JP2002004183A - Dyed polyester fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an easily recyclable eco-friendly dyed polyester fiber structure generating little amount of dioxins in the incineration of the fiber, that is, combustion, heat-recovery and gas cooling processes and in the waste gas treating (dust collecting) process. SOLUTION: The fiber structure composed of a dyed polyester fiber contains <=0.01 wt.% halogens based on the total weight of the fiber structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an environment-friendly and easy-to-recycle property in which the generation of dioxins is suppressed in each of the combustion process of waste incineration, heat recovery and gas cooling, and exhaust gas treatment (dust removal). And a dyed polyester fiber structure.

[0002]

2. Description of the Related Art Recycling methods for polyester molded products are roughly classified into three types: material recycling, chemical recycling, and thermal recycling.

The material recycling method removes impurities (colored PET resin is also an impurity) as much as possible from waste polyester molded products such as PET bottles collected separately and then forms pellets or flakes through many processes. Although it is a method of recycling as a fiber raw material, it is difficult at present to apply it to a dyed polyester fiber structure.

The chemical recycling method mostly utilizes solvolysis. In hydrolysis using water as a solvent, terephthalic acid (hereinafter abbreviated as “TPA”) and ethylene glycol (hereinafter “EG”) are used. Abbreviated as). Further, in alcoholysis using alcohols, when methanol is used (methanolysis), it is decomposed into dimethyl terephthalate and EG, while when glycol is used (glycolysis), bis-2-hydroxyethyl terephthalate which is an oligomer of ethylene terephthalate is used. And further decomposed into TPA and EG or dimethyl terephthalate (hereinafter referred to as DMT) and EG using methanol.

Further, as a more environmentally friendly chemical recycling method, supercritical water is used as a reaction solvent for fibers and resins having an ether bond, an ester bond and an acid amide bond, so that a catalyst with wastewater treatment can be used. Research on a next-generation recycling method that can be decomposed without use is actively conducted, but it is not industrially implemented in terms of equipment cost and yield, and dyeing is also performed in this method. Because of the various difficulties involved in the application to such polyester fiber structures, they have not yet been put to practical use.

On the other hand, the thermal recycling method is
This is a method of recovering heat generated by incineration when processing mixed waste fiber and waste plastic. Although it is not strictly a recycling method, it is the most practical method at present, and it is a dyed polyester fiber structure. Is also applicable.

However, in the thermal recycling method,
It has been pointed out that dioxins may be generated in the combustion process, the heat recovery / gas cooling process, and the exhaust gas treatment (dust removal) process when incinerating waste, and in particular, dyed polyester fiber structures were recycled. In this case, there is a possibility that halogen contained in the dye may promote the generation of dioxin in order to improve the color developing property, and therefore, a preventive measure has been required.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide dioxin in each process of burning, heat recovery / gas cooling, and exhaust gas treatment (dust removal) when a dyed polyester fiber structure is incinerated. It is an object of the present invention to provide an environmentally friendly and easily recyclable polyester fiber structure in which the generation of ash is suppressed as much as possible.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, the amount of halogen contained in the dyed polyester fiber structure was set to 0.1% based on the total weight of the fiber structure. It has been found that when the content is reduced to 01% by weight or less, a polyester fiber structure free from the possibility of generating dioxins in the incineration treatment can be obtained.

Thus, according to the present invention, there is provided a fibrous structure composed of dyed polyester fibers, wherein the amount of halogen contained in the fibrous structure is 0.01% by weight based on the total weight of the fibrous structure. % Or less is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester fibers constituting the polyester fiber structure of the present invention are mainly composed of polyethylene terephthalate having terephthalic acid as an acid component and ethylene glycol as a glycol component. A polyester in which a part of the component is substituted with another difunctional carboxylic acid component, and / or a copolymerized polyester in which a part of the glycol component is substituted with a diol component other than the glycol, may be used.

The bifunctional carboxylic acids other than terephthalic acid used herein include, for example, isophthalic acid, naphthalenecarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid,
Examples thereof include aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as 4-cyclohexanedicarboxylic acid.

The polyester may be synthesized by any method. For example, direct transesterification of terephthalic acid and ethylene glycol, transesterification of a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, or a method of reacting terephthalic acid with ethylene oxide, etc. Glycol esters of acids and / or
Or a first-stage reaction for producing the low polymer thereof, and a second-stage reaction for subjecting the first-stage reaction product to a polycondensation reaction by heating under reduced pressure to a desired degree of polymerization. You can do it.

The polyester may contain a matting agent, an ultraviolet absorber, an antioxidant, and the like. It is rather preferable to contain such an agent from the viewpoint of performance as a final product. . In addition, if necessary, a catalyst,
Additives such as stabilizers, anti-coloring agents, flame retardants, fluorescent whitening agents, antistatic agents, heat-resistant agents, colorants, and inorganic particles may be contained.

[0015] The polyester fibers referred to in the present invention include:
Even if it is a solid fiber having no hollow portion, it may be a hollow fiber having a hollow portion, and the outer shape and the shape of the hollow portion in the cross section of the polyester fiber may be circular or irregular. Good. Further, the fineness is not particularly limited.

The polyester fiber preferably has a tan δ peak temperature of 90 to 110 ° C. in dynamic viscoelasticity measurement. Further, the polyester fiber preferably has a glass transition temperature Tg of 70 ° C. or less.

That is, the peak temperature of tan δ is 90 to 11
Polyester fiber of 0 ° C and glass transition temperature Tg of 70 ° C
Since the following polyester fibers have excellent dye exhaustion, high color developability and high color fastness can be obtained even when dyeing is performed only with a dye containing no halogen, which will be described later.

As the polyester fiber having a tan δ peak temperature of 90 to 110 ° C., a so-called high-speed spun fiber (hereinafter referred to as US) spun at a spinning speed of 5000 m / min or more.
Y is preferable), and polyester fibers having a glass transition temperature Tg of 70 ° C. or lower are preferably polyester fibers obtained by copolymerizing a polyoxyalkylene glycol such as adipic acid or polyoxyethylene glycol. Is done.

The above-mentioned polyester fiber may be subjected to a drawing, heat treatment, false twisting, air entanglement or the like in another step.

The polyester fiber is used as a fiber structure such as a woven fabric, a knitted fabric, and a nonwoven fabric. In the case of a woven or knitted fabric, there is no particular limitation on its structure and form.For example, in a woven structure, a plain weave, a satin weave, a twill weave, etc. Can be used for

In the present invention, it is important that the polyester fiber structure is dyed under conditions such that the amount of halogen contained in the dyed fiber structure is as small as possible.

That is, a normal polyester fiber structure is
The polyester fiber structure is dyed with a halogen-free dye in the present invention.

As the above-mentioned halogen-free dye, a disperse dye is preferably exemplified, and among them, use of a disperse dye having a molecular weight of 380 or more is preferable from the viewpoint of the color fastness.

The organic / inorganic ratio of the disperse dye is preferably from 0.55 to 1.0, and more preferably from 0.6 to 0.8. Here, the organic / inorganic ratio is defined as a portion having an organic characteristic of a dye main body and a portion having an inherent electrostatic characteristic opposite thereto, as described in Dyeing Theory Chemistry (by Nobuhiko Kuroki). Which corresponds to a so-called hydrophobic part and a hydrophilic part. And this organic /
Those having similar inorganic ratios are said to have high affinity.

Specific examples of the disperse dyes include benzene azo (monoazo, disazo, etc.) and heterocyclic azo (thiazole azo, benzothiazole azo, quinoline azo, pyridine azo), which have no halogen atoms such as Cl and Br in the molecule. , Imidazole azo, thiophenone azo, etc.),
Anthraquinone-based, condensation-based (quinophthaline, styryl,
And coumarin).

In general, it is said that a halogen-free disperse dye has inferior coloring property. However, in the present invention, the molecular weight is 380 or more, and the organic / inorganic ratio is 0.55 to 0.55.
By using a disperse dye of 0.85, good color developability can be imparted. Further, as described above, tan δ
When a polyester fiber having a peak temperature of 90 to 110 ° C. or a polyester fiber having a glass transition temperature Tg of 70 ° C. or lower is used, even a dye containing no halogen can impart practically sufficient coloring properties. It is possible.

The method of dyeing is beam dyeing, cheese dyeing,
Conventionally known dyeing methods such as package dyeing, immersion stirring dyeing including liquid flow dyeing and the like, and thermosol dyeing can be arbitrarily adopted. The dyeing may be performed at a temperature for 15 minutes or more, preferably for about 60 minutes. Above all, immersion stirring dyeing is preferable because high color development, high exhaustion and high fastness can be imparted.

The polyester fiber structure dyed by the above method contains only 0.01% by weight or less of halogen based on the total weight of the fiber structure, and there is no possibility of generating dioxins in the incineration treatment. .

[0029]

Next, the present invention will be described in more detail by way of examples. In addition, each physical property in an Example was measured by the following method.

(1) Chromogenicity The coloring was evaluated by a transmission spectrophotometer (U.S.A.) manufactured by Shimadzu Corporation.
V1200), the dye exhaustion rate was determined from the transmission absorbance of the undiluted solution (before staining) and the transmission absorbance of the residual dye solution after staining according to the following formula.

[0031]

(Equation 1)

(2) Halogen Content The content of halogen (Br and / or Cl) in the fibers constituting the fiber structure was measured using a fluorescent X-ray analyzer manufactured by Rigaku Corporation.

(3) Combustion test JIS L1091 which is a method for testing the flammability of textile products
Combustion gas from the combustion test performed according to (A-1 method) was collected, and qualitative analysis was performed on the presence or absence of detection of volatile halide by gas mass analysis (GC-MS).

Example 1 12.5 mol% of adipic acid
A copolymerized polyethylene terephthalate polymer containing 0.07% by weight of titanium oxide was spun at a speed of 1400 m.
/ Min, preheating temperature 68 ° C, set temperature 150
The film was drawn 3.5 times at a temperature of 5 ° C. to obtain a copolyester yarn of 55.6 dtex / 24 filaments.

After the obtained drawn yarn (Tg: 50 ° C.) was formed into a fabric according to a conventional method, the fabric was score roll 400
(Manufactured by Kao) at 1 g / l at 80 ° C. for 20 minutes. After washing with water and drying, it was pre-set at 190 ° C. for 1 minute. Then, the temperature was raised from room temperature at a rate of 2 ° C./min in the following dyeing bath,
The dyeing | staining process was carried out at 60 degreeC for 60 minutes.・ Dye CIDisperse Blue 354 10% owf (Non-halogen-containing dye: KPBrill.Blue FR-S: (manufactured by Nippon Kayaku Co., Ltd.)) ・ Dispers VG 0.5g / l ・ Acetic acid 0.2cc / l ・ Bath ratio 1: 30 Next, the stained sample was reduced and washed in the following washing bath at 80 ° C. for 20 minutes: NaOH 2 g / l Hydrosulfite 2 g / l Amyrazine D 2 g / l (Nonionic activator manufactured by Dai-ichi Kogyo Seiyaku) After the reduction washing, it was sufficiently washed with water, dried and final set (160 ° C. × 1 minute).

[Example 2] In Example 1, the dye was CIdisperse Blue 87 (KPLig) which is a non-halogen-containing dye.
ht Blue BGL-S200: (Nippon Kayaku Co., Ltd.)) except that the procedure was the same as in Example 1. Table 1 shows the physical properties of the obtained fabric.

[Example 3] In Example 1, the dye was CIdisperse Blue 60 (KPTur) which is a non-halogen-containing dye.
quoise Blue GLS-S200: (Nippon Kayaku Co., Ltd.) except that the procedure was the same as in Example 1. Table 1 shows the physical properties of the obtained fabric.

Example 4 Example 4 was carried out in the same manner as in Example 1, except that a normal drawn yarn made of polyethylene terephthalate polymer was used instead of the copolymerized polyester yarn. Table 1 shows the physical properties of the obtained fabric.

Example 5 The procedure of Example 1 was repeated, except that a high-speed spun yarn made of polyethylene terephthalate polymer spun at a spinning speed of 6000 m / min was used instead of the copolyester yarn. did.
Table 1 shows the physical properties of the obtained fabric.

Comparative Example 1 In Example 1, CIdisperse Blue 5 which is a dye containing a bromo group (-Br) was used.
6 (KPBlue EBL-E: (manufactured by Nippon Kayaku Co., Ltd.)), except that the procedure was as in Example 1. Table 1 shows the physical properties of the obtained fabric.

Comparative Example 2 In Example 1, CIDisperse Blue 1 which is a dye containing a bromo group (-Br) was used.
83 (KPBlue BR-SF: (manufactured by Nippon Kayaku Co., Ltd.)) was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained fabric.

Comparative Example 3 In Example 1, CIDisperse Red 54 which is a dye containing a chlorine group (-Cl) was used.
(Sumikaron Scarlet SE-3GL: (manufactured by Sumitomo Chemical Co., Ltd.)). Table 1 shows the physical properties of the obtained fabric.

Comparative Example 4 In Example 4, CIDisperse Red 54, which is a dye containing a chlorine group (-Cl), was used.
(Sumikaron Scarlet SE-3GL: (manufactured by Sumitomo Chemical Co., Ltd.)) was carried out in the same manner as in Example 4. Table 1 shows the physical properties of the obtained fabric.

[0044]

[Table 1]

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toyoshi Suzuki 3-4-1, Amihara, Ibaraki-shi, Osaka Teijin Limited Osaka Research Center F-term (reference) 4H057 AA01 BA08 BA90 DA01 DA17 4L002 AA07 AB02 AC06 DA01 DA04 EA00 4L035 BB34 BB91 EE20 4L048 AA20 AA21 AA42 AA44 AA46 AB07 AC07 EB05

Claims (5)

[Claims] 1. A fiber structure comprising dyed polyester fibers, wherein the amount of halogen contained in the fiber structure is 0.01% by weight based on the total weight of the fiber structure.
A dyed polyester fiber structure characterized by the following. 2. The dyed polyester fiber structure according to claim 1, wherein the peak temperature of tan δ in the dynamic viscoelasticity measurement of the polyester fiber is 90 to 110 ° C. 3. The dyed polyester fiber structure according to claim 1, wherein the polyester fiber is a polyester fiber spun at a spinning speed of 5000 m / min or more. 4. The polyester fiber according to claim 1, wherein the polyester fiber is a polyethylene terephthalate-based copolymerized polyester fiber.
The dyed polyester fiber structure according to any one of the above. 5. The dyed polyester fiber structure according to claim 4, wherein the glass transition temperature Tg of the polyethylene terephthalate copolymerized polyester fiber is 70 ° C. or less.