JP2008133569A - Flame-retardant finishing agent for polyester fiber and its processing method - Google Patents

Abstract

The present invention provides a polyester system that exhibits excellent durability and flame retardancy even in cationic dyed polyester blended materials, and that can reach the target flame retardance even in applications that require high flame retardancy such as car seat applications. Provided are a flame retardant processing agent for fibers and a processing method using the same.
Flame retardant processing comprising an aqueous dispersion or O / W emulsion containing one or more organic phosphorus compounds and one or more pyrolytic organic chemical foaming agents. Preferably, the foaming agent is contained in a proportion of 5 to 45% by weight in the total amount with the organic phosphorus compound. Using this flame retardant processing agent, it is processed by a high temperature exhaust method, or after applying a flame retardant processing agent by dipping or coating, heat treatment is performed at 80 ° C. or higher, thereby forming a polyester fiber or this. Adds flame retardancy to textile products.
[Selection figure] None

Description

  TECHNICAL FIELD The present invention relates to a flame retardant processing agent capable of imparting flame retardancy to a polyester fiber or a textile product such as a fabric made of the same, and a flame retardant processing method using the same.

  Conventionally, halogen-based compounds such as hexabromocyclododecane (HBCD) have been used in water as a flame-retardant processing agent for imparting flame retardancy to post-processing fiber products such as polyester fibers or fabrics made of the same. Dispersed or emulsified ones have generally been used. However, polyester fibers treated with such a halogen-based flame retardant agent may generate harmful halogenated gases such as bromodioxin when burned, and there is an increasing demand for dehalogenation.

  In addition, HBCD that has been used for exhaustion processing has been found to have poor decomposition and high accumulation, and there is a demand for de-HBCD.

  In contrast, flame retardants using phosphorus compounds such as organophosphates are used, but condensed phosphates have little sorption even if they are attached to the surface, and the surface deposits are reduced and cleaned. Drop off by alkaline soaping (RC), water washing, dry cleaning, etc. For this reason, it tends to be insufficient in durability and flame retardancy.

  On the other hand, known low molecular weight phosphates have good sorption after processing, but have insufficient durability and flame retardancy for water washing and dry cleaning.

  Further, in order to satisfy the flameproof performance, it is necessary to process a large amount of the flame retardant, and due to the large amount of processing, there is a problem that the texture and hue are lowered.

  When the treatment amount is appropriate, the durable flame retardancy for curtain applications is a blend of cationic dyeable polyester (CD-PET) even if the regular flame retardancy of regular polyester (Reg-PET) is obtained. Is difficult to develop the durability and flame retardancy, and the target performance could not be realized even for car seat applications.

In order to solve the above problems, for example, flame retardant processing agents using two or more specific phosphate esters have been proposed (Patent Documents 1 and 2). However, there has not yet been obtained a fabric that can solve the above-mentioned problems and can impart sufficient durability flame retardance even for fabrics that are more difficult to express flame retardancy, such as blends of cationic dyeable polyesters.
JP 2004-225175 A JP 2004-225176 A

  In view of the above, the present invention solves the problem of lack of flame retardance peculiar to phosphorus-based flame retardants, exhibits excellent durability flame retardancy even in materials having a high CD mixing ratio, and is used for car seats. Another object of the present invention is to provide a flame retardant processing agent that reaches the target flame retardant even in applications that require high flame resistance, and a flame retardant processing method using the same.

  The present inventors are not known that the pyrolytic organic chemical foaming agent works alone as a flame retardant for polyester fibers, but when used in combination with an organic phosphorus compound as a secondary agent, As a result, the present inventors have found that flame retardancy is greatly improved, and based on this, the present invention has been completed.

  The flame retardant processing agent for polyester fibers of the present invention is an aqueous dispersion or O containing one or more organic phosphorus compounds and one or more pyrolytic organic chemical foaming agents. / W type emulsion.

  In the flame retardant processing agent, the pyrolyzable organic chemical foaming agent is preferably contained at a ratio of 5 to 45% by weight in the total amount with the organic phosphorus compound.

  A flame retardant processing method for a polyester fiber of the present invention is a flame retardant processing method for imparting flame retardancy to a polyester fiber or a fiber product comprising the same, using the flame retardant agent of the present invention. It is assumed that heat treatment is performed at 80 ° C. or higher after applying the flame retardant treatment or applying the flame retardant processing agent by dipping or coating.

  According to the flame retardant processing agent of the present invention and the flame retardant processing method using the same, an aqueous dispersion of an organic phosphorus compound and a compound used as a pyrolytic organic chemical foaming agent (hereinafter also simply referred to as a foaming agent) or By using the O / W type emulsion, it is possible to solve the problem of lack of flame retardance peculiar to phosphorus-based flame retardants while maintaining various performances of the organic phosphorus-based flame retardant. That is, the flame retardant processing agent of the present invention is superior in flame retardant performance despite its relatively low sorbability compared to conventional phosphorous flame retardant alone systems, and is difficult to endure even in a composite material of CD blend for curtain applications. It exhibits flammability and also makes it possible to develop the target flame retardancy even in car seat applications. Moreover, since the sorption property is relatively low, there is little change in the hue of the fabric.

  In addition, since a non-halogen phosphorus compound is used, there is no concern that a halogenated gas (such as bromodioxin) is generated when the polyester fiber is burned, which is also effective for environmental protection.

  Examples of organic phosphorus flame retardants used in the present invention include phosphorus compounds such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, other aromatic phosphate esters, and aromatic condensed phosphate esters Among them, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, and 2-naphthyl diphenyl phosphate can be preferably used.

  In addition, the thermal decomposition type organic chemical foaming agent used in the present invention is an azo compound, a nitroso processed product, a hydrazine derivative, a semicarbazide compound, an azide compound, a tetrazole compound, etc. In addition, a gas such as nitrogen gas or carbon dioxide gas is generated along with the decomposition.

  Specific examples of such foaming agents include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide), hydrazodicarbonamide, barium azodicarboxylate, diazo Aminobenzene, guanidine nitrile, t-butylamine nitrile, N, N′-dimethylterephthalamide, p-toluenesulfonyl azide, guanylurea nitrile, benzyl monohydrazone, phenylmethylurethane-p-sulfonylhydrazide, N-nitrourea, acetamidine Nitrile, 1,3-benzenedisulfonylhydrazide, 2,2′-azobisisobutylnitrile, 4,4′-thiobis (benzenesulfonylhydrazide), 3,3′-sulfonylbis (benzenesulfonylhydrazide) ), Benzenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, diisopropyl hydrazodicarboxylate, trihydrazino-sym-triazine, 5-phenyltetrazole, among which azodicarbonamide, 4,4′-oxybis (benzenesulfonyl hydrazide), Hydrazodicarbonamide can be preferably used.

  A commercially available thing can be utilized for the said organophosphorus flame retardant and foaming agent, and can also be manufactured by a known method. When the obtained compound is a mixture and a simple substance is required, it may be separated by a known separation means such as distillation.

  The flame retardant processing agent of the present invention is obtained by dispersing the organic phosphorus compound and the foaming agent in water or making an O / W emulsion, and at this time, a nonionic surfactant and an anionic surfactant are used. Is preferred.

  Specific examples of the nonionic surfactant include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ester, polyhydric alcohol fatty acid ester alkylene oxide adduct, higher alkylamine alkylene oxide adduct, fatty acid Amidoalkylene oxide adducts, alkyl glycosides, sucrose fatty acid esters and the like can be mentioned. Among these, one or a mixture of two or more of polyoxyethylene monostyrenated phenyl ether, polyoxyethylene distyrenated phenyl ether and polyoxyethylene tristyrenated phenyl ether can be suitably used.

  Specific examples of anionic surfactants include alkyl sulfate salts such as higher alcohol sulfates, higher alkyl ether sulfates and sulfated fatty acid esters, and alkyl sulfonates such as alkyl benzene sulfonates and alkyl naphthalene sulfonates. Furthermore, alkyl phosphate salts such as higher alcohol phosphate salts and higher alcohol alkylene oxide adduct phosphate salts are listed. In addition, alkyl aryl sulfonate salt, polyoxyalkylene alkyl ether sulfate salt, polyoxyalkylene alkyl ester phosphate salt, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, funnel oil, petroleum sulfonate, alkyl diphenyl ether sulfonate salt, etc. It is done. Among them, one or a mixture of two or more of polyoxyethylene monostyrenated phenyl ether sulfate, polyoxyethylene distyrenated phenyl ether sulfate and polyoxyethylene tristyrenated phenyl ether sulfate is preferred. Can be used.

  Although the usage-amount of such surfactant is not specifically limited, Usually, it uses in the range of 5-20 weight% with respect to the total amount of the said phosphorus compound which is a flame retardant component, and a foaming agent.

  Water dispersion or O / W type emulsification can be carried out according to a conventional method, and in order to further stabilize the dispersion state, the flame retardant processing agent of the present invention includes organic solvents such as methanol, ethanol, toluene, ethylene glycol, butyl cellosolve, etc. May be included. Moreover, you may add the protective colloid agent which stabilizes by a thickening effect | action to an emulsification and dispersion liquid. Examples of the protective colloid agent (water-soluble polymer) to be added include carboxymethyl cellulose salt, xanthan gum (xanthan gum), gum arabic, locust bean gum, sodium alginate, polyvinyl alcohol (PVA), gelatin, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide, Examples include methoxyethylene maleic anhydride copolymer, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, soluble starch, carboxymethyl starch, and cationized starch. Among these, carboxymethylcellulose salt and xanthan gum are preferable from the viewpoints of physical properties of the resulting solution and its stability. Moreover, various resin additives, such as a ultraviolet absorber and antioxidant, can also be mix | blended.

  As described later, the flame retardant finish of the present invention can be dyed in the fiber at the same time as the dye, or can be mangled so that the fiber is immersed in a solution diluted with water so that a predetermined adhesion amount is obtained. It can be suitably processed by a method such as a pad-drying thermo-cure method in which drawing, drying, and heat setting are performed, or a coating method in which a resin binder and this product and / or a flame retardant aid are mixed and thickened to coat fibers.

  That is, the flame retardant processing method of the present invention is to apply the flame retardant processing agent to polyester fibers by post-processing treatment. Examples of such post-processing processing include a high temperature exhaustion method and a pad thermostat. Method, coating method and the like.

  In the high temperature exhaustion method, the polyester fiber is immersed in a treatment bath to which a flame retardant processing agent is added, and is treated at a high temperature (usually 80 ° C. or more, preferably 110 to 140 ° C.) for a predetermined time (for example, 2 to 60 minutes). This sorbs the flame retardant onto the fiber. Preferably, a dyeing and bathing method in which the flame retardant is sorbed onto the fiber simultaneously with the dye is used. That is, it is efficient and preferable to add a flame retardant processing agent to the dyeing bath, immerse the polyester fiber in the dyeing bath, and perform exhaustion treatment at a high temperature.

  In the pad thermo method, the polyester fiber is immersed in a liquid containing a flame retardant finish, and is squeezed with a mangle or the like so as to obtain a predetermined adhesion amount, and heat treatment is performed by steaming such as dry heat treatment or heating steam treatment This sorbs the flame retardant onto the fiber. The heat treatment temperature is usually in the range of 110 to 210 ° C. Preferably, after dipping, the substrate is squeezed with a mangle, dried and heat set, and then treated by a pad dry thermocure method.

  In the coating method, a resin binder and this product and / or a flame retardant aid are mixed and thickened to coat the fiber.

  The polyester fiber to be treated includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT), as well as isophthalic acid, isophthalic acid sulfonate, adipic acid, polyethylene glycol, etc. Of the third component, especially cationic dyeable polyester. In addition, an original yarn formed by kneading a pigment when producing a yarn can be used. The textile products to be treated include various yarns, woven and knitted fabrics, non-woven fabrics, ropes, etc., and may be woven fabrics or composite materials using different yarns of the above-mentioned fibers. Includes union cloth. The fiber product may be a combination of other synthetic fibers, natural fibers, or semi-synthetic fibers by blending or the like.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

1. Preparation of Flame Retardant Finishing Agent According to the formulation (% by weight) shown in Table 1 below, each flame retardant finishing agent of Examples and Comparative Examples was prepared as an O / W type emulsion by the phase inversion emulsification method.

2. Evaluation for Curtain (Dyeing and Bathing Method) Using the flame retardant processing agents of the above examples and comparative examples, flame retardant processing by the dyeing and bathing method for regular polyester / cationic dyeable polyester mixed material (CD mixing ratio 15%). Was given.

  Specifically, using Mini-Color (manufactured by Teksam Giken) as a dyeing machine, the following dyeing bath formulation was heated from 60 ° C. at a bath ratio of 1:10 and treated at 130 ° C. for 45 minutes. The amount of flame retardant processing agent is 20% o. w. f (on the weight of fiber). After the treatment, the temperature is lowered to 80 ° C., and then the fabric is taken out. After washing with hot water for 5 minutes, the following reduction washing bath formulation, bath ratio 1:10, reduction washing at 80 ° C. for 10 minutes, and further washing with hot water for 5 minutes. After that, heat setting was performed at 180 ° C. for 30 seconds.

[Dyeing bath prescription] dark (blue)
Disperse dye Blue 2.0% owf
Cationic dye Black 2.0% owf
Acetic acid 1.0 g / L
Anhydrous sodium acetate 3.0 g / L
Flame retardant 20% owf

[Reduction cleaning bath prescription]
Soaping agent (Daiichi Kogyo Seiyaku Co., Ltd., M-2882B) 2.0 g / L
Hydrosulfite sodium 1.0 g / L
Na ₂ CO ₃ 1.0 g / L

  In the above, the sorption amount and flame retardancy of the flame retardant finish were examined. The flame retardant evaluation method is as follows.

[Flame retardance]
For woven fabrics that have been flame-retarded, those that have been processed, and those that have been subjected to water washing or dry cleaning under the following conditions, JIS L 1091 A-1 method (microburner method) and JIS L 1091 D method (45 ° coil method) ) To measure flame retardancy. In the micro burner method, after 1 minute heating and after 3 seconds of flaming, “○” indicates that the after flame is 3 seconds or less, the dust is 5 seconds or less, and the carbonized area is 30 cm ² or less. Except for “×”. In the coil method, the case where the number of flame contact was 3 times or more was “◯”, and the case where it was 2 times or less was “x”. For comparison, flame resistance was also measured for untreated fabrics.

[Water washing]
According to JIS K 3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, and a bath ratio of 1:40 was washed with water at 60 ° C. ± 2 ° C. for 15 minutes, and then rinsed at 40 ° C. ± 2 ° C. for 5 minutes Was performed three times, and centrifugal dehydration was performed for 2 minutes. Thereafter, the hot air drying at 60 ° C. ± 5 ° C. was performed once, and this was performed five times.

[Dry cleaning]
Using 12.6 mL of tetrachlorethylene per 1 g of sample and 0.265 g of charge soap (nonionic surfactant / anionic surfactant / water = 10/10/1 (weight ratio)) at 30 ° C. ± 2 ° C. for 15 minutes The treatment was performed once and this was performed 5 times.

3. Evaluation for Car Seat (Dyeing and Bathing Method) Using the flame retardant processing agent of the above examples, polyester knit was subjected to flame retardant processing by the dyeing and bathing method.

  Specifically, using Mini-Color (manufactured by Teksam Giken) as a dyeing machine, the following dyeing bath formulation was heated from 60 ° C. at a bath ratio of 1:10 and treated at 130 ° C. for 45 minutes. The amount of flame retardant processing agent is 5% o. w. f. After the treatment, the temperature is lowered to 80 ° C., and then the fabric is taken out. After 5 minutes of washing with hot water, centrifugal dehydration is performed for 2 minutes, and the following reduction cleaning bath formulation, bath ratio 1:10, reduction cleaning is performed at 85 ° C. for 15 minutes. Further, after 5 minutes of washing with hot water, centrifugal dehydration was performed for 2 minutes, and drying was performed at 110 ° C. for 3 minutes. After performing padding treatment (immersion) with a softener solution (1.0% soln), it was heated at 150 ° C. for 3 minutes.

[Dyeing bath prescription] Dark (Black)
Disperse dye 5.0% owf
Acetic acid 1.0 g / L
Anhydrous sodium acetate 3.0 g / L
UV absorber (Daiichi Kogyo Seiyaku Co., Ltd., Uniguard E-200N) 2.0% owf
Dyeing assistant (Daiichi Kogyo Seiyaku Co., Ltd., Carazole ACE-191) 0.5 g / L
Flame retardant finish 5% owf

[Reduction cleaning bath prescription]
Thiourea dioxide 1.0 g / L
Soda ash 1.0 g / L
Soaping agent (Daily Kogyo Seiyaku Co., Ltd., Amiradin D) 1.0 g / L

  With respect to the polyester knit subjected to flame retardancy, the sorption amount was examined in the same manner as described above, and the flame retardancy was examined by a horizontal method (JIS D-1201 FMVSS302). For comparison, flame resistance was also measured for untreated fabrics. The results are shown in Table 3 below, and the flame retardant evaluation criteria are shown in Table 4.

  The flame retardant agent or flame retardant processing method of the present invention is applied to polyester fiber products in general, for example, various interior uses such as curtains, cloth blinds, carpets and other rugs, wall coverings, sofas and other skin materials, black curtains, notebooks, etc. Although widely used, particularly high flame retardancy can be imparted, it can be suitably used for car seats that require a high degree of flame retardancy.

Claims (3)

  Flame retardant processing of polyester fiber comprising an aqueous dispersion or O / W emulsion containing one or more organic phosphorus compounds and one or more pyrolytic organic chemical foaming agents Agent.   2. The flame-retardant processing agent for polyester fiber according to claim 1, wherein the pyrolytic organic chemical foaming agent is contained in a proportion of 5 to 45 wt% in the total amount with the organic phosphorus compound.   A flame retardant processing method for imparting flame retardancy to a polyester fiber or a fiber product comprising the same, using the flame retardant processing agent according to claim 1 or 2, and performing a treatment by a high temperature exhaustion method, or A method for flame-retardant processing of polyester fiber, characterized in that after the flame-retardant processing agent is applied by dipping or coating, heat treatment is performed at 80 ° C. or higher.