JPH0781206B2 - Deodorant polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a polyester fiber having excellent durability and deodorizing performance.

<Prior Art> Polyester fiber has excellent performance,
Widely used for bedding, interiors, industrial materials, etc. In particular, polyester fiber products used for daily life have a problem that a bad odor is generated due to the multiplication of mites, molds and bacteria that are generated in the sweat secreted by the human body, spills of food and drink, and dust and other adhered substances. There is an increasing demand for polyester fibers having a deodorant performance with a certain property.

As a conventional method of imparting deodorant performance, a method of applying a deodorant to the surface of the fiber, a method of immersing it in a deodorant dispersion liquid, a masking method of spraying a fragrance, etc. have been proposed. There were problems such as lack of property and falling off due to washing and rubbing.

The present inventors have arrived at the present invention as a result of earnest research on a method that has excellent durability and lasts for deodorant performance.

<Problems to be Solved by the Invention> Regarding the deodorizing performance of Fe (III) or Co (II) phthalocyanine polyvalent carboxylic acid, The Textile Society of Japan 41 No.8 p.267 (198
5), processing technology 21 No. 6 p. 27 (1986) and JP-A-55-32.
Reported by 519 and others.

Fe (III) or Co (II) phthalocyanine polycarboxylic acid (hereinafter abbreviated as Mt-PaPc) has excellent deodorant performance, but when applied to the surface of fibers, it is easily dissolved by a weak alkaline aqueous solution such as soap. However, it has a drawback that it can easily fall off.

Therefore, the present inventors have conducted a study on a method of making a deodorant polyester fiber having durability by uniformly dispersing and blending Mt-PaPc in a polyester polymer and then researching the method to have the following problems. found.

(1) Mt-PaPc is uniformly dispersed and blended in a polyester polymer to facilitate fiber formation, and in order to sufficiently exert the deodorizing effect, it is present in the polymer as a color pigment and ultrafine powder. It is necessary.

However, in the case of Mt-PaPc, since the cohesiveness in the polyester is extremely strong, coarse particles are generated even if the operation of dispersing the ultrafine powder by applying a strong shearing force is performed. For this reason, there are many disadvantages such that the deodorant performance is not sufficiently exhibited, and the polyester is spun when it is clogged with a filter, or the yarn is broken during stretching.

(2) In Mt-PaPc, when adjacent carboxyl groups exist, such as octacarboxylic acid having eight carboxyl groups in the molecule, a dehydration reaction occurs due to heating between the carboxyl groups, and therefore the prediction is sufficient. Even fine powder of Mt-PaPc that has been dried by heating generates moisture when mixed in a high-temperature polyester polymer, and hydrolysis of the polyester polymer lowers the degree of polymerization, resulting in a decrease in spinnability during spinning and an intermittent effect. The fiber cannot be formed due to the yarn breakage that accompanies the jetting of various gases.

As a means to solve these difficult problems, Mt-
We also studied the method of esterifying PaPc to make it lipophilic, but it was still unsatisfactory to obtain sufficient compatibility with polyester polymer.

<Means for Solving Problems> Therefore, the inventors of the present invention focused on supporting Mt-PaPc on titanium dioxide fine particles, prepared titanium dioxide carrying Mt-PaPc, and added and mixed this to a polyester polymer. As a result, the fine particles were extremely uniformly dispersed, and Mt-PaPc
Fiber addition, which was difficult when single particles were added, can be easily performed.

Even more surprisingly, it was confirmed that by supporting Mt-PaPc on the surface of titanium dioxide, the dehydration reaction of adjacent carboxyl groups, which was severe in the case of Mt-PaPc alone, was suppressed. As a result, when adding fine particles supported on the titanium dioxide surface of Mt-PaPc to polyester,
It became possible to add it to the polymer just before spinning. Furthermore, it was confirmed that the deodorizing performance was also improved as compared with the case of adding Mt-PaPc alone.

The loading of Mt-PaPc on the surface of titanium dioxide fine particles is performed as follows, for example. That is, titanium dioxide for polyester fibers having a particle diameter of 1 μm or less is added to an alkaline aqueous solution of Mt-PaPc to form a slurry and then neutralized with an acid to precipitate Mt-PaPc on the titanium dioxide particle surface.
Can be coated. Titanium oxide carrying Mt-PaPc is washed, purified and dried. The obtained fine particles are preferably pulverized into fine particles of 1 μm or less.

Specific examples of Mt-PaPc include Fe (III) -phthalocyanine tetracarboxylic acid, Fe (III) -phthalocyanine octacarboxylic acid, Co (II) -phthalocyanine tetracarboxylic acid, and Co (II) -phthalocyanine octacarboxylic acid. Acid, etc. These Mt-PaPc preferably have few impurities and should be sufficiently purified. When the oxides and hydroxides of iron and cobalt are contained as impurities, they cause deterioration of the physical properties of the polyester fiber.

Further, it is also possible to use a carboxylic acid ester of Mt-PaPc obtained by reacting these Mt-PaPc with a compound having an alcoholic hydroxyl group in the presence of a catalyst, but these carboxylic acid esters are difficult to purify and have a high purity. It is not industrially advantageous because it is difficult to efficiently obtain high products.

Further, it is possible to use a compound in which the carboxyl group of Mt-PaPc is in the form of an alkali metal salt or an alkaline earth metal salt, but this is not preferable because it may deteriorate the physical properties of the polyester fiber.

The amount of Mt-PaPc added to polyester varies depending on the type of Mt-PaPc, the cross-sectional shape of the polyester fiber, the manufacturing method, etc., but in order to obtain practical deodorant performance, 0.5% or more by weight is required. is there.

The mixing ratio of titanium dioxide to Mt-PaPc is preferably an equal amount or more, preferably 2 times or more by weight ratio. When titanium dioxide is too small, it is not supported by titanium dioxide when neutralized and precipitated with an acid from an alkaline solution. Since PaPc is generated, it is difficult to obtain a uniform dispersion when added to polyester, which is not preferable.

Mt-PaPc-supported titanium dioxide dry fine particles are added to the polycondensation step of the polyester polymer, in the feed pellets to the extruder, and in the molten polymer immediately before spinning,
A method similar to the method of adding titanium dioxide into a polyester polymer, such as a method of forming a master pellet, can be adopted.

In addition, when it is added to the pellets fed to the extruder or to the molten polyester polymer immediately before spinning, it is highly compatible with the polyester polymer in order to quantify the additive and improve the operability and dispersibility of the addition. More preferable is a method in which a molecular polymer, a plasticizer or the like is used as a dispersion medium and added in the form of an additive composition prepared in advance and made into a slurry.

Polyester used in the present invention is polyethylene terephthalate, polybutylene terephthalate, as a modifier, carboxylic acid components such as isophthalic acid, adipic acid, diethylene glycol, methoxy polyethylene glycol, alcohol components such as pentaerythritol,
Sulfonate group-containing components such as sodium-3,5-dicarbomethoxysulfoisophthalic acid, fine particles such as silicon dioxide and carbon black, flame retardants, heat stabilizers, antioxidants, etc. It may be contained.

Hereinafter, detailed description will be made with reference to examples.

Example-1 Iron phthalocyanine octacarboxylic acid [earth screen;
Made by Nisshin Chemical Co., Ltd.] 1 kg of 1 mol of caustic soda solution 20
Add to the inside and heat at a temperature below the boiling point to dissolve, and insoluble matter is filtered off.

3 kg of titanium dioxide for polyester fiber (average particle diameter 0.2 μm, maximum particle diameter 0.7 μm) was added to and mixed with the obtained dark green aqueous solution of iron phthalocyanine octacarboxylic acid Na salt, and a small amount of titanium dioxide was mixed with a homogenizer. After the lumps are completely loosened and titanium dioxide is sufficiently dispersed, it is neutralized with hydrochloric acid to precipitate iron phthalocyanine octacarboxylic acid on the surface of titanium dioxide.

Titanium dioxide carrying iron phthalocyanine octacarboxylic acid is fractionated, washed with water until chlorine ions are no longer observed, and the cake obtained is dried at 150 ° C. and then pulverized into fine particles of 1 μm or less.

Example-2 Fine particle powder of titanium oxide carrying iron phthalocyanine octacarboxylic acid obtained in Example-1 and a molecular weight of about 1,4 butylene glycol as a dispersion medium and adipic acid are polymerized.
2,500 aliphatic polyester polyol and 100-110 ℃
Then, the mixture was subjected to an equal polymerization to obtain an additive composition.

Immediately before spinning, 6 parts by weight of the additive composition containing the iron phthalocyanine octacarboxylic acid was added to 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity [η] = 0.64, and after mixing and dispersing with a kneader, the pore size was 0.30 mm. Was extruded from the spinneret, spun by a usual method, and stretched in a water bath at 80 ° C. to obtain a polyester fiber of 3 denier.

The fiber was colored blue and the content of iron phthalocyanine octacarboxylic acid determined by analysis of the iron component in the fiber was 0.72% by weight.

Example-3 A polyester fiber colored in 3 denier blue was obtained in the same manner as in Example-2 except that polyethylene glycol having a molecular weight of 20,000 was used as the dispersion medium.

The content of iron phthalocyanine octacarboxylic acid was found to be 0.73% by weight from the result of quantitative determination of iron in the obtained fiber.

Example 4 100 kg of bis (β-hydroxylethyl) terephthalate having an esterification reaction rate of 95% was charged into a polymerization tank and heated to 280 ° C. to melt, and antimony trioxide as a catalyst was added to 1 mol of an acid component constituting the polyester. 2 × 10 ⁻⁴ mol, and the titanium oxide powder carrying the iron phthalocyanine octacarboxylic acid obtained in Example 1 was added to the polyester 3
After addition by weight%, polycondensation was finally carried out at 280 ° C. under a reduced pressure of 0.1 mmHg for 3 hours to obtain a polymer having an intrinsic viscosity [η] = 0.64.

The obtained polymer was subjected to spin-drawing by a usual method to obtain 3
A denier blue colored polyester fiber was obtained.

The content of iron phthalocyanine octacarboxylic acid was found to be 0.72% by weight from the result of quantitative determination of iron in the obtained polyester fiber.

Comparative Example A polymer having an intrinsic viscosity [η] = 0.64 was obtained in the same manner as in Example 4 except that only titanium oxide was added in an amount of 2.25% by weight based on the produced polyester, instead of the titanium oxide supporting iron phthalocyanine octacarboxylic acid. Obtain and fiberize 3
A denier white polyester fiber was obtained.

Deodorization performance evaluation method Ammonia and hydrogen sulfide were used.

Put 7 g of fiber in a glass bottle with a narrow mouth, and the initial concentration is 400 ppm for ammonia and 10 for hydrogen sulfide.
Seal it at 0 ppm, leave it at 25 ° C and let it stand for 60 minutes, then
The residual concentration in the narrow-neck glass bottle was measured by the Kitagawa gas detector.

The results are shown in Table 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location D01F 6/92 302

Claims (1)

[Claims] 1. A polyester polymer containing fine particles of titanium dioxide having a particle size of 1 μm or less, on which Fe (III) or Co (II) phthalocyanine polyvalent carboxylic acid is supported, and the content of the phthalocyanine polyvalent carboxylic acid. Is 0.5% by weight or more, and the content of titanium dioxide is equal to or more than the amount of the polycarboxylic acid. Deodorant polyester fiber.