JP4833610B2 - Flame retardant polyester fiber structure and method for producing the same - Google Patents

Description

  The present invention relates to a polyester fiber structure excellent in flame retardancy and durability and a method for producing the same.

  Conventionally, methods for imparting flame retardancy to polyester fiber structures are broadly classified into methods for producing flame-retardant raw yarns and methods for post-processing with flame-retardant compounds.

  Examples of the former method include a method of copolymerizing a flame retardant compound during fiber production, or a method of blending a flame retardant compound.

  As the latter method, a method of treating with a compound containing a halogen element such as hexabromocyclododecane (see Patent Document 1) has been practiced for a long time, but a halogenated gas is generated during combustion. Therefore, in recent years, treatment with a phosphorus compound not containing a halogen element has been proposed from the viewpoint of environmental protection (see Patent Documents 2 and 3).

  On the other hand, in the former method, the yarn-forming property at the time of fiber production decreases, and, for example, in the case of a woven or knitted fabric, the flame-retardant performance may be greatly reduced due to the fabric structure or basis weight, and the flame-retardant raw yarn alone Since satisfactory flame retardant performance cannot be obtained, there are further problems such as post-processing with a flame retardant compound.

  In the latter method, there are problems that the flame retardant bleeds, the texture is cured, and the fastness is lowered.

Furthermore, the cationic dyeable polyester has a serious drawback that sufficient flame retardancy cannot be imparted. A method of using a phosphonium salt has been proposed for making a fiber structure containing a cationic dyeable polyester flame retardant (see Patent Document 4), but there are problems such as a decrease in dyeability.
Japanese Patent Publication No.53-8840 JP 2000-328445 A JP 2000-154465 A JP-A-2005-9041

In view of the background of the prior art, an object of the present invention is to provide a polyester fiber structure using a cationic dyeable polyester fiber excellent in flame retardancy and durability and a method for producing the same.

  The present invention employs the following means in order to solve the above problems.

That is, the flame-retardant polyester fiber structure of the present invention is a fiber structure in which a cationic dyeable polyester fiber and a polyester fiber are mixed, and the cationic dyeable polyester fiber has an intrinsic viscosity of 0. 40 or more and 0.55 or less , and the polyester fiber has an intrinsic viscosity of 0.68 or less .

  In a preferred embodiment of the flame retardant polyester fiber structure of the present invention, the fiber structure contains a flame retardant compound.

  Moreover, according to the preferable aspect of this invention, said flame retardant compound is at least 1 sort (s) of flame retardant compound chosen from the phosphorus type compound group shown by the following general formulas 1-4.

In the method for producing a flame-retardant polyester fiber structure according to the present invention, a fiber structure in which a cationic dyeable polyester fiber and a polyester fiber are mixed is treated at a temperature of 120 ° C. or higher in a water bath having a pH of 4 or lower. A method for producing a flame-retardant polyester fiber structure according to the present invention as described above .

  One preferred embodiment of the method for producing a flame-retardant polyester fiber structure of the present invention is one in which a dye and a flame-retardant compound are contained in the water bath.

In the method for producing a flame-retardant polyester fiber structure of the present invention, a fiber structure in which the above-mentioned cationic dyeable polyester fiber and polyester fiber are mixed is treated at a temperature of 120 ° C. or higher in a pH 4 water bath. Then, it is a manufacturing method of the flame-retardant polyester fiber structure concerning the above-mentioned this invention characterized by providing a flame-retardant compound.

  One of the preferred embodiments of the method for producing a flame-retardant polyester fiber structure of the present invention is one in which a dye is contained in the water bath or the flame-retardant compound treatment bath.

  According to the present invention, a cationic dyeable polyester fiber-containing fiber structure having excellent flame retardancy can be stably supplied. The fiber structure having the function of the present invention can be effectively used for general clothing use, bedding use, industrial use and the like.

The present inventors have problems mentioned above, i.e., the result of intensive studies for applying the stable flame retardancy to the polyester-based fiber structure which mix a cationic-dyeable polyester fiber, constituting the fiber structure The present inventors have investigated that this problem can be solved by setting the intrinsic viscosity of the cationic dyeable polyester fiber to 0.55 or less.

That is, according to the knowledge of the present inventors, in general, the intrinsic viscosity of the cationic dyeable polyester is as high as 0.69 as compared with the intrinsic viscosity of polyethylene terephthalate of 0.65, which acts as a so-called “candle core”. It spreads and burns. For this reason, by setting the intrinsic viscosity of the cationic dyeable polyester to 0.55 or less, the combustion behavior can be brought close to that of polyethylene terephthalate, and flame retardancy can be achieved. The lower limit of the intrinsic viscosity of the cationic dyeable polyester having an intrinsic viscosity of 0.55 or less is about 0.40 . That is, the range of intrinsic viscosity is 0.40 or more and 0.55 or less.

In the flame-retardant polyester fiber structure of the present invention, a cationic dyeable polyester having an intrinsic viscosity of 0.40 or more and 0.55 or less in that the desired effect of the present invention can be best exhibited. The fiber content is preferably 20% by weight or more based on the total weight of the fibers in the fiber structure. According to various findings by the present inventors, the preferable content of the cationic dyeable polyester fiber having an intrinsic viscosity of 0.40 or more and 0.55 or less is based on the total weight of the fibers in the mixed fiber structure. 20% by weight or more and less than 100% by weight

  Examples of the polyester fibers used in the present invention include polyester fibers containing an aromatic component and aliphatic polyester fibers. Examples of the polyester fiber containing an aromatic component include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate or a copolymer of these and a third component such as isophthalic acid, isophthalic acid sulfonate, adipic acid and polyethylene glycol. be able to. Examples of the aliphatic polyester fibers include poly L lactic acid, poly D lactic acid and homopolymers composed of D and L lactic acid, or polylactic acid-glycolic acid copolymers.

  A flame retardant compound may be copolymerized or blended with the polyester fiber of the present invention.

  The polyester fiber used in the present invention may contain various additives that are usually used in order to improve productivity and properties in the production process and processing process of the raw yarn. For example, additives such as heat stabilizers, antioxidants, light stabilizers, UV absorbers, antistatic agents, colorants, smoothing agents, plasticizers, antibacterial agents, fungicides, and deodorants are added to polyester fibers. It can be included.

  In the present invention, these polyester fibers can be used alone or in admixture of two or more, and short fibers, long fibers or these may be mixed.

The cationic dyeable polyester fiber used in the present invention is a polymer composed of dicarboxylic acid and glycol, and specifically includes polyethylene terephthalate, polypropylene glycol, polybutylene terephthalate, and the like as main components, and further cationic dyeing. -SO ₃ M group (M is an alkali or alkaline earth metal, and in the case of alkaline earth metal, it represents a half valence) or a phosphonium sulfonate group, and has ester forming ability It is preferable that a compound having one or more functional groups having a copolymer is copolymerized. This cationic dyeable polyester fiber has ethylene terephthalate as the main repeating unit, and preferred sulfonate compounds as the copolymer component include 5-sodium sulfoisophthalic acid and its ester derivatives, 5-lithium sulfoisophthalic acid. And ester derivatives thereof, 5- (tetraalkyl) phosphonium sulfoisophthalic acid and derivatives thereof, sodium p-hydroxyethoxybenzenesulfonate, potassium 2,5-bis (hydroxyethoxy) benzenesulfonate and the like.

  The copolymerization rate of the sulfonate compound is 0.5 to 6.0 mol%, preferably 1.0 to 4.0 mol%, more preferably 1.3 to 2.0 mol%, relative to the component. is there. Those in which a polyalkylene oxide glycol component having a molecular weight of 400 to 6000 is copolymerized with the cationic dyeable polyester can also be used. In addition, a flame retardant compound may be copolymerized or blended in the cationic dyeable polyester fiber of the present invention.

  The cationic dyeable polyester fiber used in the present invention may contain various commonly used additives for improving the productivity and properties in the production process and processing process of the raw yarn. For example, additives such as heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, antistatic agents, colorants, smoothing agents, plasticizers, antibacterial agents, fungicides and deodorants may be included. it can. In the present invention, these cationic dyeable polyester fibers can be used alone or in admixture of two or more, and short fibers, long fibers, or these may be mixed.

The fiber structure of the present invention uses a mixture of the cationic dyeable polyester fiber and the polyester fiber .

  In addition, other fibers, for example, natural fibers such as cotton, wool, silk and hemp, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as nylon, polypropylene, polyethylene, and acrylic, as long as the effects of the present invention are not impaired. Can be used in combination.

  As the polyester-based fiber structure of the present invention, fabric-like materials such as woven fabrics, knitted fabrics and nonwoven fabrics, and those in the form of yarns such as yarns, strings and ropes can be used, but are not limited thereto. It is not a thing.

In the flame-retardant polyester fiber structure of the present invention, it is essential that the intrinsic viscosity of the cationic dyeable polyester fiber constituting the fiber structure is 0.40 or more and 0.55 or less.

  As a method for producing such an intrinsic viscosity fiber, a method of adjusting the degree of polymerization at the time of polymer production to form a yarn and an intrinsic viscosity suitable for forming a yarn, for example, an intrinsic viscosity of 0.65 or more. There is a method in which after forming into a yarn using a polymer, the fiber is adjusted to a desired intrinsic viscosity by post-treatment. The latter method is preferable because the intrinsic viscosity can be freely changed.

For example, the intrinsic viscosity of the cationic dyeable polyester correlates with the molecular weight of the polymer, so that the molecular weight can be lowered by hydrolyzing the cationic dyeable polyester under an acidic pH of 4 or less . It can be lowered as desired to 40 or more and 0.55 or less.

  In addition, the intrinsic viscosity in the present invention refers to a value measured using an Ostwald viscometer after dissolving 0.10 g of a sample in 10 ml of orthochlorophenol at a temperature of 25 ° C. The sample may be arbitrarily taken out from the fiber structure.

  As a method for adjusting the intrinsic viscosity in the post-treatment, the treatment is preferably performed at a temperature of 120 ° C. or higher, preferably 130 ° C. or higher, in a water bath having a pH of 4 or less, preferably 3.5 or less. The pH, treatment temperature, and treatment time of the treatment water bath can be set according to the purpose. However, according to the knowledge of the present inventors, the lower limit value of the pH of the treated water bath should be about 2, and the preferred pH range of the treated water bath is 2 or more and 4 or less. The temperature of the treated water bath is preferably in the range of 120 ° C. or higher and 140 ° C. or lower.

  In the water bath having a pH of 4 or less according to the present invention, at least one salt composed of a monovalent cation and a divalent anion can be added. The addition of such a salt is preferable in order to stably obtain the desired intrinsic viscosity fiber. Examples of the salt include potassium sulfate, sodium sulfate, ammonium sulfate, lithium sulfate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium sulfite, sodium hydrogen carbonate and the like.

  The addition amount of the specific salt of this invention is 0.01 to 15% with respect to the weight of a polyester-type fiber structure, Preferably it is 0.1 to 7%.

  In the flame-retardant polyester fiber structure of the present invention, a flame-retardant compound can be contained. The flame retardant compound is not particularly limited, but from the viewpoint of recent environmental protection, a phosphorus compound containing no halogen element is preferably used.

  As a phosphorus compound, it can be used as a 1 type, or 2 or more types of mixture from the compounds shown by the following general formulas 1-4.

  The preferable content of the flame retardant compound is determined by the intrinsic viscosity of the cationic dyeable polyester and the mixed dose with the polyester fiber, but is 0.01 to 10% with respect to the weight of the fiber structure. 0%, preferably 0.1 to 5.0%.

  In the present invention, the flame retardant compound is applied by mixing in a water bath having a pH of 4 or less to adjust the intrinsic viscosity, and simultaneously exhausting and adsorbing the flame retardant compound. Any method of exhausting and adsorbing the active compound can be employed.

  As a method of providing a flame retardant compound after adjusting the intrinsic viscosity, a method of treating at a temperature of 100 to 135 ° C. for 10 to 60 minutes in a water bath containing the flame retardant compound, Employing a method of immersing the fiber structure in the aqueous solution containing the solution, squeezing it with a mangle or the like so as to obtain a predetermined adhesion amount, drying at 100 to 140 ° C., and heat-treating at a temperature of 150 to 200 ° C. for 1 to 10 minutes. Can do.

  In the present invention, dyeing can be performed simultaneously by mixing a disperse dye for polyester fibers and a cationic dye for cationic dyeable polyester during the intended flame retardant treatment. The dye can be mixed in a water bath having a pH of 4 or less or in a water bath containing a flame retardant compound.

  The flame-retardant polyester fiber structure of the present invention is suitably used for applications such as general clothing, bedding, curtains, sheets, seat covers, tents, and curing materials.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Moreover, the quality evaluation in an Example was implemented with the following method.
<Intrinsic viscosity>
A sample of 0.10 g was dissolved in 10 ml of orthochlorophenol at a temperature of 25 ° C., and measured using an Ostwald viscometer.
<Flame retardance>
It measured according to JIS L 1091 A-1 method (micro burner method) and JIS L 1091 D method (coil method).
<Washing durability>
The water-washing was performed according to JIS L 1042, and the dry cleaning was performed according to JIS L 1018. After washing was performed 5 times, flame retardancy was measured.
<Dyeing fastness>
Tests for fastness to dry friction and fastness to wet friction were performed by the method specified in JIS L 0849, and the grade was determined using a gray scale for contamination.
Examples 1 to 13, Reference Examples 1 to 5, Comparative Examples 1 to 8
Tables 1 and 2 show the results of evaluating the performance by using the following fabrics and flame retardant compounds.
(fabric)
Textile A: Polymerized polymer was synthesized from dimethyl terephthalate and ethylene glycol as raw materials, threaded to obtain false twisted yarn made of 130 dtex and 40 filaments of polyethylene terephthalate.

This processed yarn is used as warp and weft to make a plain fabric, scoured at a temperature of 95 ° C. by a conventional method, dried at 130 ° C., heat-set at 180 ° C., and a fabric with a basis weight of 180 g / m ² . . The intrinsic viscosities of the warp yarn and the weft yarn constituting the woven fabric were both 0.62.

  Fabric B: Polymerized from dimethyl terephthalate, dimethyl (5-sodium sulfo) isophthalic acid, and ethylene glycol as raw materials to form a polymer in which the copolymerization rate of the sulfonate compound is 1.5 mol% with respect to the acid component. A false twisted yarn of 130 dtex 40 filament made of cationic dyeable polyester was obtained.

This processed yarn is used as warp and weft to make a plain fabric, scoured at a temperature of 95 ° C. by a conventional method, dried at 130 ° C., heat-set at 180 ° C., and a fabric with a basis weight of 180 g / m ² . . The intrinsic viscosities of the warp yarn and the weft yarn constituting the fabric were both 0.68.

Fabric C: The processed yarn used in fabric A is used as warp yarn, the processed yarn used in fabric B is used as horizontal yarn to make a plain fabric, scoured at a temperature of 95 ° C. by a conventional method, and dried at 130 ° C. Heat setting was performed at 180 ° C. to obtain a woven fabric having a basis weight of 180 g / m ² .

The weight of the cationic dyeable polyester fiber in the woven fabric was 38% per unit weight. Moreover, the intrinsic viscosity of the warp yarn constituting the woven fabric was 0.62, and the intrinsic viscosity of the weft yarn was 0.68.
(Flame retardant compounds)
Compound A: An aqueous dispersion containing a compound represented by the following general formula 5 at a concentration of 40% by weight was used.

  Compound B: An aqueous dispersion containing a compound represented by the following general formula 6 at a concentration of 40% by weight was used.

  Compound C: An aqueous dispersion containing a compound represented by the following general formula 7 at a concentration of 40% by weight was used.

  Compound D: An aqueous dispersion containing a compound represented by the following general formula 8 at a concentration of 40% by weight was used.

(Processing method)
Under the conditions shown below, using a liquid dyeing machine, treatment at a bath ratio of 1/20 at 60 ° C. for 60 minutes, followed by hot water washing at 80 ° C. for 20 minutes, water washing for 10 minutes, drying at 120 ° C. and 170 Heat set at ° C.
(A) Phosphoric acid was used for pH adjustment.
(B) Sodium sulfate was added in an amount of 0.4 to 4% as necessary.
(C) The flame retardant was added with the compounds A, B, C and D.
(D) For the polyethylene terephthalate fiber, the disperse dye Sumicaron Blue E-RPD was used at a concentration of 0.3% based on the fiber weight. For cationic dyeable polyester fibers, the cationic dye Kayacrill Blue GSL-ED was used at a concentration of 0.3% based on the fiber weight.

Tables 1 and 2 collectively show the results of Examples 1 to 13, Reference Examples 1 to 5, and Comparative Examples 1 to 8. Among them, Reference Examples 1 to 5 are those using the woven fabric B, using the cation dyeable polyester fiber alone, not being mixed with the polyester fiber, and included in the present invention. This is not a reference example.
As can be seen from Tables 1 and 2, those according to the present invention have excellent flame retardancy.

Claims (9)

It is a fiber structure in which a cationic dyeable polyester fiber and a polyester fiber are mixed. The cationic dyeable polyester fiber has an intrinsic viscosity of 0.40 or more and 0.55 or less , and the polyester The flame retardant polyester fiber structure , wherein the fiber has an intrinsic viscosity of 0.68 or less .   2. The flame-retardant polyester according to claim 1, wherein the cationic dyeable polyester fiber having an intrinsic viscosity of 0.55 or less is contained in an amount of 20% by weight or more based on the total weight of the fiber in the fiber structure. Fiber structure.   The flame-retardant polyester fiber structure according to claim 1 or 2, wherein the fiber structure contains a flame-retardant compound. The flame retardant polyester fiber structure according to claim 3, wherein the flame retardant compound is at least one selected from phosphorus compounds represented by the following general formulas 1 to 4.

  The flame retardant according to any one of claims 1 to 4, wherein the fiber structure is clothing, bedding, curtains, roll curtains, sheets, seat covers, notebooks, wall cloths, ceiling cloths, carpets, tents, or curing sheets. Polyester fiber structure. Cationic dyeable polyester fiber and polyester fiber structure that mix and polyester fibers, in any one of claims 1 to 5, characterized in that at a temperature of 120 ° C. or higher in pH4 following water bath The manufacturing method of the flame-retardant polyester fiber structure of description . The method for producing a flame retardant polyester fiber structure according to claim 6, wherein the water bath contains a dye and a flame retardant compound. The method for producing a flame-retardant polyester fiber structure according to claim 6 , wherein the flame-retardant compound is added after the treatment in the water bath having a pH of 4 or less. The method for producing a flame retardant polyester fiber structure according to claim 8 , wherein a dye is contained in the water bath or the treatment bath with the flame retardant compound.