JP2007131968A - Flame-retardant finishing agent for polyester fiber and method for processing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant finishing agent for polyester fiber excellent in sorption properties, durability of flame-retardancy and to provide a method for processing by using the same. <P>SOLUTION: The method for processing the flame-retardant finishing agent uses a water dispersion or water emulsion comprising a mixture of one or more kind of biphenylyl phosphate compounds represented by general formula (I) and a mixture of one or more kind of monophosphate compounds represented by general formula (II). (In the formula, X, Y are each an integer of 1-3, R<SB>1</SB>, R<SB>2</SB>, R<SB>3</SB>or R<SB>4</SB>are each the same or different, hydrogen or a lower alkyl group.). <P>COPYRIGHT: (C)2007,JPO&INPIT

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. However, condensed phosphates have little sorption even if they are attached to the surface. Drop off by alkaline soaping (reduction cleaning), 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.

  Furthermore, even if the durable flame retardancy of regular polyester (Reg-PET) is obtained, it has been considered difficult to express the durable flame retardancy if a cationic dyeable polyester (CD-PET) is mixed.

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 insufficient flame retardancy due to the low sorption origin inherent in phosphorus-based flame retardants, has good sorption properties and excellent washing durability, and is particularly cationic dyeable. An object of the present invention is to provide a flame retardant processing agent capable of obtaining a sufficient durability flame resistance even for fabrics that are more difficult to express flame retardant, such as a polyester blend, and a flame retardant processing method using the same.

In order to solve the above-described problems, the flame retardant processing agent for polyester fibers of the present invention includes one or a mixture of two or more biphenylyl phosphate compounds represented by the general formula (I) and a general formula ( It is assumed to be an aqueous dispersion or an aqueous emulsion containing one or a mixture of two or more of the monophosphate compounds represented by II).

(Wherein, X and Y are integers of _{1 to} 3, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms or lower alkyl groups, which may be the same or different.)

  In the flame retardant processing agent of the present invention, the biphenylyl phosphate compound (I) is 40 to 95% by weight in the flame retardant component, and the monophosphate compound (II) is 5 to 60% by weight in the flame retardant component (however, in total 100% by weight) is preferable.

  Further, in the flame-retardant processing method for polyester fiber of the present invention, the flame retardant processing agent is used for the treatment by the high temperature exhaust method, or is applied to the polyester fiber or a fiber product comprising the same by dipping or coating. Thereafter, heat treatment at 80 ° C. or higher is performed.

  According to the flame retardant processing agent of the present invention, by using two kinds of compounds represented by the general formulas (I) and (II) in combination, a more flame-resistant expression such as a blended product of a cationic dyeable polyester is obtained. However, it is possible to exhibit durable flame resistance even with difficult fabrics.

  In addition, since a non-halogen phosphorous compound is used, there is no concern about the generation of halogenated gas (such as bromodioxin) during combustion of the polyester synthetic fiber, which is also effective for environmental protection.

  As described above, the biphenylyl phosphate compound used in the present invention is a compound in which X in the formula (I) is an integer of 1 to 3, and among them, diphenyl monoorxenyl phosphate is preferable.

The monophosphate compound used in the present invention is a compound in which Y in formula (II) is an integer of 1 to 3, and R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom or a lower alkyl group. Of these, triphenyl phosphate, tricresyl phosphate and cresyl diphenyl phosphate are preferred.

  Commercially available phosphorus compounds represented by these formulas (I) and (II) can be used, and can also be produced by known methods. 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.

  Although the compound of formula (II) is not durable and flame retardant, it is highly sorbed after dyeing, and the compound of formula (I) is relatively difficult to sorb among low molecular weight phosphate esters. In the present invention, by using these together, it is possible to obtain a flame retardant having higher sorption and remaining in the fabric after RC, soaping, water washing, and dry cleaning, and exhibiting durable flame retardancy.

  When the phosphorus compound is dispersed or emulsified in water, a nonionic activator and / or an anionic activator 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 phosphorus compound which is a flame retardant component.

  In the flame retardant processing agent of the present invention, the content of the phosphorus compound as a flame retardant component is usually in the range of 30 to 50% by weight.

  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 150 ° 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, diphenyl monoorthoxenyl phosphate, TPP (triphenyl phosphate), TCP (tricresyl phosphate), and CDP (cresyl diphenyl phosphate) are all manufactured by Daihachi Chemical Industry Co., 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 in the dyeing and bathing method Using the flame retardant processing agents of the above Examples and Comparative Examples, the polyester fiber fabric (regular polyester / cationic dyeable polyester = 90/10 fabric) is flame-retardant processed by the dyeing and bathing method. gave.

  Specifically, using Mini-Color (manufactured by Tecsum Giken) as a dyeing machine, the following bath formulation was heated from 60 ° C. at a bath ratio of 1:10 and treated at 135 ° C. for 30 minutes. 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, hydrosulfite sodium 2.0 g / L, soda ash 1.0 g / L and Tripol TK (Daiichi Kogyo Seiyaku ( 1.0 g / L was used, and reduction cleaning was performed at a bath ratio of 1:30 at 80 ° C. for 10 minutes, and after 5 minutes of hot water washing, heat setting was performed at 180 ° C. for 30 seconds. The processing amount of the flame retardant finish is 20% o. w. f (on the weight of fiber).

[Bath prescription]
Dianix Red AC-E 0.20% owf
Dianix Yellow AC-E 0.12% owf
Dianix Blue AC-E 0.02% owf
Acetic acid 1.0 g / l
Anhydrous sodium acetate 3.0 g / l
Flame retardant x% owf

  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 processed with flame retardancy, those that have been processed and those that have been washed or dry-cleaned under the following conditions are JIS L 1091 A-1 method (micro burner method) and JIS L 1091 D method (coil method). The flame retardancy was measured. 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. Pad Dry Thermocure Method Using the flame retardant processing agent of the above examples, a polyester fiber fabric (regular polyester 100% fabric) was subjected to flame retardant processing by the pad dry thermocure method.

  Specifically, after immersing the fabric in a solution obtained by diluting a flame retardant to 15% with water, the fabric was squeezed to 50% with a mangle, dried at 110 ° C. for 2 minutes, and cured at 180 ° C. for 1 minute. . Then, using soda ash 1.0 g / L and Tripol TK (Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 g / L as chemicals, soaping was performed at a bath ratio of 1:30 at 80 ° C. for 10 minutes. After 5 minutes of hot water washing, it was dried.

  Thus, the sorption amount and flame retardancy were examined in the same manner as described above for the polyester fiber woven fabric subjected to flame retardancy. For comparison, flame resistance was also measured for untreated fabrics. The results are shown in Table 3 below.

  The use of the polyester fiber treated by the flame retardant or flame retardant processing method of the present invention is not particularly limited. For example, various interior uses such as curtains, cloth blinds, carpets and other rugs, wall coverings, sofas and other skins. Widely used in materials, black curtains, notebooks, etc.

Claims (3)

Contains one or a mixture of two or more biphenylyl phosphate compounds represented by general formula (I) and one or a mixture of two or more monophosphate compounds represented by general formula (II) A flame retardant processing agent for polyester fibers which is a water dispersion or water emulsion.

(Wherein, X and Y are integers of _{1 to} 3, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atoms or lower alkyl groups, which may be the same or different.)   The biphenylyl phosphate compound (I) is contained in the flame retardant component in an amount of 40 to 95% by weight, and the monophosphate compound (II) is contained in the flame retardant component in an amount of 5 to 60% by weight. Flame retardant for polyester fiber.   The flame retardant processing agent according to claim 1 or 2 is used for a treatment by a high temperature exhaustion method, or after being applied to a polyester fiber or a fiber product comprising the same by dipping or coating, a heat treatment at 80 ° C or higher is performed. A flame retardant processing method for a polyester fiber, characterized by comprising: