JP2002327370A - Flame proof agent for polyester based textile materials and flame proof method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame proof method for polyester based textile materials high in exhaustion ratio using a water dispersion of fine particles of a brominated cycloalkane compound such as nonaromatic hexabromocyclododecane(HBCD) or the like. SOLUTION: This flame retardant for polyester based textile materials comprising a water dispersion of fine particles comprises 100 pts.wt. of the brominated cycloalkane compound such as the nonaromatic hexabromocyclododecane(HBCD) or the like, 1-40 pts.wt. preferably 1-20 pts.wt. of a dispersing agent, 1-40 pts.wt. preferably 1-20 pts.wt. of a nonionic surfactant having HLB <=10 and as necessary 1-40 pts.wt. preferably 1-20 pts.wt. of a protective colloid agent for more stably dispersing the HBCD or the like and finely dispersing if necessary heating at 40-90 deg.C, and the method using the flame proof agent by impregnating or pudding the flame proof agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flameproofing agent for a polyester fiber material and a flameproofing method.

[0002]

2. Description of the Related Art Conventionally, as a flameproofing method for polyester fiber products, a brominated cycloalkane compound such as non-aromatic hexabromocyclododecane (HBCD) has been used.
There is known a method of using an aqueous dispersion obtained by finely dispersing and dispersing a fine particle using a dye and a dispersant commonly used in the textile industry by a dipping method or a padding method (Japanese Patent Publication No. 53-8840).

However, this method has many problems,
Above all, it is well known that the exhaustion rate of HBCD or the like to the fiber material is extremely low and the efficiency is extremely low. This is not only because the loss of HBCD and the like during flameproofing is large and the economics of this method is impaired, but also diversification,
In addition, it may be difficult to surely provide a stable and superior flameproofing performance required for a polyester fiber product to be upgraded. Also, as a result, a large amount of water-insoluble HBCD remaining in the processing solution not only increases the burden required for wastewater treatment, but also causes contamination of the can body and damage when performing flameproofing in the same bath during dyeing. It is known to cause secondary problems that can be fatal in practice, such as stains on dyes.

[0004] In order to solve such a problem, some methods have already been proposed, and some of them have been put to practical use. For example, in order to increase the exhaustion rate of HBCD and the like, an additive having an effect of promoting adsorption is blended. For example, a brominated diphenyl compound (JP-A-62-57985) and a special phosphorus compound such as Nikkaphy Non-TS-55
(Nichika Chemical Co., Ltd.) has been proposed. In addition, a method of adjusting and blending a low-melting HBCD compound and a high-melting HBCD compound separated by using an organic solvent in a specific amount has been proposed (Japanese Patent Publication No. 3-35430), but the problem remains to be solved. It can be said that there is.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to firstly make the exhaustion rate of HBCD and the like as high as possible. As a result, the economic efficiency of this method is improved, and at the same time, it is easy to reliably provide a stable and superior flameproofing performance required for diversified and upgraded polyester fiber products. . Also,
The reduction in HBCD and the like remaining in the treatment liquid as a result of the increase in the exhaustion rate not only reduces the burden required for wastewater treatment, but also reduces the need for flameproofing in the same bath during dyeing. It is possible to reduce the occurrence of secondary problems such as contamination and contamination of a material to be dyed, which are fatal in practical use. Additives that have already been proposed for this purpose, such as brominated diphenyl compounds and phosphorus compounds, must hesitate to use them in view of their large impact on the environment and ecosystems. Absent. Therefore, in the present invention, the additives and the like to be used are selected from those having as little influence on the environment and ecosystem as possible. Also,
For the same reason, in the present invention, the organic solvent is not used at all, including addition to the flameproofing agent, as well as in the production process such as separation.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention.

That is, non-aromatic hexabromocyclododecane (HBCD) finely dispersed using a known dispersant commonly used in the dye and textile industries.
It is well known that an aqueous dispersion of a brominated cycloalkane compound such as HBCD has a very low exhaustion efficiency of HBCD and the like when used for flameproofing by a dipping method or a padding treatment method (Japanese Patent Publication No. Sho 53). -8840). However, the present inventor has proposed that an aqueous dispersion such as HBCD has a hydrophilic group containing a polyhydric alcohol or a low adduct of ethylene oxide or propylene oxide which is not suitable as a dispersant.
Nonionic surfactants having an LB value of 10 or less, for example, sorbitan monofatty acid ester, sorbitan difatty acid ester, sorbitan sesquifatty acid ester, sorbitan trifatty acid ester, glycerin monofatty acid ester, diglycerin monofatty acid ester, polyglycerin fatty acid ester, Fatty acid sugar esters, or alkylphenols, fatty acids, or low addition products of fatty alcohols such as ethylene oxide or propylene oxide,
One or more kinds are added to 1 to 40 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of HBCD or the like, and if necessary, while heating to 40 to 90 ° C,
By preparing and using an aqueous dispersion liquid in which fine particles are dispersed, the exhaustion rate of HBCD and the like has been significantly improved.

On the other hand, according to the present invention, it is possible to disperse hydrophobic HBCD and the like in water as easily and stably as possible during the production and storage of the flameproofing agent and during flameproofing using the same. Required. However, a nonionic surfactant having an HLB value of 10 or less having a hydrophilic group, such as a polyhydric alcohol or a low-addition product of ethylene oxide or propylene oxide, which has an adsorption-promoting effect and is used in the present invention, is used as a dispersant. Inappropriate, by itself, hydrophobic HBC
D and the like cannot be easily and stably dispersed in water. Therefore, it is necessary to add a dispersant suitable for easily and stably dispersing HBCD or the like in water. Among the dispersants commonly used in aqueous dispersions, strong electrolyte type anionic surfactants, for example, lignin sulfonate, aliphatic or aromatic sulfonate, formalin condensate of aromatic sulfonate, polystyrene Sulfonates, sulfates of ethylene oxide adducts of styrenated phenols or styrenated alkyl phenols, sulfates of aliphatic alcohols, and sulfates of ethylene oxide adducts of alkyl phenols, fatty acids, or aliphatic alcohols, etc. It can be used for the purpose, and by adding one or more of these to 100 parts by weight of HBCD or the like, 1 to 40 parts by weight, preferably 1 to 20 parts by weight, The result can be obtained.

Further, HBCD and the like are more stably dispersed in water to improve the storage stability, dilution stability, and fine particle dispersion efficiency of the flame retardant for polyester fiber material comprising an aqueous dispersion. , As a protective colloid agent,
For example, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose,
Hydroxyethyl cellulose, hydroxypropyl cellulose, casein, gelatin, glue, alginate,
By adding 1 to 40 parts by weight, preferably 1 to 20 parts by weight of a water-soluble polymer such as starch, dextrin and xanthan gum to 100 parts by weight of HBCD or the like,
Good results can be obtained.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Commercially available, for example, having an average particle size of about 10 μm
Considering sedimentation of particles and filter phenomena, it is problematic to use the HBCD powder as it is as a flameproofing agent. Therefore, if necessary, use a wet or dry pulverizer to reduce HBCD to an average particle size. 5 μm or less in diameter, preferably 2 μm
It is necessary to pulverize and atomize to the following. HBC
The pulverization / micronization of D is preferably performed by adding a part or all of the dispersant. However, in the present invention, an additive having an adsorption promoting effect, which is used to increase the exhaustion rate of HBCD or the like,
It may be performed at any stage before or after the addition of the nonionic surfactant having an HLB value of 10 or less, and may be performed simultaneously with mixing.

[0011]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Preliminary grinding of HBCD 1 (Preparation 1 of 60% micronized HBCD 1) 60 parts of a commercially available HBCD powder having an average particle diameter of about 10 μm was mixed with a dispersant, Hytenol NF-13 (Nippon Oil & Fats Co., Ltd.) Dispersed in 34 parts of water containing 6 parts of a distyrenated phenol ethylene oxide adduct (sulfuric acid ester ammonium salt) is pulverized by a sand mill to an average particle size of 5 μm or less, preferably 2 μm or less (for example, 1.864 μm). .

Example 2 Preliminary grinding 2 of HBCD 2 (Preparation 2 of 60% finely divided HBCD) 60 parts of a commercially available HBCD powder having an average particle size of about 10 μm was mixed with a dispersant, Labelin FW (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Water containing 6 parts of naphthalene sulfonate formalin condensate) 34
The resulting dispersion is pulverized by a sand mill so as to have an average particle size of 5 μm or less, preferably 2 μm or less (for example, 1.853 μm).

Comparative Example 1 The 60% finely divided HBCD obtained in Example 1 was
25.0 parts of water is added to 5.0 parts and stirred sufficiently to obtain a uniform aqueous dispersion.

Example 1-1 The 60% finely divided HBCD obtained in Example 1 was used in the amount of 7%.
To 5.0 parts of water, 21.0 parts of water and 4.0 parts of sorbitan dioleate are added, and the mixture is sufficiently stirred while heating to 80 ° C. to obtain a uniform aqueous dispersion.

Example 1-2 The 60% finely divided HBCD obtained in Example 1 was used
20.7 parts of water and 4.3 parts of diethylene glycol monolaurate are added to 5.0 parts, and sufficiently stirred to obtain a uniform aqueous dispersion.

Example 1-3 The 60% finely divided HBCD obtained in Example 1 was used in the form of 7
To 5.0 parts of water, 21.0 parts of water and 4.0 parts of glycerin monopalmitate are added, and the mixture is sufficiently stirred while heating to 80 ° C. to obtain a uniform aqueous dispersion.

Example 1-4 The 60% finely divided HBCD obtained in Example 1
20.7 parts of water and 4.3 parts of sorbitan monooleate are added to 5.0 parts, and the mixture is sufficiently stirred while heating to 80 ° C to obtain a uniform aqueous dispersion.

Example 2-1 The 60% finely divided HBCD obtained in Example 2
To 5.0 parts of water, 21.0 parts of water and 4.0 parts of sorbitan monooleate were added, and the mixture was sufficiently stirred while heating to 60 ° C. to obtain a uniform aqueous dispersion.

Example 3 45.0 parts of a commercially available HBCD powder having an average particle diameter of about 10 μm was mixed with 4.5 parts of Hytenol NF-13 (a sulfate ester ammonium salt of a distyrenated phenol ethylene oxide adduct of Nippon Oil & Fats), 4.5 parts of sorbitan mono What was dispersed in 46.2 parts of water containing 4.3 parts of oleic acid ester was sand-milled to have an average particle size of about 2 μm or less (for example, 1.744 μm).
m).

Comparative Example 2 A commercially available product A (HBCD 44.2%, measured value) was used as it was.

Comparative Example 3 A commercial product B (HBCD 39.4%, measured value) was used as it was.

Flameproofing In order to evaluate the HBCD exhaustion performance of the flameproofing agent, it is necessary to first perform flameproofing. As a method of performing post-processing flameproofing on a polyester fiber material, there is a dipping method or a padding method. Therefore, the flameproofing treatment was performed by the dipping method (the same bathing treatment as the dyeing bath), and was performed according to the dyeing test under the following conditions. Dyeing tester Mini color dyeing machine (Texam C
o. LTDJAPAN) Test cloth Commercial PET test cloth Bath ratio 1:10 Temperature 130 ° C Time 60 minutes

Performance Evaluation Measurement of Bromine (Br) Sorption Amount (% owf) It goes without saying that the flameproofed test cloth must be finally evaluated in terms of flameproof performance. There are many types of evaluation test methods, the correlation between different test methods is delicate, and it is difficult to specify one test method serving as a common standard. However, in the case of a halogen-based flame retardant, its flame retardant performance depends on the amount of the flame retardant sorbed on the test cloth, that is,
It should be governed by the amount of halogen (% owf) sorbed on the test cloth. Further, the first object of the present invention is to provide HBCD
, Ie, the sorption amount (% owf) of Br sorbed on the test cloth is made as high as possible. Therefore,
The sorption amount of Br sorbed on the test cloth was measured by a flask combustion method, and was used as a standard for evaluating the flameproofing performance.

The results are shown in the table below. Table 1 shows that the amounts of the flameproofing agents added are 10, 20, 30, and 40% ow, respectively.
f is the amount (% owf) of Br sorbed on the PET test cloth when the flameproofing was performed under the above conditions.

Table 2 shows the flameproofing agents 10, 2
When the flameproofing is performed at 0, 30, and 40% owf, the ratio (exhaustion rate ·%) of Br effectively sorbed to the test cloth among the Br contained in the used flameproofing agent. .

As is apparent from Tables 1 and 2, fine particles are dispersed using only a dispersant, for example, Hytenol NF-13 (a sulfate ammonium salt of a distyrenated phenol ethylene oxide adduct of Nippon Oil & Fats). The non-aromatic brominated cycloalkane compound, hexabromocyclododecane (HBCD) aqueous dispersion,
Although the exhaustion efficiency is very poor, it can be seen that the addition of a nonionic surfactant having an HLB value of 10 or less succeeded in dramatically improving the exhaustion rate of HBCD.

[0028]

According to the present invention, the exhaustion rate of HBCD and the like has been drastically improved. As a result, the flameproofing agent and the flameproofing method for the polyester fiber material have been significantly improved in economical efficiency. At the same time, it has become possible to reliably provide a stable and superior flameproofing performance required for diversified and sophisticated polyester fiber products. In addition, the reduction in HBCD and the like remaining in the processing solution as a result of the improvement in the exhaustion rate not only reduces the load required for wastewater treatment, but also when performing flameproofing in the same bath during dyeing, etc. Such as can body contamination and dyed object contamination
In practice, it can also reduce the occurrence of secondary problems that can be fatal. Also, in the present invention, additives to be used are selected from those having the least effect on the environment and ecosystem as much as possible, and the organic solvent is added to the flameproofing agent as well as the production process such as separation. No use, including use in

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[Procedure amendment]

[Submission date] April 15, 2002 (2002.4.1
5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

Example 1 Pre-pulverization of HBCD 1 (Preparation 1 of 60% micronized HBCD) 60 parts of a commercially available HBCD powder having an average particle size of about 10 μm was mixed with a dispersant, Hytenol NF-13 ( Daiichi Kogyo Seiyaku Co., Ltd. ) Dispersed in 34 parts of water containing 6 parts of a distyrenated phenol ethylene oxide adduct (manufactured by K.K. Co., Ltd.) in a sand mill so as to have an average particle size of 5 μm or less, preferably 2 μm or less (for example, 1.864 μm). Smash.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Example 3 45.0 parts of a commercially available HBCD powder having an average particle size of about 10 μm was mixed with Hytenol NF-13 (a sulfated ammonium salt of a distyrene-modified phenol ethylene oxide adduct manufactured by Dai - ichi Kogyo Seiyaku Co., Ltd.) Dispersed in 46.2 parts of water containing 0.5 parts of sorbitan monooleate and 4.3 parts of sorbitan monooleate are ground with a sand mill to an average particle size of about 2 μm or less (eg, 1.744 μm).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

The results are shown in the table below. Table 1 shows that
10, 20, 30, 40% ow of flame retardant
When flameproofing is performed under the above conditions, the PET test cloth
It is the amount of sorbed Br (% owf).* Dispersant NF-13 Hytenol NF-13 (Daiichi Kogyo Pharmaceutical
Distyrenated phenol ethylene oxide
Ammonium sulfate of adduct) FW Ravelin FW (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Phthaline sulfonate formalin condensate) ** Additive with adsorption promoting effect SDO Sorbitan dioleate DEML Diethylene glycol monolaurate ester
GMP Glycerin monopalmitate SMO Sorbitan monooleate

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

Table 2 shows the flameproofing agents 10, 2
Used when flameproofing is performed at 0, 30, 40% owf
Of the Br contained in the flameproofing agent
This is the ratio of the deposited Br (exhaustion rate ·%).* Dispersant NF-13 Hytenol NF-13 (Daiichi Kogyo Pharmaceutical
Distyrenated phenol ethylene oxide
Ammonium sulfate of adduct) FW Ravelin FW (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Phthaline sulfonate formalin condensate) ** Additive with adsorption promoting effect SDO Sorbitan dioleate DEML Diethylene glycol monolaurate ester
GMP Glycerin monopalmitate SMO Sorbitan monooleate

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Change

[Correction contents]

As apparent from Tables 1 and 2, dispersants such as Hytenol NF-13 ( Daiichi Kogyo Seiyaku Co., Ltd.)
Ltd. sulfate ammonium salt of distyrenated phenol ethylene oxide adduct) was only allowed to fine particles dispersed using a bromide cycloalkane compounds in non-aromatic-based, aqueous dispersion of hexabromocyclododecane (HBCD) is Although the exhaustion efficiency is very poor, by adding a nonionic surfactant having an HLB value of 10 or less to this,
It can be seen that the exhaustion rate of HBCD was significantly improved.

Claims (6)

[Claims] 1. A dispersant and an HLB value of 10 which are unsuitable as a dispersant for a brominated cycloalkane compound such as non-aromatic hexabromocyclododecane (HBCD).
A flameproofing agent for a polyester-based fiber material, comprising an aqueous dispersion obtained by adding the following nonionic surfactant and, if necessary, heating to 40 to 90 ° C. and dispersing into fine particles. 2. The dispersing agent according to claim 1, wherein the dispersing agent is a strong electrolyte type anionic surfactant such as lignin sulfonate, aliphatic or aromatic sulfonate, or aromatic sulfonate formalin. Condensates, polystyrene sulfonates, sulfates of ethylene oxide adducts of styrenated phenols or styrenated alkyl phenols, sulfates of aliphatic alcohols, or sulfuric acids of alkyl phenols, fatty acids, or ethylene oxide adducts of aliphatic alcohols An ester salt or the like can be used, and one or more of these can be used. 3. The compounding ratio of the dispersant described in claim 1 and 2 is 1 to 100 parts by weight of a brominated cycloalkane compound such as non-aromatic hexabromocyclododecane (HBCD). 40 parts by weight, preferably 1 to 20 parts by weight, of a flameproofing agent for polyester fiber material. 4. The nonionic surfactant having an HLB value of 10 or less, which is not suitable as a dispersant and which is described in claim 1, is a polyhydric alcohol, or a low addition product of ethylene oxide or propylene oxide. Non-ionic surfactants having an HLB value of 10 or less having a hydrophilic group of, for example, sorbitan monofatty acid ester, sorbitan difatty acid ester, sorbitan sesquifatty acid ester, sorbitan trifatty acid ester, glycerin monofatty acid ester, diglycerin monofatty acid ester , Polyglycerin fatty acid ester, fatty acid sugar ester, or
A flameproofing agent for a polyester fiber material, characterized by using one or more of alkylphenols, fatty acids, or low-addition products of aliphatic alcohols such as ethylene oxide or propylene oxide. 5. The non-aromatic hexabromocyclododecane (HBCD) according to claim 1 or 4, wherein a nonionic surfactant having an HLB value of 10 or less, which is unsuitable as a dispersant, is mixed. ) And other brominated cycloalkane compounds 1
1 to 40 parts by weight, preferably 1 to 100 parts by weight,
20 parts by weight of a flameproofing agent for a polyester fiber material. 6. The method of claim 1, wherein the flameproofing agent for a polyester fiber material is produced by a dipping method or a padding method. Flameproofing method for polyester fiber material.