JP3285677B2 - Flameproofing agent and method for flameproofing polyester fiber products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flameproofing agent and a flameproofing method for polyester fiber products. More specifically, the present invention relates to a method for imparting a durable flame retardant having excellent washing resistance and dry cleaning resistance to a regular polyester fiber product and a composite fiber product of a regular polyester fiber and a cationic dyeable polyester fiber. The present invention relates to a flame processing agent and a flame prevention processing method.

[0002]

2. Description of the Related Art Conventionally, as a flameproofing agent by a post-processing method such as a polyester fiber product, particularly a curtain, an aqueous dispersion in which a brominated cycloalkane compound is finely dispersed by an ordinary surfactant is used as a dye bath. A method used in the same bath treatment or pad treatment is known (JP-B-53-884).
0). Such a flameproofing agent imparts stable durable flameproofing to a curtain or the like made of only regular polyester fibers. However, with the diversification and luxury of curtains and the like these days,
Light-shielding curtains, which are multilayer fabrics composed of cationic polyester fibers on the inside and regular polyester fibers on both sides, and curtains made of jacquard fabrics of regular polyester fibers and cationic dyeable polyester fibers, are widely used. No stable durable flame resistance can be imparted to the curtain.

[0003] As a method of improving the flame resistance of polyester fiber products, a low melting brominated cycloalkane compound having an adsorption promoting effect (carrier effect) is added to a normal high melting brominated cycloalkane compound as a flame retardant. To improve the adsorption of the flame retardant to the fiber (Japanese Examined Patent Publication No. 3-35430), or to blend a phosphate ester-based flame retardant to obtain a synergistic effect of the flame retardant action of bromine and phosphorus. (Japanese Patent Application Laid-Open No. 63-201271) is known.
However, even with these methods, the durable flame resistance obtained for a composite fiber product of a regular polyester fiber and a cationic dyeable polyester fiber, which is difficult to obtain flame resistance, is still insufficient. In addition, these methods use a low-melting-point compound, and thus cause a problem of contamination of the can in the dyeing machine in the dyeing bath and bath treatment method.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polyester fiber product, especially a composite fiber product of a regular polyester fiber and a cationic dyeable polyester fiber, which solves the problems of the prior art. An object of the present invention is to provide a flameproofing agent and a flameproofing method which can impart stable and excellent durable flameproofness and do not cause contamination of a can in a dyeing machine in the same dyeing bath treatment.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained an aqueous dispersion in which a brominated cycloalkane compound is finely dispersed by using a specific self-emulsifying polyester compound. By treating polyester fiber products as a flameproofing agent, stable and excellent durable flameproofing can be imparted, and no contamination of the can in the dyeing machine during the dyeing bath treatment. And completed the present invention.

That is, according to the present invention, a brominated cycloalkane compound is converted to a compound represented by the following general formulas (I), (II) and (I):
A flameproofing agent for polyester fiber products is provided which contains a dispersion liquid obtained by dispersing fine particles in water using at least one of the self-emulsifying polyester compounds represented by II).

[0007]

Embedded image

According to the present invention, there is also provided a flameproofing method for a polyester fiber product, which comprises treating the polyester fiber product with the above flameproofing agent. Brominated cycloalkane compounds useful in the present invention include, for example,
1,2,3,4,5,6-hexabromocyclopentane, 1,2,4,6-tetrabromocyclooctane,
1,2,5,6,9,10-hexabromocyclododecane. These compounds are known and can be produced by a method known per se.

The compounds of the general formulas (I), (II) and (III)
The self-emulsifying polyester compound represented by, specifically, bishydroxyalkyl terephthalate or a mixture of bishydroxyalkyl terephthalate and bishydroxyalkyl isophthalate, and a polyalkylene glycol selected from polyethylene glycol, polypropylene glycol and polybutylene glycol Having a molecular weight of 300 to 50,000, preferably 5000 to 20,000. And the polyalkylene glycol part is 1-150, preferably 5
Consists of 0-100 moles of alkylene oxide units. These compounds are also known compounds and are produced by a known method.

In the flameproofing agent of the present invention, the blending ratio of the brominated cycloalkane compound and the self-emulsifying polyester compound is based on the weight of the brominated cycloalkane compound.
Self-emulsifying polyester compound 0.5 to 3 with respect to 0 parts
It is preferably 0 parts, especially 1 to 20 parts. In addition, the flameproofing agent of the present invention may contain a normal surfactant or a protective colloid as needed. Useful surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene-polyhydric alcohol ethers, ether compounds such as polyoxyalkylene-alkylphenyl ethers, and the ether compound and the alkyl group having carbon atoms of Examples thereof include ester compounds with 12 to 18 fatty acids, and sulfate compounds of the above ether compounds. Examples of the protective colloid agent include polyvinyl alcohol, carboxymethyl cellulose, starch and the like.

The flameproofing method of the present invention which is carried out using such a flameproofing agent is a known method, for example, a dipping method using a jet dyeing machine, a beam dyeing machine, a cheese dyeing machine or the like. And a continuous treatment such as a pad-dry-cure method, a thermosol method, and a coating method. In particular, a remarkable effect is obtained in the same dyeing bath treatment at 130 to 135 ° C.

[0012]

In the flame retardant of the present invention, the brominated cycloalkane compound is dispersed in water by a self-emulsifying polyester compound to form fine particles and dispersed in water, so that the polyester compound is stable around the brominated cycloalkane compound particles. To form and disperse, the brominated cycloalkane compound and the polyester compound are adsorbed on the polyester fiber in a coexisting form, and since the polyester compound also acts as a solubilizing agent for the brominated cycloalkane compound, the adsorbability to the fiber is further improved. Be improved. Then, the synergistic effect of the radical scavenging effect of HBr generated during combustion and the melting point lowering effect of the polyester fiber by the polyester compound promotes the flame drop phenomenon and improves the flame resistance. However, this flameproofing action is achieved by uniformly adsorbing the fiber in a form in which the brominated cycloalkane compound and the polyester compound coexist, and the dispersion of the brominated cycloalkane compound and the self-emulsifying polyester compound It cannot be obtained by the treatment in a separate bath or by the combination thereof.

In addition, the self-emulsifying polyester compound improves the high-temperature dispersibility of the brominated cycloalkane compound, thereby preventing contamination of the can body in the dyeing machine in the dyeing bath and bath treatment method.

[0014]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In addition, the adsorption rate of the flameproofing agent, the flameproofing property, the suitability for use in the dyeing bath, and the contamination of the can body were evaluated by the following methods. (1) Adsorption rate

[0015]

(Equation 1)

The details of the flameproofing treatment and the soaping are described in Example 1. (2) Flameproofness Firefighting law 45 degree micro-burner method (flaming 3 second test) and coil after washing with water or after dry cleaning in accordance with Fire Service Agency Public Notice No. 11 "Standard for Washing Resistance Regarding Fireproof Performance" It was measured by the method. Pass / fail judgment is 45
The test was performed when the residual flame time in the micro burner method was 3 seconds or less and the number of flame contacts in the coil method was 3 times or more. (3) Suitability for dye bath use The following adjustment liquid 3 is added to a pot of a color pet (manufactured by Nippon Dyeing).
Put 00ml, wrap a polyester knit (white cloth) around the holder and fasten both ends with rubber bands. 40 ℃ to 1
The temperature is raised to 20 ° C. at a rate of 3 ° C./min, held at 120 ° C. for 1 minute, then cooled to 90 ° C., and the polyester knitted fabric is removed from the holder. Then, after dehydration and drying, the casing spot state on the cloth is visually judged.

Adjustment liquid disperse dye (CI Disperse Red 60) 1 g / L Cationic dye (CI Basic Blue 54) 1 g / L Flame retardant 10 g / L 90% acetic acid 0.5 cc / L Dyeing machine: 12 color pets (Nippon Dyeing)評 価 Evaluation 〇 No casing spot.

Δ: Some casing spots are observed. × Casing spots are strongly observed. (4) Can body contamination 300 ml of the above-mentioned adjustment liquid is put into a pot of a color pet,
The temperature was raised from 40 ° C. to 130 ° C. at a rate of 3 ° C./min, and 13
Hold at 0 ° C. for 30 minutes, then cool to 90 ° C.
After filtration through 5A filter paper, the degree of contamination of the pot is visually determined.

Evaluation: Almost no contamination of the filtration residue and the pot is observed. △ Slight contamination of the filtration residue and pot. X: Contamination of the filtration residue and the pot is often observed. In the examples, as the brominated cycloalkane compound, isomers having different melting points are mixed.
5,6,9,10-Hexabromocyclododecane (HB
CD) with a solvent having a melting point of 190 ° C or higher
The mixture was used while changing the mixing ratio of the two components separated into those having a temperature of 60 ° C. or lower.

Example 1 95% and 160% HBCD having a melting point of 190 ° C. or higher
A 5% mixture at a temperature of not more than 5 ° C. was used, and a 10% emulsion of a condensation polymer of bishydroxyethyl terephthalate and polyethylene glycol (average molecular weight: about 9000) represented by the following formula was used as a self-emulsifying polyester compound.

[0021]

Embedded image

The above polyester resin 10% emulsion 100
g in 400 g of water. HBCD450g into it
Was added with stirring to prepare a crude dispersion. This coarse dispersion was finely dispersed by a wet mill (sand mill) for 60 minutes. Then, low-substituted carboxymethylcellulose (Nikka Chemical: Nikka Gum C, a product stabilizer)
Then, 50 g of a 3% solution of -60) was added, and the mixture was uniformly mixed to obtain a total amount of 1000 g of a finely divided dispersion (composition A).
The average particle size of the dispersion was 0.4 micron (Suga Test Instruments Co., Ltd. laser diffraction particle size distribution analyzer: SALD-
1100).

Using this finely divided dispersion, a polyester test cloth was treated by the same bathing method as described below. Test cloth: Multi-layered fabric composed of cationic dyeable polyester fiber on the inside and regular polyester fiber on both sides (basis weight: 250 g / m ² ) Processing machine: Mini color dyeing machine (manufactured by Texam Giken) Processing conditions: Disperse dye (CI Disperse Red 60) 1.0% owf Cationic dye (CI Basic Red 29) 0.5% owf (CI Basic Yellow 51) 0.2% owf (CI Basic Blue 54) 1.3% owf Composition A (flame retardant) 10% owf 90 % Acetic acid 0.5 cc / L Bath ratio 1:15 From 40 ° C to 130 ° C at a rate of 2 ° C / min,
The temperature was maintained at the same temperature for 1.0 hour, and the same bathing treatment was performed.
Thereafter, the temperature is lowered to 60 ° C., the work cloth is taken out, and washed with water for 5 minutes.
Minutes. After that, hydrosulfite 2g /
L, 2 g / L of soda ash and 2 g / L of a nonionic surfactant (manufactured by Nikka Kagaku: Sunmol BR-70), from 80 to
Reduction washing was performed at 90 ° C. for 15 minutes. Perform water washing again for 10 minutes, dry the work cloth, and cure (180 ° C x 30 seconds)
Was performed.

Example 2 85% of HBCD having a melting point of 190 ° C. or higher and 160%
The same operation as in Example 1 was performed except that a mixture of 15% or lower at 15 ° C. or less was used. The resulting dispersion (Composition B) had an average particle size of 0.4 microns.

Example 3 75% of HBCD having a melting point of 190 ° C. or more and 160%
The same operation as in Example 1 was performed except that a mixture of 25% or lower at 25 ° C. or less was used. The resulting dispersion (Composition C) had an average particle size of 0.4 microns.

Example 4 65% of HBCD having a melting point of 190 ° C. or higher and 160%
The same operation as in Example 1 was carried out except that a mixture of 35% or lower at 35 ° C. or less was used. The resulting dispersion (Composition D) had an average particle size of 0.4 microns.

Example 5 55% of HBCD having a melting point of 190 ° C. or more and 160%
The same operation as in Example 1 was performed except that a mixture of 45% or lower at 45 ° C. or less was used. The resulting dispersion (Composition E) had an average particle size of 0.4 microns.

Example 6 75% of HBCD having a melting point of 190 ° C. or higher and 160%
Except that a 25% mixture having a temperature of not higher than 25 ° C. was used, and a 10% solution of a polycondensation product (average molecular weight: about 7,500) of bishydroxyethyl terephthalate and polybutylene glycol represented by the following formula was used as a self-emulsifying polyester compound. The same operation as in Example 1 was performed. The resulting dispersion (composition F) had an average particle size of 0.4 microns.

[0029]

Embedded image

Example 7 75% of HBCD having a melting point of 190 ° C. or more and 160%
Except that a 25% mixture at a temperature of not higher than 25 ° C. was used and a 10% emulsion of a condensation polymer (average molecular weight: about 9000) of bishydroxyethyl isophthalate and polyethylene glycol represented by the following formula was used as a self-emulsifying polyester compound. The same operation as in Example 1 was performed. The average particle size of the resulting dispersion (Composition G) was 0.4 microns.

[0031]

Embedded image

Example 8 75% of HBCD having a melting point of 190 ° C. or higher and 160%
A mixture of 50% of bishydroxyethyl terephthalate and 50% of bishydroxyethyl isophthalate represented by the following formula as a self-emulsifying polyester compound and a polycondensate of polyethylene glycol (average molecular weight: about 9000) The same operation as in Example 1 was performed except that a 10% solution of the emulsified product was used. The resulting dispersion (composition H) had an average particle size of 0.4 microns.

[0033]

Embedded image

Comparative Example 1 50 g of a 30% solution of a sulfated product of a 15 mol adduct of nonylphenol with ethylene oxide was mixed and dissolved in 450 g of water. A mixture of 95% of HBCD having a melting point of 190 ° C. or more and 5% of HBCD having a melting point of 160 ° C. or less was added thereto with stirring to prepare a crude dispersion. This coarse dispersion was finely dispersed by a wet mill (sand mill) for 60 minutes. Next, 50 g of a 3% liquid of low-substituted carboxymethylcellulose (Nikka Chemical: Nikka Gum C-60), which is a product stabilizer, was added, and the mixture was uniformly mixed to give a total amount of 1000 g of the finely divided dispersion (composition I). I got The average particle size of the dispersion was 0.6 microns. Thereafter, the same operation as in Example 1 was performed.

Comparative Example 2 75% of HBCD having a melting point of 190 ° C. or higher and 160%
The same operation as in Comparative Example 1 was carried out except that a mixture of 25% or lower at 25 ° C. was used. The resulting dispersion (Composition J) had an average particle size of 0.6 microns.

Comparative Example 3 65% of HBCD having a melting point of 190 ° C. or higher and 160%
The same operation as in Comparative Example 1 was performed except that a mixture of 35% or lower at 35 ° C. or lower was used. The resulting dispersion (Composition K) had an average particle size of 0.6 microns.

Comparative Example 4 50 g of a 30% solution of a sulfated product of a 15 mol adduct of nonylphenol with ethylene oxide was dissolved in 250 g of water. A mixture of 75% of HBCD having a melting point of 190 ° C. or more and 25% of HBCD having a melting point of 160 ° C. or less was added thereto while stirring to prepare a crude dispersion. This coarse dispersion was finely dispersed by a (sand mill) for 60 minutes. Next, 50 g of a 3% liquid of low-substituted carboxymethylcellulose (Nikka Chemical: Nikka Gum C-60) as a product stabilizer was added, and the mixture was uniformly mixed to obtain a total of 800 g of a finely divided dispersion. Next, 30% of a sulfated product of a 15 mol adduct of ethylene oxide of nonylphenol with 100 g of tricresyl phosphate which is a phosphoric ester flame retardant
50 g of the liquid was added, and 50 g of water was gradually added with uniform stirring to obtain 200 g of an emulsion. 200 g of tricresyl phosphate emulsion was added to 800 g of the above-mentioned HBCD micronized dispersion, and the mixture was uniformly mixed.
(Composition L) was obtained. Composition L had an average particle size of 0.6 microns. Thereafter, the same operation as in Example 1 was performed.

Comparative Example 5 Composition J of Comparative Example 2 and the 10% emulsion of the polyester compound used in Example 1 were treated in combination according to the following formulation. Thereafter, the same operation as in Example 1 was performed. Formulation Disperse dye (CI Disperse Red 60) 1.0% owf Cationic dye (CI Basic Red 29) 0.5% owf (CI Basic Yellow 51) 0.2% owf (CI Basic Blue 54) 1.3% owf Composition C 10%, 15% owf PET resin (10% solution) 5.0% owf 90% acetic acid 0.5cc / L or more The compositions of the dispersions of Examples 1 to 8 and Comparative Examples 1 to 4 are shown in Tables 1 and 2 below.

[0039]

[Table 1]

[0040]

[Table 2]

In Examples 1 to 8 in which HBCD was dispersed with a self-emulsifying polyester compound based on the average particle size of the fine particle dispersion, Comparative Example 1 in which HBCD was dispersed with an ordinary surfactant was used.
4 shows excellent dispersibility into fine particles as compared with Nos. 1 to 4. This indicates that the self-emulsifying polyester resin is also effective as a finely divided dispersant. The performance evaluation results of the treated cloths of Examples 1 to 8 and Comparative Examples 1 to 5 are shown in Tables 3 and 4 below.

(1) Flame resistance and adsorption amount

[0043]

[Table 3]

(2) Suitability for combined use of dye bath and contamination of can body

[0045]

[Table 4]

As can be seen from Tables 3 and 4, the treated cloths of Examples 1 to 8 using the flameproofing agent obtained by dispersing the HBCD of the present invention in fine particles with a self-emulsifying polyester compound were obtained by the 45 ° microburner method and the coil method. Examples 3, 4, and 5 using a mixture of 75 to 55% of HBCD having a melting point of 190 ° C. or higher and 25 to 45% of a HBCD having a melting point of 160 ° C. or lower are obtained. At 45 °
0 seconds of residual flame by micro burner method, 4 times of flame contact by coil method
It shows stable high-performance and durable flame resistance of 5 times. On the other hand, in Comparative Examples 1 to 4 which are the conventional methods, the flameproof variation is large and the durability flameproof is not obtained. In addition, it can be seen that the combined use of the HBCD micronized product and the self-emulsifying polyester resin with the ordinary surfactant of Comparative Example 5 cannot provide the flameproofing effect as obtained in the examples. From these results, it is understood that HBCD is effective for durable flame resistance by dispersing HBCD into fine particles with a self-emulsifying polyester compound according to the present invention.

In Examples 1 to 8 in which HBCD was made into fine particles with a self-emulsifying polyester compound in comparison with Comparative Examples 1 to 4 in which HBCD was made into fine particles with a self-emulsifying polyester, in terms of suitability for use in a dyeing bath and contamination of cans. Pretty good. However,
When HBCD having a melting point of 160 ° C. or lower is mixed at 45%, the mixture tends to be slightly lowered (Example 5). From these results, it can be seen that the self-emulsifying polyester processed product forms a stable interfacial film around the HBCD particles, and thus also improves the high-temperature dispersibility of the low-melting point product of HBCD, which has conventionally been a problem.

As described above, the flameproofing agent of the present invention provides stable high-performance and durable flameproofing properties, excellent suitability for combined use with a dyeing bath, and suitability for the same bathing treatment without staining of cans. You can see that.

[0049]

According to the flameproofing agent and the flameproofing method of the present invention, even a composite fiber product comprising a regular polyester fiber and a cationic dyeable polyester fiber, which has not been able to obtain a stable flameproofness in the past, is stable. Thus, it is possible to impart a high-performance durable flameproof property, and it is possible to effectively prevent stains on work cloths and contamination of can bodies by the same dyeing and bath treatment method.

Claims (4)

(57) [Claims] 1. A dispersion in which a brominated cycloalkane compound is finely dispersed in water using at least one of self-emulsifying polyester compounds represented by the following general formulas (I), (II) and (III). Flameproofing agent for polyester fiber products containing liquid. Embedded image 2. The brominated cycloalkane compound is hexabromocyclododecane, and hexabromocyclododecane has a melting point of not less than 190 ° C.
The flameproofing agent according to claim 1, which is a mixture with 35 to 25% of a product having a temperature of 60C or less. 3. A method for flameproofing a polyester fiber product, comprising treating the polyester fiber product with the flameproofing agent according to claim 1. 4. The brominated cycloalkane compound is hexabromocyclododecane, and hexabromocyclododecane has a melting point of not less than 190 ° C.
The flameproofing method according to claim 3, wherein the mixture is a mixture of 35 to 25% with a temperature of 60C or less.