JPH11189977A - Polyester fiber structure and method for producing the same - Google Patents

Abstract

(57) [Summary] [Problem] To provide a flame-retardant polyester fiber which does not generate harmful gas during combustion, and which is provided with mold resistance and water repellency having washing durability and dry cleaning durability. provide. A polyester fiber structure, comprising a linear or cyclic phosphazene compound 1.5 to 10% owf,
0.1 to 5% owf of a benzimidazole compound and a urethane compound containing a polyfluoroalkyl group.
A polyester fiber structure containing 1 to 5% owf.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester fiber structure and a method for producing the same. More specifically, the present invention relates to a polyester fiber structure having flame retardancy, mold resistance and water repellency, and a method for producing the same.

[0002]

2. Description of the Related Art Polyester-based textile products are widely used for clothing and interior use. In these textile products, bacteria that propagate from the human body attached to the surface of the fiber and dirt in the air as a nutrient source are propagated. Microorganisms such as mold and the like generate odors, cause skin disorders and diseases, and are adversely affected by hygiene.

[0003] On the other hand, in order to minimize the damage caused by fires caused by matches, cigarettes, etc., interior materials used in hotels, hospitals, movie theaters and the like are regulated by the Fire Service Law.

Under these circumstances, in order to create a safe and comfortable living environment, it has been desired to develop a fiber product having fungicidal properties, water repellency, antifouling properties and flame retardancy at the same time. I have. However, a method of spraying a compound having fungicidal properties on fibers with a solution or an emulsion is disclosed in JP-A-57-171771,
This alone has no lasting effect, and the fungicide falls off due to washing or the like. Japanese Patent Application Laid-Open No. 3-27183 proposes a method in which an acrylic resin is used in combination, but the texture of the fiber cloth is impaired. Further, when the fiber is treated with the flame-retardant polyester, the viscosity at the time of melting becomes high and the drip property is deteriorated, so that the necessary flame retardancy cannot be obtained.

The method of imparting flame retardancy by post-processing in the form of a woven or knitted textile product has the advantage that it can be freely processed as required. Are most commonly used. But,
Halogen compounds are liable to generate harmful gases when burned, and in recent years, global environmental issues have been emphasized in recent years, and momentum for technical improvement is increasing.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a flame-retardant polyester fiber structure which does not generate harmful gas upon combustion.
Another object of the present invention is to provide a polyester fiber structure imparted with mold resistance and water repellency having washing durability and dry cleaning durability, and a method for producing the same.

[0007]

In order to achieve the above object, a polyester fiber structure of the present invention has the following constitution.

That is, a polyester fiber structure, wherein a linear or cyclic phosphazene compound represented by the following formula (I) or (II) is 1.5 to 10% owf
And a benzimidazole compound at 0.1 to 5% owf,
A urethane-based compound containing a polyfluoroalkyl group is used in an amount of 0.1 to 0.2.
It is a polyester fiber structure containing 1 to 5% owf.

[0009]

Embedded image (X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.)

Embedded image (X _{1 to} X ₄ in the formula (II) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) The polyester fiber structure of the present invention The method for manufacturing a product has the following configuration.

That is, the solid content is 5.0 to 20% owf
After treating the polyester fiber structure at 100 ° C. or higher in a dyeing bath containing the phosphazene compound, the benzimidazole-based compound is treated with 0.1 to 10% owf, This is a method for producing a polyester fiber structure in which a mixed aqueous solution containing 0.1 to 10% owf of a urethane-based compound containing a fluoroalkyl group is applied and heat-treated.

Further, the polyester fiber structure is immersed in a dispersion containing the phosphazene compound, and after elimination and drying, after exhaustion treatment of the phosphazene compound in an atmosphere at 150 ° C. or higher, 0.1 to 10% owf for benzimidazole compound and 0.1 to 10% owf for urethane compound containing polyfluoroalkyl group
This is a method for producing a polyester fiber structure in which a mixed aqueous solution is applied and heat-treated.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the present invention, the polyester fibers are not particularly limited, but those having polyethylene terephthalate, polybutylene terephthalate or ethylene terephthalate units as main repeating components (specifically, 90 mol% or more of the repeating units), Fibers composed of the main repeating component (specifically, 90 mol% or more of the repeating unit) can be preferably used. Among them, polyester fibers composed of a polyester having an ethylene terephthalate unit of 90 mol% or more as a repeating component are preferable, and polyester fibers composed of a polyester having an ethylene terephthalate unit of 95 mol% or more as a repeating component are more preferable. 100 mol% ethylene terephthalate unit
It is further preferable that the polyester fiber is a polyester fiber made of a polyester (ie, polyethylene terephthalate) as a repeating component.

The components that may be copolymerized with the polyester include aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, and naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; Aliphatic diols such as tetramethylene glycol and hexamethylene glycol, and aliphatic or aromatic diols such as 1,4-cyclohexanedimethanol and bisphenol A can be used.

The cross-sectional form of these polyester fibers may be round or irregular. The form of the fiber structure may be a nonwoven fabric, a woven fabric, or a knitted fabric.

The purpose of the phosphazene compound used in the present invention is mainly to impart flame retardancy to the polyester fiber, and it is important that the phosphazene compound is applied to the polyester fiber structure at a ratio of 1.5 to 10% owf. 1.5% owf
If it is less than 10%, the flame retardancy is insufficient, and if it exceeds 10% owf, the texture of the fiber structure is impaired. Further, in order to enhance the exhaustion of the polyester, the total number of phenoxy groups in the phosphazene compound in the formula (I) or (II) is preferably two or more. In particular, in formula (I), the number is preferably 2 or more and 6 or less, and in formula (II), it is preferably 2 or more and 6 or less. When all the substituents X and Y in the phosphazene are amino groups, the washing durability is low. When all the phenoxy groups are used, the dry cleaning property is insufficient.

The phosphazene compound used in the present invention depends on the phosphorus element content in the compound in order to obtain flame retardancy, for example, in order to pass the JIS-L1091D method (the number of times of flame contact). 0.2%
It is preferable to provide the compound of the present invention so as to contain owf or more of a phosphorus element. On the other hand, when 10% owf or more is applied, the amount of phosphorus element for obtaining flame retardancy can be sufficiently applied, but the texture becomes hard, which is not preferable.

In the actual use of the phosphazene compound of the present invention, it is preferable to use it by finely dispersing it in water. The method for finely dispersing in water is not particularly limited, but the following method is preferably used from the viewpoint of dispersion efficiency. That is, the phosphazene compound of the present invention, a dispersant, and water are mixed, stirred, and dispersed. Generally, this dispersion is crushed and dispersed by a glass bead crusher. As another method, after dissolving in a solvent capable of dissolving the phosphazene compound of the present invention, it may be mixed with water while stirring and emulsified for use.

As a method for exhausting the phosphazene compound into the polyester fiber in the present invention, a treatment in a bath, a pad dry / curing method and the like can be used. The in-bath treatment method is a method in which a polyester is exhausted at a temperature of 100 ° C. or more in a finely dispersed dispersion of a phosphazene compound. In addition, a phosphazene compound can be charged into a dyeing bath to simultaneously perform dyeing and flame retarding.
In this case, the amount of the phosphorus element in the phosphazene compound of the present invention is adjusted so as to be exhausted by 0.2% owf or more with respect to the polyester fiber in consideration of the efficiency of exhaustion of the polyester fiber. Other dyes used for ordinary dyeing,
A pH adjuster, a leveling agent and the like are appropriately added. From the viewpoint of the exhaustion efficiency of the phosphazene compound of the present invention, the bath ratio is 1: 5 to 5: 1.
1: 100 is preferred, and 1: 5 to increase exhaustion.
1:30 is more preferred. The treatment temperature in the bath treatment is 100 ° C. or higher. If the treatment temperature is lower than 100 ° C., it is difficult to sufficiently impart a flame retardant to the polyester fiber. From the viewpoint of the exhaustion efficiency, it is preferable to perform the treatment in a bath at a temperature of 120 ° C to 135 ° C for 30 to 60 minutes, and then perform the usual washing and drying. Furthermore, reduction treatment may be performed after treatment in a bath, or heat treatment may be performed after drying.

On the other hand, the pad dry / curing method means that polyester fibers are immersed in a dispersion of the phosphazene compound of the present invention, drained with a mangle, dried at 100 ° C. or more, and then exhausted at 150 ° C. or more. Can be used. From the viewpoint of uniform application of the phosphazene compound of the present invention, 100 to 12
It is preferable to dry at a temperature of 0 ° C. and then to perform a heat treatment at a temperature of 170 to 200 ° C. for 10 to 180 seconds.

From the viewpoint of uniform exhaustion to the polyester fiber and stability of the dispersion, the particle size of the phosphazene compound of the present invention is 1
0 micron or less is preferable, 5 micron or less is more preferable, and 1 micron or less is further more preferable.

Next, specific examples of the benzimidazole compound used in the present invention include 2- (4-thiazolyl) benzimidazole and 2-methoxycarbonylamino-benzimidazole, but are not limited thereto. Not something. The amount of the benzimidazole-based compound to be attached is 0.1 to 5% owf, preferably 0.1 to 3% owf, to the fiber. 0.1%
If it is less than owf, there is a problem that sufficient antibacterial and fungicidal properties cannot be obtained.

The urethane compound containing a polyfluoroalkyl group used in the present invention is preferably a compound represented by the following formula (III).

Embedded image In the above formula (III), Rf is a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and one having a perfluoroalkyl group at the terminal is usually used. Containing hydrogen or chlorine atoms,
Alternatively, an oxyperfluoroalkylene-containing group can be used. A preferred embodiment of the Rf group is a perfluoroalkyl group, and those having 4 to 12 carbon atoms are particularly preferred. X represents -R-, -CON (Rf) -Q-, or -S
O ₂ N (R ₁ ) —Q— (where R represents an alkylene group, R ₁ represents a hydrogen atom or a lower alkyl group, and Q represents a divalent organic group), and has 1 to 20 carbon atoms. Alkylene groups are preferred. A and A1 are each _{-O -, - N (R 2} ) - ( where, R ₂ is a hydrogen atom or a lower alkyl group) are preferred. Z is a non-hydrophilic monovalent organic group, which includes an alkyl group, an aryl group, and a hetero atom;
Examples thereof include -Rf, but a lower alkyl group is preferable from the viewpoint of water repellency and oil repellency. Y is a divalent organic group,
Usually, those having 24 or less carbon atoms, particularly those having 6 to 15 carbon atoms, are selected, and those containing at least one aromatic or aliphatic ring are preferably used from the viewpoint of rigidifying urethane molecules and improving durability. Further, n is one or more positive numbers, and particularly, positive numbers 1 to 3 are selected.

The amount of the polyfluoroalkyl group-containing compound to be attached is 0.1 to 5% owf with respect to the fiber. If the content is less than 0.1% owf, sufficient water repellency cannot be obtained, and the antifungal property becomes insufficient. On the other hand, 5% o
If it exceeds wf, it is not practically preferable in terms of cost.

The benzimidazole compound and the polyfluoroalkyl group-containing compound may be applied in the following manner.
A 10% owf and a 0.1 to 10 owf% mixed aqueous solution of a polyfluoroalkyl group-containing compound are applied to the fiber surface by any method such as immersion treatment, spray treatment, foam treatment, gravure treatment, and the like, and dried at 100 to 200 ° C. And heat treatment. In the case of an aqueous solution in which the concentration of the benzimidazole compound is less than 0.1% owf, sufficient fungicidal performance cannot be obtained. On the other hand, in the case of an aqueous solution exceeding 10% owf, the water repellency is reduced, and it is not practically preferable in terms of cost.

In addition, even if the mixed liquid contains a suitable amount of a blocked isocyanate compound, the mixed liquid may be used.

As the heat treatment, a tenter one-step finish in which drying and setting are performed simultaneously can be employed. 1
Heat treatment at a temperature lower than 50 ° C. is not sufficient in terms of durability. On the other hand, when the temperature exceeds 210 ° C., there is a risk of yellowing and embrittlement of the fiber, which is not practically preferable.

Here, the reason why the product of the present invention is more durable in fungicide performance than the conventional spray method is that the benzimidazole compound used in the present invention is absorbed into the fiber by heat treatment. It is thought to be.

Hereinafter, the present invention will be described in more detail with reference to examples. The performance evaluation in the examples was performed by the following method.

<Washing Method> Household washing machine VH-3410
(Toshiba Corporation), weak alkaline detergent "Zab"
(Registered trademark, manufactured by Kao Corporation) 0.2% by weight, temperature 40 ° C
After treating at a ± 2 ° C bath ratio of 1:30 for 5 minutes, drainage dehydration is performed, and rinsing for 2 minutes is repeated twice while overflowing. This is one wash.

<Evaluation of Flame Retardancy> Measured according to JIS L-1091D method (number of times of flame contact).

<Evaluation of mold resistance> JIS Z-2911
Measured according to 6.2.2 (Textile test; wet method).

<Evaluation of water repellency> Measured by JIS L-1092 spray method.

[0034]

(Example 1, Comparative Example 1) Both warp and weft are 15
Plain woven fabric using 100% polyester fibers of 0 denier-48 filaments processed yarn is 1 g / l of Sandet G-29 (manufactured by Sanyo Chemical Industries, Ltd.), sodium hydroxide (30 g).
%) After refining in a treatment solution containing 2 g / l at 80 ° C. for 15 minutes, drying, intermediate setting at 150 ° C. for 30 seconds, dyeing and flame retardant of the following formulation (above) A bath ratio of 1:
It was treated at 130 ° C. for 60 minutes as 20.

<Blending of Dyeing and Flame Retardant Treatment Liquid> Disperse Dye Dianix Yellow F3G-E 0.1% owf Dianix Red ACE 0.06% owf Dianix Blue FBL-E 0.03% owf Auxiliary Ionnet TD-2081 1.0 g / l Fixer PH-500 1.0 g / l Flame retardant tetraphenoxydiaminocyclotriphosphazene (50% by weight dispersion) 10.0% owf Next, Sandet G-29 (manufactured by Sanyo Chemical Co., Ltd.) 1 g /
1, 2 g / l of sodium hydroxide (30% by weight) and 1 g / l of hydrosulfite at 80 ° C. × 2
After reducing and washing under the condition of 0 minutes, after washing with hot water at 60 ° C. for 10 minutes,
Further, it was washed with water. Then, in the above general formula, R
f is C ₉ F ₁₉ CH ₂ CH ₂ O, X is CONH (CH ₂ ) ₆ ,
A is NH, A1 is O, Y is (CH ₂ ) ₆ , Z is C ₉ F ₁₉ C
H ₂ CH ₂ , a polyfluoroalkyl group-containing urethane compound having n = 2 is 0.1% ows, 2-methoxycarbonylaminobenzimidazole is 0.05% ows,
0.1% ows, 1.0% ows, 5.0% ows,
A treatment solution containing 8.0% ows was prepared, and the dyed fabric was immersed, squeezed at a pickup rate of 100%, dried with a pin tenter at 120 ° C. × 2 minutes, and then dried at 170 ° C. × 30.
Heat treatment was performed for a second to obtain a polyester-based fiber structure. The obtained fiber structure was evaluated for flame retardancy, mold resistance and water repellency, and the results are shown in Table 1.

As shown in Table 1, the flame retardancy was acceptable when the number of times of flame contact was 3 or more. When the content of the fungicide was less than 0.1% owf (Comparative Example 1-1), the fungicide was insufficient. In addition, 5% owf or more (Comparative Example 1-2)
The water repellency decreased.

(Example 2, Comparative Example 2) As a flame retardant, a phosphazene compound represented by the above formula (II) (phenoxy group:
Except that the total ratio of amino groups is 50:50)
The same processing and evaluation as in Example 1 were performed, and the results are shown in Table 1. Regarding the flame retardancy, all passed 3 or more times of flame contact. When the content of the fungicide was less than 0.1% owf (Comparative Example 2-1), the fungicide was insufficient. 5
At% owf or more (Comparative Example 2-2), the water repellency was reduced.

Example 3 and Comparative Example 3 A fabric which had been dyed and flame-retarded under the same conditions as in Example 1 was replaced with 2-methoxycarbonylaminobenzimidazole in 2.0% ows.
In the above general formula, Rf is C ₉ F ₁₉ CH ₂ CH ₂ O, X
Is CONH (CH ₂ ) ₆ , A is NH, A1 is O, Y is (C
H ₂ ) ₆ , a polyfluoroalkyl group-containing urethane compound in which Z is C ₉ F ₁₉ CH ₂ CH ₂ and n = 2 is 0.05% o
ws, 0.1% ows, 1.0% ows, 5.0% ow
Each of the treatment solutions containing s was adjusted, and the dyed fabric was immersed.
After drying at 20 ° C. for 2 minutes, heat treatment was performed at 170 ° C. for 30 seconds to obtain a polyester fiber structure. The resulting fiber structure was evaluated for mold resistance, water repellency, and flame retardancy, and the results are shown in Table 2. For comparison, the dyed and flame-retardant treated cloth of Example 3 was replaced with a polyfluoroalkyl group-containing acrylic compound at 10.0% o.
The sample was immersed in a treatment solution containing 2.0% ows of ws, 2-methoxycarbonylaminobenzimidazole and treated under the same conditions as in Example 3 (Comparative Example 3-2). The results are shown in Table 2. Although mold resistance and water repellency were sufficient, flame retardancy was reduced.

Example 4, Comparative Example 4 Using the same fabric used in Example 1, tetraphenoxydiaminocyclotriphosphazene (50% by weight dispersion) was dissolved in 3% ows,
% Ows, 10% ows, and 20% ows, the cloth was immersed in the treatment bath, squeezed at a pickup rate of 100%, dried with a pin tenter at 120 ° C. for 1 minute, and then dried at 180 ° C.
C. x 1 minute. Then, in the general formula:
Rf is C ₉ F ₁₉ CH ₂ CH ₂ O, X is CONH (C
H ₂ ) ₆ , A is NH, A1 is O, Y is (CH ₂ ) ₆ , Z is C
₉ F ₁₉ CH ₂ CH ₂ , 0.1% ows of a polyfluoroalkyl group-containing urethane compound having n = 2 and 1.0% ows of 2-methoxycarbonylaminobenzimidazole
After preparing a treatment solution containing s and immersing the dyed fabric which has been previously subjected to the flame retardant treatment, squeezing at a pickup rate of 100%, drying with a pin tenter at 120 ° C. for 2 minutes, and heat-treating at 170 ° C. for 30 seconds to obtain a polyester A system fiber structure was obtained. The fungicidal properties, water repellency, and flame retardancy of the obtained fiber structure were evaluated, and the results are shown in Table 3. As shown in Table 3, sufficient flame retardancy, mold resistance and water repellency were obtained. However, at the level where 1.0% owf was added as a flame retardant (Comparative Example 4-1), although mold resistance and water repellency were obtained, sufficient flame retardancy was not obtained.

[0040]

[Table 1]

[Table 2]

[Table 3]

[0041]

Industrial Applicability The polyester fiber structure obtained by the present invention does not generate harmful gas during combustion, is environmentally friendly, maintains flame-retardant performance that meets flameproof standards, and has a washing property. It has mold resistance and water repellency with excellent durability. In addition, it is possible to combine the flame retardancy and water repellency of polyester fibers, which has been difficult so far, and it is possible to broaden the product development in the curtain field.

Claims (4)

[Claims] 1. A polyester fiber structure, comprising a linear or cyclic phosphazene compound represented by the following formula (I) or (II): 1.5 to 10% owf, and a benzimidazole compound 0.1. To 5% owf, and 0.1 to 5% of a urethane compound containing a polyfluoroalkyl group
owf-containing polyester fiber structure. Embedded image (X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.) (X _{1 to} X ₄ in the formula (II) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) 2. The polyester fiber structure according to claim 1, wherein the total number of phenoxy groups in the phosphazene compound is 2 or more. 3. A dye bath containing a linear or cyclic phosphazene compound represented by the following formula (I) or (II) having a solid content of 5.0 to 20% owf, wherein the bath ratio is 1: 5
After treating the polyester fiber structure at 100 ° C. or more, the benzimidazole compound was added to 0.1 to 100.
A method for producing a polyester fiber structure, comprising applying a mixed aqueous solution containing a urethane-based compound containing 1 to 10% owf and 0.1 to 10% owf, followed by heat treatment. Embedded image (X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.) (X _{1 to} X ₄ in the formula (II) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) 4. A polyester fiber structure is immersed in a dispersion containing a linear or cyclic phosphazene compound represented by the following formula (I) or (II), and
After drying, the phosphazene compound is exhausted in an atmosphere of 150 ° C. or more, and then the benzimidazole compound is 0.1 to 10% owf, and the urethane compound containing a polyfluoroalkyl group is 0.1 to 10% owf. A method for producing a polyester fiber structure, comprising applying a mixed aqueous solution containing the mixture and performing a heat treatment. Embedded image (X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.) (X _{1 to} X ₄ in the formula (II) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.)