JP2007182652A - Flame-retardant finishing agent for polyester fiber and its processing method - Google Patents

Abstract

An object of the present invention is to exhibit excellent durability and flame retardancy even in a material having a high mixing ratio of cationic dyeable polyester, and to achieve the target flame retardance even in applications requiring high flame retardance such as car seat applications. A flame retardant processing agent for polyester fibers and a processing method using the same are provided.
At least one organophosphorus flame retardant (I) and at least one nitrogen flame retardant (II) selected from the group consisting of a guanidine compound, a guanylurea compound and a melamine compound are included. The flame retardant processing agent which is a water dispersion or a water emulsion contained is used.
[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 use is mixed with cationic dyeable polyester (CD-PET) even if the durable flame retardancy of regular polyester (Reg-PET) is obtained. In particular, when the mixing ratio (CD mixing ratio) is 50% or more, it is difficult to develop the durability and flame retardancy, and the target performance cannot be realized 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.

  In order to solve the above-mentioned problems, the flame retardant for polyester fiber of the present invention comprises at least one organophosphorus flame retardant (I), a guanidine compound, a guanylurea compound, and a melamine compound. It shall be an aqueous dispersion or aqueous emulsion containing at least one nitrogen-based flame retardant (II) selected from the group.

  The flame retardant processing agent of the present invention contains 55 to 95% by weight of the organic phosphorus flame retardant (I) in the flame retardant component and 5 to 45% by weight of the nitrogen flame retardant (II) in the flame retardant component. It is preferable to do.

  Further, the flame retardant processing method of the polyester fiber of the present invention, after applying the flame retardant processing agent to a polyester fiber or a fiber product comprising the same by a treatment by high temperature exhaustion method, dipping or coating, A heat treatment at 80 ° C. or higher is performed.

  According to the flame retardant of the present invention, the combined use of the above-mentioned two types of flame retardants eliminates the problem of lack of flame retardance peculiar to phosphorus flame retardants, and the conventional phosphorus flame retardant alone Despite its relatively low sorption, it has excellent flame retardant performance, and in curtain applications, it exhibits durable flame resistance even in composite materials with a high CD blend ratio. It becomes possible to reach. 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 the organic phosphorus flame retardant (I) used in the present invention include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, other aromatic phosphate esters, aromatic condensed phosphate esters, etc. Among them, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, and 2-naphthyl diphenyl phosphate can be suitably used.

  Further, as the nitrogen-based flame retardant (II), one or a mixture of two or more nitrogen compounds selected from guanidine compounds, guanylurea compounds, melamine compounds and ammonium polyphosphates are used. Melamine phosphate, melamine sulfate, melamine cyanurate, and guanylurea phosphate can be suitably used.

  A commercially available thing can be utilized for the said organophosphorus flame retardant and nitrogen flame retardant, and it can also be manufactured by a well-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.

  When the above organic phosphorus flame retardant or nitrogen flame retardant is dispersed or emulsified in water, a nonionic active agent and / or an anionic active agent is used.

  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. Preferably, polyoxyethylene distyrenated phenyl ether or polyoxyethylene tristyrenated phenyl ether is 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. Preferably, polyoxyethylene distyrenated phenyl ether sulfate salt or polyoxyethylene tristyrenated phenyl ether sulfate salt is 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 said phosphorus compound and nitrogen compound which are flame retardant components.

  In order to stabilize the dispersion state, the flame retardant processing agent of the present invention may contain an organic solvent such as methanol, ethanol, toluene, ethylene glycol, or butyl cellosolve. Furthermore, a protective colloid agent that is stabilized by a thickening action may be added to the emulsion / dispersion. 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 will be described later, the flame retardant processing agent of the present invention is squeezed with a mangle so that a predetermined adhesion amount is obtained by immersing the fiber in a solution which is dyed in the fiber simultaneously with the dye, or in a solution diluted with water. It can be processed by a method such as a pad dry thermocuring method for drying and heat setting, a coating method in which a resin binder and this product and / or a flame retardant aid are mixed and thickened to coat fibers.

  The flame-retardant processing method of the present invention comprises a step of applying the above-mentioned flame-retardant processing agent to a polyester fiber by a post-processing treatment and subjecting it to a heat treatment at 80 ° C. or more. As an example of such a post-processing treatment, Includes a high temperature exhaustion method, a pad thermo method, a 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 heat 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, treatment is performed by a pad-dry thermo-curing method in which the film is squeezed with mangle, dried and heat-set.

  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 Each flame retardant finishing agent of Examples and Comparative Examples was prepared according to the formulation (% by weight) shown in Table 1 below. In Table 1, all of diphenyl monoorthoxenyl phosphate, 2-naphthyl diphenyl phosphate, and TPP (triphenyl phosphate) are manufactured by Daihachi Chemical Industry Co., Ltd. Polynized melamine phosphate, melamine sulfate, and guanylurea phosphate are manufactured by Sanwa Chemical Co., Ltd., and melamine cyanurate is manufactured by Nissan Chemical Industries, Ltd. In the above preparation, the surfactant used for emulsifying and dispersing is “Neugen EA-87” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. It is "Hitenol NF-13" manufactured by Pharmaceutical Co., Ltd.

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 50%). 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 30 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 5 minutes of washing with hot water, the following reduction washing bath formulation, bath ratio 1:30, 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 times 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.

(Washing) According to JIS K 3371, a weak alkaline first-class detergent is used at a rate of 1 g / L, and a bath ratio of 1:40 is washed at 60 ° C. ± 2 ° C. for 15 minutes, and then at 40 ° C. ± 2 ° C. This was performed 5 times, with a 5-minute rinse 3 times, a centrifugal dehydration for 2 minutes, and then a hot air drying at 60 ° C. ± 5 ° C. once.

(Dry cleaning) Using 12.6 mL of tetrachloroethylene and 0.265 g of charge soap (nonionic surfactant / anionic surfactant / water = 10/10/1 (weight ratio)) per 1 g of sample, 30 ° C. ± 2 ° C. The treatment for 15 minutes was defined as one time, and this was performed five times.

3. Evaluation in 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., then the fabric is taken out, washed with hot water for 5 minutes, then subjected to centrifugal dehydration for 2 minutes, and subjected to the following reduction washing bath formulation, bath ratio 1:30, reduction washing at 85 ° C. for 15 minutes. Further, after 5 minutes of washing with hot water and water, centrifugal dehydration was performed for 2 minutes, followed by drying at 110 ° C. for 3 minutes. After performing padding treatment (immersion) with a softening agent solution (1.0% soln), it was heated at 150 ° C. for 3 minutes.

[Dyeing bath prescription] Dark (Black)
Disperse dye Yellow 2.0% owf
Disperse dye Red 0.9% owf
Disperse dye Blue 1.6% owf
Acetic acid 0.2 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 used for polyester fiber products in general, for example, curtains, cloth blinds, carpets and other rugs, wall interior materials, etc., 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)

At least one organophosphorus flame retardant (I);
Containing at least one nitrogen-based flame retardant (II) selected from the group consisting of guanidine-based compounds, guanylurea-based compounds, and melamine-based compounds,
A flame retardant processing agent for polyester fibers which is a water dispersion or water emulsion.   The organophosphorous flame retardant (I) is contained in an amount of 55 to 95% by weight in the flame retardant component, and the nitrogenous flame retardant (II) is contained in an amount of 5 to 45% by weight in the flame retardant component. Item 2. A flame retardant processing agent for polyester fiber according to Item 1.   After applying the flame retardant processing agent according to claim 1 or 2 to a polyester fiber or a fiber product made of the same by a high-temperature exhaust method, dipping or coating, heat treatment at 80 ° C. or higher is performed. A flame-retardant processing method for polyester fiber,