JP2007070751A - Flame retardant of polyester-based fiber and method for processing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant for polyester-based fibers having good sorption, excellent in durable flame retardancy and free from problems such as smoking and increase of haze rate and to provide a processing method using the flame retardant. <P>SOLUTION: The flame retardant is obtained by emulsifying or dispersing one or mixture of biphenylyl phosphate compounds represented by general formula (I) (wherein X is an integer of 1-3) into water by using a surfactant. <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.

  Therefore, flame retardants using phosphorus compounds such as organophosphates are used, but condensed phosphate esters have little sorption even if they are attached to the surface, and the surface deposits are reduced by washing (RC ) And so forth, such as alkaline soaping, dry cleaning, etc., so that it tends to be deficient in durability and flame retardancy (for example, Patent Document 1).

On the other hand, known low molecular weight phosphates have good sorption properties but high volatility and have the following problems.
(1) Smoke is generated during heat treatment of flame retardant processing.
(2) When used as an automobile interior material, the problem of haze (problem in which the windshield becomes cloudy) occurs.
(3) In order to decompose and volatilize below the flash point of the polyester fiber, it is difficult to provide sufficient flameproof performance.
(4) In order to satisfy the flameproof performance, it is necessary to treat the flame retardant in a large amount, and the texture is lowered due to the large amount of the treatment.
JP 2000-328445 A Japanese Patent Publication No. 5-37180

  The present inventor can use the biphenylyl phosphate compound (Patent Document 2), which has been proposed to be used for a specific resin composition, for flame-retardant processing of polyester fibers, while intensively studying in view of the above problems. As a result of further studies, a flame retardant processing agent that can solve the above-mentioned problems of the prior art is obtained by using this as a treatment liquid emulsified or dispersed in an aqueous medium under certain conditions. I found out that

  That is, the present invention solves the problem of insufficient flame retardance due to the low sorption derived from phosphorus-based flame retardants, and has a relatively low molecular weight, so that the sorption is good and the washing durability is excellent, and Due to low volatility, there is no smoke during processing, the level of haze is at the level of condensed phosphate ester, decomposition and volatilization below the flash point of polyester fiber does not occur, and the problem of reduced texture due to mass treatment It aims at providing the flame retardant processing agent which does not produce, and the flame retardant processing method using the same.

In order to solve the above-mentioned problems, the flame retardant processing agent for polyester fibers of the present invention uses one of the biphenylyl phosphate compounds represented by the general formula (I) or a mixture thereof as a surfactant. It is assumed that it is emulsified or dispersed in water (claim 1).

  However, in formula, X is an integer of 1-3.

  As said surfactant, the combination of a nonionic surfactant and an anionic surfactant, or one of these can be used (Claim 2).

  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, a heat treatment at 80 ° C. or higher is performed (claim 3).

  According to the flame retardant processing agent of the present invention, the low molecular weight phosphoric acid ester has good sorption, while the problems of the above-mentioned fuming and cloudiness increase, which have been regarded as the disadvantages of conventional low molecular weight phosphorus compounds. Does not occur. Accordingly, it is possible to easily obtain a polyester fiber (product) that has flame retardancy excellent in durability against washing, dry cleaning, and the like necessary for interior use and is suitable for automobile interior materials. Since a non-halogen phosphorous compound is used, there is no fear that halogenated gas (such as bromdioxin) is generated when the polyester synthetic fiber is burned, which is also effective for environmental protection.

  The biphenylyl phosphate compound (hereinafter also referred to as phosphorus compound) used in the flame retardant processing agent of the present invention is a compound represented by the formula (I) as described above, and X is an integer of 1 to 3. These phosphorus compounds may be used alone or in any combination of two or more.

Among these phosphorus compounds, those having a structure represented by the following formula (i) (X = 1) are preferred, and those represented by the following formula (ii) (diphenyl monoorthoxenyl phosphate) are most preferred. .

  The phosphorus compound represented by the above formula (I) can be produced by a known method (see Japanese Patent Publication No. 5-37180). 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 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 or polyoxyethylene tristyrenated phenyl ether sulfate 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.

  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.

  As described above, the flame retardant processing agent of the present invention is an aqueous dispersion or aqueous emulsion of a phosphorus compound represented by the general formula (I), and is dyed in the same manner on a polyester fiber, pad dry thermocuring. By treating with a method, a coating method, etc., effective sorption can be shown, and the conventional smoke generation problem and cloudiness problem can be remarkably solved.

  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. The third component is copolymerized, such as 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 Example 1 and Comparative Examples 1 and 2 was prepared according to the formulation (% by weight) shown in Table 1 below. In Table 1, “TPP” is triphenyl phosphate manufactured by Daihachi Chemical Co., Ltd., and “PX-200” is resorcin bis (di-2,6-xylyl phosphate) manufactured by Daihachi Chemical 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 Dyeing Bath Method Using the flame retardant processing agent of Example 1 and Comparative Examples 1 and 2 above, flame retardant processing was performed on the polyester fiber fabric (regular polyester 100% woven tropical) by the dyeing bath method. .

  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 presence or absence of smoke during heat setting, the sorption amount of the flame retardant, the flame retardancy and the haze value were examined. The evaluation methods for flame retardancy and haze are 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”.

(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.

[Haze value]
The difference from the BLANK value was compared with a haze meter (Suga Test Instruments Co., Ltd .: direct reading haze computer). Details are as follows. A 100 cm ² test piece was placed in a 4 cm diameter glass bottle, and a 4.7 cm square glass plate was placed on the bottle without any gaps. The glass bottle in this state was immersed in an oil bath at 110 ° C., and after standing for 3 hours, the glass plate was removed and measured with a haze meter. Moreover, the measured value about the same unused glass plate was obtained as a blank (BLANK).

2. Pad Dry Thermocure Method Using the flame retardant processing agent of Example 1 and Comparative Examples 1 and 2 above, flame retardant by a pad dry thermocure method for polyester fiber fabric (regular polyester 100% woven tropical). Processed.

  Specifically, after immersing the fabric in a solution obtained by diluting the flame retardant to 15% with water, the fabric was squeezed to 70% with a mangle, dried at 110 ° C. for 2 minutes, and cured at 180 ° C. for 2 minutes. . 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 presence or absence of fuming and the flame retardancy of the polyester fiber fabric subjected to flame retardancy were examined in the same manner as described above. Moreover, the flame retardance was measured also about the untreated textile as a blank. The results are shown in Table 3 below.

3. Evaluation by Back Coating Method The coating formulation shown in Table 4 below was applied to a polyester fiber fabric (regular polyester 100% fabric) so that the coating amount in terms of solid was 70 g / m ² (Dry). This was followed by drying and sorption of the flame retardant compound by heating at 150 ° C. for 90 seconds.

  The haze value was compared with the BLANK value using a haze meter in the same manner as described above.

Flame retardancy was evaluated according to the following criteria using a JIS D-1201 FMVSS (302) flammability tester (horizontal method).
◎: Self-extinguishing, flame disappears immediately after digestion of fire source ○: Self-extinguishing, residual flame after digestion of fire source, extinguishes within measurement start point XX: Flammability (burnt)

  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. Further, since the problem of haze is improved, it is particularly preferably used as an automobile interior material such as a car seat skin material.

Claims (3)

A flame retardant processing agent for polyester fibers, wherein one or a mixture of biphenylyl phosphate compounds represented by the general formula (I) is emulsified or dispersed in water using a surfactant.

(In the formula, X is an integer of 1 to 3.)   The combination of a nonionic surfactant and an anionic surfactant, or one of these is used as the surfactant, the difficulty for polyester fibers according to claim 1 Burning agent.   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 polyester fiber, characterized by comprising: