading an insect-repellent agent having a low viscosity and easily volatilized into a polymer. In particular, it is an object to solve the problem in the case of producing an insect-controlling polyester fiber by kneading the above-mentioned insect-controlling agent into a polyester polymer having a high melt molding temperature.

That is, in the present invention, when the insect repellent having a low viscosity and being easily volatilized as described above is kneaded into a polyester polymer having a high melt molding temperature to produce an insect repellent polyester fiber, a conventional insect repellent is used. This insect repellent is kneaded into polyester fiber easily and efficiently without causing smoke, so that an insect repellent polyester fiber having sufficient strength and sufficient strength can be stably obtained. This is an issue.

[0009]

According to the present invention, in order to solve the above problems, a low viscosity insect repellent is mixed with an aliphatic polyester to obtain a viscous mixed liquid which can be sent by a gear pump. Immediately before spinning the polyester polymer, this mixture was rapidly kneaded into the polyester polymer and then spun to produce an insect-proof polyester fiber.

The above insect repellent used for producing the insect repellent polyester fiber is a compound which is well compatible with the polyester polymer, has stability even at high temperatures, and has a high insect repellent effect and is safe. It is preferable to select and use, for example, dialkyl terephthalate, dialkyl adipate, dialkyl fumarate and the like, wherein the alkyl group having 1 to 8 carbon atoms is used, and as the dialkyl terephthalate,
Examples thereof include orthodialkyl phthalate, isodialkyl phthalate and teredialkyl phthalate. The insect repellents generally have a viscosity at 25 ° C. of 100 cps or less.

The aliphatic polyester to be mixed with the above-mentioned low-viscosity insect repellent has a high viscosity so that it is not difficult to inject it into the polyester polymer and has a small heating loss, and further, the polyester polymer. It is preferable to use one that has a low reactivity with and maintains a high molecular state.

Here, such an aliphatic polyester generally has a viscosity at 25 ° C. of 15,000 cp.
s or more, but the viscosity is 100,000 cps
If it exceeds, it is generally difficult to inject it into the polyester polymer. Therefore, a polymer having a molecular weight of 100,000 cps or less should be used, and the average molecular weight thereof should be 3500 or more, preferably 4000 or more.
If it exceeds 0000, it is generally difficult to inject it into the polyester polymer. Therefore, it is preferable to use one having an average molecular weight of 20,000 or less, and further use an aliphatic polyester having a heating loss of 2% or less and a hydroxyl value of 20 mgKOH / g or less. It is preferable to use it. In addition, the above-mentioned heating loss shows the value when heating from 60 ° C. to 310 ° C. at 10 ° C./min.

Examples of such aliphatic polyesters include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and glutaric acid, and ethylene glycol, propylene glycol, 1,3-butanediol and pentyl. Glycol, hexyl glycol,
A copolymer of glycol such as diethylene glycol or polyethylene glycol, polypropylene glycol, a polyalkylene glycol such as polybutylene glycol, or at least one end of a polyester obtained from these aliphatic dicarboxylic acid and glycol is propyl alcohol, Those blocked with monohydric alcohols such as butyl alcohol and amyl alcohol are used.

The aliphatic carboxylic acid having 3 to 8 carbon atoms is usually used as the acid component of the aliphatic polyester, and the fatty acid glycol having 2 to 6 carbon atoms is usually used as the glycol component. Adipic acid is most preferable as the acid component, and ethylene glycol and 1,3 butadiol are the most preferable as the glycol component. Furthermore, it is preferable to use propyl alcohol as the monohydric alcohol that blocks the ends of the polyester.

When the above-mentioned low-viscosity insect repellent and the viscous aliphatic polyester are mixed, the above-mentioned insect repellent and the aliphatic polyester are usually mixed with each other.
0:90 to 50:50, preferably 20:80 to 50:
The mixed solution of the insect repellent and the aliphatic polyester mixed in such a manner that the viscosity is such that a gear pump can deliver the solution, generally the viscosity at 25 ° C. is 1
It should be at least 00 cps, preferably at least 300 cps.

In addition, when the mixed solution of the insect repellent and the aliphatic polyester mixed as described above is rapidly kneaded with the polyester polymer immediately before spinning the polyester polymer, a kneader having a static kneading element,
For example, a static mixer (trade name) manufactured by Kenix Co., or a loss-ISG-mixer (trade name) manufactured by Tokushu Kika Kogyo Co., Ltd. is used.

When the polyester polymer is kneaded with a mixed solution of an insect repellent and an aliphatic polyester, spinning and the like are performed well, and the obtained insect repellent polyester fiber has sufficient insect repellent performance. Therefore, 1 to 6 of the above mixed solution is added to the polyester polymer.
%, Preferably 2 to 4% by weight, and 0.1% by weight of the insect repellent in the obtained insect repellent polyester fiber.
The above content is preferably 0.5% by weight or more, more preferably 0.5% by weight or more. However, if the amount of the insect repellent contained in the polyester fiber is too large, the physical properties of the polymer are deteriorated, so it is generally difficult to contain the repellent in an amount of 10% by weight or more.

[0018]

In the method for producing the insect-repellent polyester fiber according to the present invention, the low-viscosity insect-repellent agent is mixed with the viscous aliphatic polyester as described above to prepare a viscous mixed solution which can be sent by a gear pump. Since this mixture was immediately kneaded into the polyester polymer immediately before spinning the polyester polymer,
The above insect repellent together with the aliphatic polyester is well kneaded into the polyester polymer, so that the conventional insect repellent is less likely to be evaporated and scattered.

It is also said that the above insect repellent vaporizes when the polyester polymer is rapidly kneaded with the mixed solution of the low viscosity insect repellent and the aliphatic polyester, and then the polyester polymer is spun. A small amount of insect repellent is sufficiently contained and an insect repellent polyester fiber having sufficient strength can be stably produced.

[0020]

EXAMPLES In the following, various examples in which the type of viscous aliphatic polyester to be mixed with a low-viscosity insect repellent is changed in the method for producing insect repellent polyester fibers according to the present invention will be described.

Example 1 In this example, as a low-viscosity insect repellent, a liquid insect repellent having a viscosity of 13 cps at 25 ° C. (Osaka Kasei Co., Marcamite ED) was used.
On the other hand, as the viscous aliphatic polyester mixed with this low-viscosity insect repellent, the average molecular weight is 4
Viscosity at 2,000 ° C., 25 ° C., 25,000 cps, loss on heating is 1.8%, hydroxyl value is 18.8 mg KOH
/ G of adipic acid-based polyester was used.

Then, in this example, an experiment was conducted using various mixed solutions in which the mixing ratio of the insect repellent and the adipic acid-based polyester was changed.

Here, in Experimental Example 1, 25 parts by weight of the adipic acid-based polyester was used per 75 parts by weight of the insect repellent, and in Experimental Example 2, 50 parts by weight of the insect repellent was added. On the other hand, the adipic acid-based polyester is added at a ratio of 50 parts by weight, and in Experimental Example 3, the adipic acid-based polyester is added at a ratio of 75 parts by weight to 25 parts by weight of the insect repellent. Three
These were kneaded with a main roll to obtain each mixed liquid.

Experimental Examples 1 to 3 obtained as described above
As a result of measuring the viscosities of the respective mixed liquids at 25 ° C., the viscosity of the mixed liquid in Experimental Example 1 was 260 cps, the viscosity of the mixed liquid in Experimental Example 2 was 1950 cps, and the viscosity of the mixed liquid in Experimental Example 3 was 8000 cps.

Next, after adding 3 parts by weight of each of the above mixed solutions to 100 parts by weight of a molten polymer of polyethylene terephthalate having a number average molecular weight of 21,000,
This was rapidly kneaded using a static mixer (made by Kenix Co.) and a BKH mixer (made by Sulzer Co., Ltd.) provided in a polymer flow path, and then spun by a spinneret by a usual method and stretched to obtain a fineness 7. A 78 denier insect repellent polyester fiber was produced.

When the yarn spun from the spinneret was drawn, the heat setting temperature during drying was set to 130 ° C. or lower in order to prevent the insect repellent from evaporating.

As a result of spinning as described above, in the case of the mixture of Experimental Example 1 in which 25 parts by weight of adipic acid-based polyester was added to 75 parts by weight of the insect repellent and the viscosity was 260 cps in the above case, However, there was a drop of polymer from the spinneret, and an undrawn yarn could not be obtained.

On the other hand, adipic acid type polyester is mixed with the above insect repellent at a ratio of 50:50 or more,
When each of the mixed solutions of Experimental Examples 2 and 3 having a viscosity of 300 cps or higher was used, the polymer did not drip from the spinneret, and the insect repellent smoke was small.

As a result, when kneading the mixed solution obtained by mixing the above insect repellent and the adipic acid polyester with the molten polymer of polyethylene terephthalate and spinning the mixture, 5 parts of the adipic acid polyester is added to the insect repellent.
It is mixed at a ratio of 0:50 or more and its viscosity is 300 cp.
It has been found that it is preferable to use s or more.

Next, when the fiber strength and elongation of the insect-repellent polyester fiber produced by using the mixed solution in the above Experimental Example 2 were measured, the fiber strength of the insect-repellent polyester fiber was 4.27 g / d. Elongation is 4
It was 3.6% and had sufficient fiber strength and elongation.

As a result of measuring the content of the insect repellent in the insect repellent polyester fiber, the content of the repellent was 1.11% by weight, and the residual rate of the repellent was as high as about 81%. The content of the insect repellent was analyzed by gas chromatography after dissolving the insect repellent polyester fiber.

Further, with respect to the insect-repellent polyester fiber produced by using the mixed solution in the above-mentioned Experimental Example 2, the change over time in the content of the insect-repellent agent in this insect-repellent polyester fiber and the change over time in the repelling rate against Dermatophagoides farinae were examined. It was

The content of the insect repellent in the insect repellent polyester fiber was analyzed by gas chromatography after dissolving the fiber after a predetermined number of days.

Regarding the repellent rate against Dermatophagoides farinae, according to the Osaka Prefectural Institute of Public Health, the diameter is 3
Place a petri dish of cm on a viscous sheet, and place six identical petri dishes around the petri dish so as to contact the petri dish in the center,
Samples in the treated and untreated sections cut out to a diameter of 3 cm were alternately placed in the six surrounding petri dishes, and 0.01 g of a powder sample containing no mite was placed on each specimen, while in the central petri dish. Put the mites with the feed removed, keep the humidity at 75%, leave it in the hot air at 25 ° C, count the number of mites that have invaded the medium of the 6 petri dishes, and calculate the repellent rate by the following formula. did.

Repellent rate (%) = [(number of invading mites in control group-
Number of invading mites in test area) / number of invading mites in control area] × 100

Table 1 below shows the changes over time in the content of the insect repellent agent in the insect repellent polyester fiber and the repelling rate against mites, measured as described above.

[0037]

[Table 1]

As is clear from these results, the insect-repellent polyester fiber produced by using the mixed solution in the above-mentioned Experimental Example 2 has a small change in the content of the insect-repellent agent over time, and has a repellent rate against mites over a long period of time. The value was stable and high.

(Example 2) In this example, the same insect repellent as in Example 1 was used as the low viscosity insect repellent, while the average viscosity of the aliphatic polyesters mixed with the repellent was average. The molecular weight is 8,000, the viscosity at 25 ° C. is 75,000 cps, and the weight loss on heating is 1.
A sebacic acid polyester having 3% and a hydroxyl value of 18.6 mgKOH / g was used.

Also in this example, as in the case of Example 1, an experiment was conducted using various mixed solutions in which the mixing ratio of the above insect repellent and the above sebacic polyester was changed.

Here, in Experimental Example 4, 25 parts by weight of the above polyester sebacate was added to 75 parts by weight of the above insect repellent, and in Experimental Example 5, 50 parts by weight of the above insect repellent was used. The above-mentioned polyester sebacate is added at a ratio of 50 parts by weight, and in Experimental Example 6, the above-mentioned polyester sebacate is added at a ratio of 75 parts by weight to 25 parts by weight of the above insect repellent, and three rolls each These were kneaded to obtain each mixed solution.

As a result of measuring the viscosities of the above mixed solutions used in Experimental Examples 4 to 6 at 25 ° C., the viscosity of the mixed solution in Experimental Example 4 was 290 cps, the viscosity of the mixed solution in Experimental Example 5 was 2760 cps, The viscosity of the mixed solution in Experimental Example 6 was 18000 cps.

Then, except using these mixed solutions,
Each insect-repellent polyester fiber was manufactured in the same manner as in Example 1 above.

In the case where each insect-controlling polyester fiber was produced in this manner, an experimental example using a mixed solution obtained by adding 25 parts by weight of the above-mentioned polyester sebacate to 75 parts by weight of the insect-repellent agent as described above In the case of No. 4, while there was a drop of polymer from the spinneret during spinning, a mixed solution containing the above-mentioned sebacic polyester in a ratio of 50:50 or more to the insect repellent was used. In Experimental Examples 5 and 6, no polymer was dropped from the spinneret.

In Experimental Example 4, the polymer dropped from the spinneret during spinning, but the amount of polymer drop was smaller than in Experimental Example 1 in Example 1 above.

As a result, as the aliphatic polyester to be mixed with the low-viscosity insect repellent, one having a high viscosity is preferably used for spinning, and an aliphatic polyester having such a high viscosity is used. As a result, it was possible to increase the amount of insect repellent contained in the insect repellent polyester fiber.

Example 3 In this example, as the aliphatic polyester mixed with the low viscosity insect repellent, 0.3 mol of polyethylene glycol having an average molecular weight of 2000 and 0.3 mol of ethylene glycol were used per 1 mol of adipic acid. A liquid polyester obtained by adding 0.7 mol and 0.2 mol of amyl alcohol was used.

The liquid polyester thus obtained had a viscosity at 25 ° C. of 3000 cps, a loss on heating of 4.6% and a hydroxyl value of 22.5 mgKOH /
It was g.

In Experimental Example 7, the liquid polyester was added to the low viscosity insect repellent at 75:25.
The mixed solution mixed in the ratio of was added to polyethylene terephthalate in the same manner as in each of the experimental examples described above. In this case, since the viscosity of the mixed solution was as low as 27 cps, it was not possible to add this mixed solution to polyethylene terephthalate.

In Experimental Example 8, 50:50 of the liquid polyester was added to the low viscosity insect repellent.
The mixed solution mixed in the ratio of was added to polyethylene terephthalate in the same manner as in each of the experimental examples described above. In this case, the viscosity of the mixed solution was 200 cps, and 1 part by weight of the mixed solution could be added to 100 parts by weight of the polyethylene terephthalate. A polymer drop occurred.

Further, in Experimental Example 9, a mixed solution prepared by mixing the liquid polyester with the low viscosity insect repellent at a ratio of 25:75 was added to polyethylene terephthalate in the same manner as in the above Experimental Examples. I did it. Also in this case, as in the case of Experimental Example 8 described above, 1 part by weight of this mixed solution could be added to 100 parts by weight of polyethylene terephthalate, but when 2 parts by weight or more were added, the spinning spinneret was used. A polymer drop occurred.

As is clear from this result, when the viscosity of the aliphatic polyester to be mixed in addition to the above-mentioned low-viscosity insect repellent is low, it is necessary to inject this mixed solution into the polyester polymer or perform spinning. However, it was not possible to incorporate a large amount of insect repellent into the polyester fiber.

[0053]

As described above in detail, in the method for producing an insect-controlling polyester fiber according to the present invention, the viscosity of a low-viscosity insect-controlling agent is mixed with a viscous aliphatic polyester and the viscosity can be sent by a gear pump. Was prepared and the mixture was kneaded into the polyester polymer immediately before spinning of the polyester polymer, so that the above insect repellent together with the aliphatic polyester was kneaded into the polyester polymer. It is rare that the insect repellent evaporates and scatters as in the past.

In the present invention, the polyester polymer is rapidly kneaded with a mixed solution of the low-viscosity insect repellent and the aliphatic polyester as described above, and the polyester polymer is spun. Evaporation of the insect repellent was reduced.

As a result, when the insect-repellent polyester fiber is manufactured by the method for manufacturing insect-repellent polyester fiber according to the present invention, the insect-repellent polyester fiber having sufficient strength and sufficient strength can be stably obtained. It became so.

[Procedure amendment]

[Submission date] June 12, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

Here, the above-mentioned insect repellent used for producing the insect repellent polyester fiber is a compound which is well compatible with the polyester polymer, has stability even at high temperature, and has a high insect repellent effect and is safe. Is preferably selected and used, for example, dialkyl phthalate
DOO, a dialkyl adipate and dialkyl fumarates such as, the number of carbon atoms in the alkyl group is to use a thing of 1-8, as the dialkyl phthalates, include ortho-dialkyl phthalate, isophthalate dialkyl phthalates, tele dialkyl phthalate You can These insect repellents generally have a viscosity of 1 at 25 ° C.
It is less than 00 cps.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

In addition, in kneading the polyester polymer with the mixed solution of the insect repellent and the aliphatic polyester, spinning is carried out well, and the obtained insect repellent polyester fiber has sufficient insect repellent performance. , 1 to 6 of the above mixture for polyester polymer
%, Preferably 2 to 4% by weight, and 0.1% by weight of the insect repellent in the obtained insect repellent polyester fiber.
Or more, preferably 0.5% by weight or more, more preferably
The content should be 0.8 % by weight or more. However, if the amount of the insect repellent contained in the polyester fiber is too large, the physical properties of the polymer are deteriorated, so that it is generally difficult to contain the repellent in an amount of 10% by weight or more.

Claims (2)

[Claims] 1. A low-viscosity insect repellent is mixed with an aliphatic polyester to prepare a viscous mixed solution which can be sent by a gear pump, and the mixed solution is added to a polyester polymer immediately before spinning of the polyester polymer. A method for producing an insect-repellent polyester fiber, which comprises rapidly kneading and then spinning this. 2. An aliphatic polyester having an average molecular weight of 3500 or more, which is mixed with a low-viscosity insect repellent and has a viscosity of 25.
Using an aliphatic polyester having a viscosity of 15000 cps or more at 0 ° C., the insect repellent and the aliphatic polyester are mixed at a ratio of 50:50 to 10:90,
A mixed solution having a viscosity of 100 cps or more at 0 ° C. was prepared, and immediately before spinning of the polyester polymer, this mixed solution was rapidly kneaded with the above polyester polymer, and then this was spun to obtain 0.1% by weight of the above insect repellent. A method for producing an insect-repellent polyester fiber, comprising producing the insect-repellent polyester fiber contained above.