JP2011012352A - Flame retardant for polyester fiber, method for producing flame-retardant polyester fiber product using the same, and flame-retardant polyester fiber product obtained from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant for polyester fibers which is excellent in exhaustion and durability, and little in hardening.SOLUTION: The flame retardant for polyester fibers contains tris(2,3-dibromopropyl)isocyanurate and a polyester resin represented by formula (1) [wherein, Ris H or a group represented by formula (2)] and having a weight-average molecular weight of 5,000 to 200,000.

Description

  The present invention relates to a flame retardant processing agent for polyester fiber, and more particularly to a flame retardant processing agent containing tris (2,3-dibromopropyl) isocyanurate which is a bromine-containing flame retardant. Moreover, this invention relates to the manufacturing method of a flame-retardant polyester fiber product using such a flame-retardant processing agent for polyester fibers, and the flame-retardant polyester fiber product obtained by it.

  Conventionally, durable flame retardant processing of polyester fiber is performed by infiltrating the interior of the fiber with an alicyclic halogen compound represented by hexabromocyclododecane (hereinafter abbreviated as “HBCD”) by a high temperature exhaustion method or a thermosol method. The mainstream method is based on the fixing method. However, since HBCD is a persistent and highly accumulative substance, it was designated as a first-class monitoring chemical in September 2004. For this reason, the textile industry has also announced a policy of complete abolition with a time limit.

  In recent years, various phosphorus-based flame retardant compounds have been studied as flame retardant components replacing such HBCD. For example, Japanese Patent Application Laid-Open No. 2000-328445 (Patent Document 1) discloses that an emulsion composition is prepared by emulsifying and dispersing resorcinol bis (diphenyl phosphate) in water in the presence of a surfactant. A method for flame-retardant processing of polyester fibers adsorbed on fiber-based fibers has been disclosed, whereby it is possible to stably supply excellent flame-retardant polyester fibers that are less durable and have low light fastness. ing.

  Japanese Patent Laid-Open No. 2002-88368 (Patent Document 2) discloses a flame retardant process in which resorcinol bis (diphenyl phosphate) is emulsified and dispersed in water using a specific nonionic surfactant and / or anionic surfactant. The chemical | medical agent is disclosed, By this, it is also disclosed that a flame retardance can be favorably and safely imparted to the polyester fiber by a dye bath and bath treatment, and an excellent durable flame retardancy is imparted.

  Furthermore, JP-A-2006-299486 (Patent Document 3) discloses a flame-retardant processing agent for polyester fibers containing a phosphorus compound and a specific polyester resin, and a method for producing flame-retardant polyester fibers using the same. Thus, it is also disclosed that flame resistance with excellent durability is imparted to the polyester fiber.

  However, these phosphorus-based flame retardant compounds have a low exhaust rate to the polyester fiber, so it is difficult to obtain a flame-retardant effect equivalent to that of HBCD. Released into the environment. For this reason, studies on halogen-based flame retardant compounds are being continued along with studies on phosphorus-based flame retardant compounds.

  For example, Japanese Patent Application Laid-Open No. 2005-68576 (Patent Document 4) is obtained by melt-kneading polyester, a bromine-containing flame retardant, and one or more additives among a compatibilizer, a lubricant, and a bleed inhibitor. Further disclosed is a fiber for flame retardant polyester-based artificial hair formed from the above composition, thereby providing flame resistance while maintaining heat resistance and high elongation of ordinary polyester fiber. Yes.

  However, the flame-retardant polyester fiber described in Patent Document 4 is obtained by molding a composition obtained by melt-kneading polyester and a bromine-containing flame retardant in advance into a fiber shape. There was still room for study on the method of applying the.

JP 2000-328445 A JP 2002-88368 A JP 2006-299486 A JP 2005-68576 A

  The present invention has been made in view of the above-described problems of the prior art, and can impart a flame resistance with excellent durability to the polyester fiber, and can suppress the texture hardening of the polyester fiber product. It aims at providing the flame retardant finishing agent. Another object of the present invention is to provide a polyester fiber product having no flame curing and having excellent flame retardancy and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors, first, tris (2,3-dibromopropyl) isocyanurate, which is a brominated flame retardant, is excellent in exhaustion to polyester fibers. The present inventors have found that the polyester fiber can be imparted with flame retardancy having excellent durability and can reduce the environmental load.

  However, it has been found that polyester fiber products that are exhausted with tris (2,3-dibromopropyl) isocyanurate and imparted flame retardancy tend to cause texture hardening. Therefore, as a result of further earnest studies, the present inventors have processed tris (2) by treating polyester fiber with tris (2,3-dibromopropyl) isocyanurate in the presence of a specific polyester resin. , 3-Dibromopropyl) isocyanurate increases the exhaust rate of the polyester fiber to improve the flame retardancy of the polyester fiber and suppresses the texture hardening of the obtained flame-retardant polyester fiber product. As a result, the present invention has been completed.

  That is, the flame retardant processing agent for polyester fibers of the present invention includes tris (2,3-dibromopropyl) isocyanurate and the following formula (1):

In [formula (1), ^{R 1} is HO- group or HO ^(R 2 _{O) a} - represents a group, ^{R 2} represents an alkylene group having 2 to 4 carbon atoms, a is an integer of 1 to 200, When a is 2 or more, R ² O may be the same or different, and when R ² O is 2 or more, R ² O may be random addition or block addition, and b is R ⁴ is an integer of 2 to 100, and a plurality of R ^{4 s} in a molecule each independently represent a hydrogen atom or a —SO ₃ X group (X represents a hydrogen atom, an alkali metal or an amine), A may be the same or different, and R ³ is a hydrogen atom or the following formula (2):

(Equation (2) ^{R 4} in has the same meaning as ^{R 4} in the formula (1))
Represents a group represented by
And a polyester resin having a weight average molecular weight of 5,000 to 200,000.

In such a flame retardant for polyester fiber, the tris (2,3-dibromopropyl) isocyanurate is present in an emulsified and dispersed state, and the polyester resin is a self-emulsifying and dispersing polyester resin. preferable. Further, as the polyester resin, the above formula (1) and (2) in ^{R 4} is -SO ₃ X groups, those wherein X is an alkali metal is preferable.

  Moreover, the method for producing a polyester fiber product of the present invention is a method characterized in that the polyester fiber is treated with the flame retardant for polyester fiber of the present invention, and the polyester fiber product of the present invention is such a method. It can be manufactured by a method.

  ADVANTAGE OF THE INVENTION According to this invention, the flame retardance excellent in durability can be provided to a polyester fiber, and also the provision of the flame retardant processing agent for polyester fibers which can suppress the texture hardening of a polyester fiber product is attained. Moreover, according to the flame retardant processing agent for polyester fibers of the present invention, it is possible to obtain a polyester fiber product having no flame curing and having excellent flame resistance.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

<Flame retardant for polyester fiber>
First, the flame retardant processing agent for polyester fibers of the present invention will be described. The flame retardant processing agent for polyester fibers of the present invention (hereinafter simply referred to as “flame retardant processing agent”) is represented by tris (2,3-dibromopropyl) isocyanurate and formula (1) described below, and has a weight. It contains a polyester resin having an average molecular weight of 5,000 to 200,000. In such a flame retardant, normally, tris (2,3-dibromopropyl) isocyanurate and the polyester resin are stably present in a state of being emulsified and dispersed in water.

  With such a flame retardant, tris (2,3-dibromopropyl) isocyanurate can penetrate into the inside of the polyester fiber, thereby imparting flame resistance with excellent durability to the polyester fiber. In particular, in the presence of the polyester resin, tris (2,3-dibromopropyl) isocyanurate, which is in a molten state at the flame-retardant processing temperature, can maintain a stable emulsified state, so that it easily penetrates into the polyester fiber. Therefore, the exhaustion rate tends to increase. As a result, it is possible to impart more excellent flame retardancy. In addition, texture hardening does not occur in the obtained polyester fiber product. Furthermore, it becomes possible to reduce the variation in flame retardance between batches of flame retardant processing or between parts of polyester fiber products.

(Tris (2,3-dibromopropyl) isocyanurate)
The tris (2,3-dibromopropyl) isocyanurate (hereinafter abbreviated as “TDBPIC”) used in the present invention is not particularly limited, and “TAIC-6B” manufactured by Nippon Kasei Co., Ltd., Suzuhiro Chemical Co., Ltd. Commercially available TDBPICs such as “Fire Cut P-660CN” manufactured by the Company can be used.

  In the present invention, such TDBPIC is used in a state of being emulsified and dispersed in water. When emulsifying and dispersing TDBPIC, it is possible to prevent aggregation of TDBPIC and form a stable emulsified dispersion state by using the polyester resin, but it may be emulsified and dispersed using a surfactant. Examples of such surfactants include nonionic surfactants and anionic surfactants.

  The nonionic surfactant is not particularly limited, and examples thereof include polyoxyalkylene ether, polyoxyalkylene alkyl ether, polyoxyalkylene aryl ether, and polyoxyalkylene alkyl polyhydric alcohol ether. The anionic surfactant is not particularly limited, and examples thereof include alkylbenzene sulfonates, α-olefin sulfonates, polyoxyalkylene ether sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene aryl ether sulfates, Polyoxyalkylene alkyl polyhydric alcohol ether sulfate, alcohol sulfate sulfate, polyoxyalkylene ether phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene aryl ether phosphate, polyoxyalkylene alkyl polyvalent Examples thereof include phosphate esters such as alcohol ether phosphate esters and alcohol phosphate esters, and salts thereof. Examples of the salt include alkali metal salts and amine salts. Examples of the alkali metal salts include lithium, sodium, and potassium salts. Examples of the amine salt include salts of primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine and allylamine; salts of secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine and diallylamine. A salt of a tertiary amine such as trimethylamine, triethylamine, tripropylamine or tributylamine; a salt of an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine; Among these salts, alkali metal salts are preferred from the viewpoint of improving the emulsion dispersion stability of the polyester resin when used in combination with a polyester resin (preferably a self-emulsifying and dispersing polyester resin) described later.

  Such nonionic surfactants and anionic surfactants may be used singly or in combination of two or more. Moreover, a nonionic surfactant and an anionic surfactant can also be used together. Among these surfactants, particularly when a surfactant having an aromatic functional group as a hydrophobic group is used, an excellent emulsion or dispersion can be obtained. Thus, the surfactant comprises an alkylene oxide adduct of styrenated phenol. Nonionic surfactants and anionic surfactants consisting of esterification products of alkylene oxide adducts of styrenated phenols are preferred.

(Polyester resin)
The polyester resin used in the present invention has the following formula (1):

It is a compound represented by these.

In the above (1), R ¹ represents a HO— group or a HO (R ² O) _a — group, and R ² represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, and butylene, and an ethylene group is particularly preferable from the viewpoint of water solubility and dispersibility.

a is an integer of 1 to 200, more preferably 1 to 150. When a exceeds the upper limit, the viscosity of the polyester resin becomes too high and handling becomes difficult. When a is 2 or more, R ² O may be the same or different, and when R ² O is 2 or more, it may be random addition or block addition.

b is an integer of 2 to 100, and an integer of 2 to 30 is preferable. If b is less than the lower limit, it becomes difficult to obtain a stable flame-retardant effect. On the other hand, if the upper limit is exceeded, the viscosity of the polyester resin becomes too high and handling becomes difficult. A plurality of a in a molecule may be the same or different, and R ⁴ present in a molecule independently represents a hydrogen atom or a —SO ₃ X group, and X represents a hydrogen atom. Represents an alkali metal or an amine. Examples of the alkali metal include sodium and potassium. Examples of amines include primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, and allylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, and diallylamine; trimethylamine, triethylamine, Tertiary amines such as tripropylamine and tributylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

In the above (1), R ³ is a hydrogen atom or the following formula (2):

Represents a group represented by Here, ^{R 4} in the formula (2) has the same meaning as ^{R 4} in the formula (1).

Such a polyester resin includes an aromatic dicarboxylic acid or a derivative thereof and the following formula (3):
HO— (R ² O) _a —H (3)
It can manufacture by a well-known method from the alkylene glycol represented by these. Here, R ² and a in the formula (3) are synonymous with R ² and a in the formula (1).

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, and alkali metal salts or amine salts of aromatic dicarboxylic acids having a sulfonic acid group such as sulfoterephthalic acid, sulfoisophthalic acid, and sulfophthalic acid. Examples of the derivatives thereof include, for example, dimethyl esters, diethyl esters, dipropyl esters, and dibutyl esters of these aromatic dicarboxylic acids, alkyl esters having 1 to 4 carbon atoms, chlorides of these aromatic dicarboxylic acids, anhydrous anhydrides, and the like. Examples include phthalic acid. These aromatic dicarboxylic acids or derivatives thereof can be used singly or in combination of two or more.

  Examples of the alkylene glycol represented by the formula (3) include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and a random copolymer of ethylene oxide and propylene oxide having hydroxyl groups at both ends. A polymer or a block copolymer is mentioned. These alkylene glycols can be used individually by 1 type, and can also be used in combination of 2 or more type.

The polyester resins having the same value of a in a plurality present in the formula (1), for example, when R ² is ethylene, transesterification reaction involving dehydration of the aromatic dicarboxylic acid and polyethylene glycol of a certain molecular weight Or a transesterification reaction involving removal of methanol between the dimethyl ester of the aromatic dicarboxylic acid and polyethylene glycol having a certain molecular weight. In the formula (1), a polyester resin having a repeating unit in which a is 1 and a repeating unit in which a is 2 or more includes a dihydroxyethyl ester of the aromatic dicarboxylic acid, a polyalkylene glycol having a certain molecular weight, and It can manufacture by performing transesterification reaction with deethylene glycol of.

  The polyester resin used in the present invention has a weight average molecular weight of 5,000 to 200,000, preferably 10,000 to 50,000. If the weight average molecular weight of the polyester resin is less than the lower limit, the emulsion dispersion state of TDPIC in the flame retardant processing bath becomes difficult to stabilize, so there is a possibility that TDPIC spots or scum may occur on the polyester fiber. There is a possibility that the texture hardening by TDPIC cannot be suppressed. On the other hand, if the upper limit is exceeded, the viscosity of the polyester resin becomes too high and handling becomes difficult. The weight average molecular weight of the polyester resin can be determined by gel permeation chromatography using monodispersed polyethylene glycol having a known molecular weight as a measurement standard substance.

  In the present invention, the polyester resin has an effect of preventing and suppressing the curing of the polyester fiber due to exhaustion of TDPIC, and even if the polyester resin requires a surfactant during emulsification and dispersion, it prevents the texture of the polyester fiber from hardening. There is no hindrance and flame retardancy is imparted by exhaustion of TDBPIC. However, since surfactants tend to reduce the exhaustion rate of TDBPIC into polyester fibers, it is preferable to use polyester resins having self-emulsifying and dispersing properties in order to reduce the amount of surfactant used. In addition to preventing texture hardening due to exhaustion of TDBPIC, it is possible to improve the exhaustion rate of TDBPIC and enhance the flame retardant effect.

The emulsifying dispersibility of the self-emulsifying dispersible polyester resin is obtained by the hydrophilic group in the polyester resin. Such a self-emulsifying dispersible polyester resin is obtained by synthesizing a polyester resin so that at least a part of R ⁴ present in the formula (1) is a —SO ₃ X group, in the formula (1). The ratio of the ethylene group occupying a plurality of R ² and the degree of polymerization a and b may be adjusted to synthesize a polyester resin having appropriate hydrophilicity. The self-emulsifying dispersible polyester resin having an oxyethylene group as a hydrophilic group (R ² in the formula (1) is an ethylene group) is excellent in the effect of improving the exhaustion rate of TDPIC and suppressing the curing of the polyester fiber. However, from the viewpoint of further stabilizing the emulsified dispersion state, a polyester resin having a sulfonic acid group is also preferable. Such a polyester resin contains 4% by mole or more (more preferably 15% by mole or more, particularly preferably 50% by mole or more) of the aromatic dicarboxylic acid used for synthesizing the polyester resin. A polyester resin in which at least part of R ⁴ present in the formula (1) prepared using an aromatic dicarboxylic acid having a sulfonic acid group such as isophthalic acid or sulfophthalic acid is a —SO ₃ X group. . Such a polyester resin having strong self-emulsifying and dispersing properties having both an oxyethylene group and a sulfonic acid group is particularly excellent in the action of stabilizing the emulsified dispersion state of TDBPIC and increasing the exhaustion rate, and has low texture hardening. A product can be obtained. Incidentally, the is no particular restriction on the counter cation X of -SO 3 _X groups, alkali metals are preferred from the viewpoint of improving the stability of the emulsified dispersion state.

  In the present invention, a nonionic surfactant or an anionic surfactant can be used as necessary in order to emulsify and disperse the polyester resin in water. There is no restriction | limiting in particular as such a nonionic surfactant, For example, polyoxyethylene alkyl ether and polyoxyethylene aryl ether are mentioned. Also, the anionic surfactant is not particularly limited. For example, alkylbenzene sulfonate, α-olefin sulfonate, polyoxyethylene alkyl sulfate, polyoxyethylene aryl ether sulfate, alkyl sulfate, polyoxyethylene aryl ether Phosphate ester and its salt are mentioned.

  In the flame retardant processing agent of the present invention, the content of the polyester resin is not particularly limited, but is preferably 0.1 to 20% by mass of the flame retardant processing agent, and more preferably 5 to 10% by mass. When the content of the polyester resin is less than the lower limit, the emulsified dispersion state of TDPIC in the flame retardant processing bath becomes difficult to stabilize, and further, the texture hardening of the polyester fiber product may not be sufficiently prevented, When the upper limit is exceeded, the polyester resin takes in water, thickens, and becomes gelled, which may make handling difficult.

  Moreover, the flame retardant processing agent of this invention WHEREIN: As for the mixture ratio of TDPIC and the said polyester resin, it is preferable that the said polyester resin is 0.1-50 mass parts with respect to 100 mass parts of TDPIC, 0.5-30 More preferably, it is part by mass. When the blending amount of the polyester resin is less than the lower limit, the emulsified dispersion state of TDPIC in the flame retardant processing bath becomes difficult to stabilize, the exhaustion rate of TDPIC to the polyester fiber decreases, and the texture of the polyester fiber product further decreases. On the other hand, when the upper limit is exceeded, the emulsified and dispersed state of TDPIC in the flame retardant processing bath is too stabilized and the exhaustion rate of TDPIC into the polyester fiber tends to decrease. .

(Flame retardant manufacturing method)
Next, the manufacturing method of the flame retardant processing agent of this invention is demonstrated. The method for producing the flame retardant processing agent of the present invention includes (i) a method of mixing a preliminarily prepared emulsion dispersion of TDPIC and an emulsified dispersion of the polyester resin, and (ii) a preliminarily prepared emulsion dispersion of TDPIC. And (iii) a method of emulsifying and dispersing TDBPIC in a previously prepared emulsified dispersion of the polyester resin.

  In the present invention, the average particle diameter (median diameter) of TDPIC and the polyester resin in an emulsified dispersion state is preferably 1.0 μm or less, and more preferably 0.6 μm or less. If the average particle size of the TDBPIC and the polyester resin in the emulsified dispersion state exceeds the upper limit, the emulsion dispersion stability of the TDBPIC and the polyester resin in the emulsified dispersion and the mixture tends to decrease. Further, in addition to the average particle diameter (median diameter) of TDBPIC and the polyester resin, when their 90% particle diameter is 1.0 μm or less (preferably 0.8 μm or less), a more stable emulsified and dispersed flame-retardant process You can get an agent.

  There is no particular limitation on the method for emulsifying and dispersing the TDBPIC or the polyester resin. However, when the TDBPIC or the polyester resin is emulsified and dispersed at the average particle diameter, a method of phase inversion emulsification using a homomixer or a wet method using a bead mill is used. It is preferable to apply a dispersion method or the like. However, when the polyester resin is a self-emulsifying and dispersing polyester resin, it is not necessary to perform the emulsifying and dispersing process using a homomixer or a bead mill.

  In the production methods (i) and (ii), first, an emulsified dispersion of TDBPIC is prepared. At this time, TDBPIC is emulsified and dispersed in water using the surfactant. As usage-amount of surfactant, 0.1-30 mass parts is preferable with respect to 100 mass parts TDBPIC, and 0.5-10 mass parts is more preferable. When the amount of the surfactant used is less than the lower limit, it tends to be difficult to stably emulsify and disperse TDPIC. On the other hand, when the upper limit is exceeded, TDPIC is applied to the polyester fiber during the flame-retardant processing. The exhaustion rate of the polyester fiber tends to decrease, and sufficient flame retardancy cannot be imparted to the polyester fiber. In the production method (ii), when a self-emulsifying dispersible polyester resin is used as the polyester resin, the exhaustion rate of TDBPIC can be increased.

  In the production methods (i) and (iii), first, an emulsified dispersion of the polyester resin is prepared. The polyester resin has an effect of suppressing the hardening of the polyester fiber due to exhaustion of TDPIC, and may be emulsified and dispersed using the nonionic surfactant or the anionic surfactant as necessary. it can. As the usage-amount of such surfactant, 10 mass parts or less are preferable with respect to 100 mass parts of said polyester resins, and 3 mass parts or less are more preferable. When the usage-amount of surfactant exceeds the said upper limit, the exhaust rate of TDPIC to the polyester fiber in the flame-retardant processing will fall, and it exists in the tendency which cannot give sufficient flame retardance to a polyester fiber. In addition, since the use of the surfactant tends to reduce the exhaustion rate of TDBPIC, the amount of the surfactant used is preferably as small as possible. Further, when the polyester resin is a self-emulsifying dispersible polyester resin, an emulsified dispersion of the polyester resin can be prepared with a small amount of surfactant or without using a surfactant. The exhaustion rate can be increased. As the self-emulsifying dispersible polyester resin, those having an oxyethylene group as a hydrophilic group are preferred, and those having a sulfonic acid group are particularly preferred.

  The production method (iii) is a method of emulsifying and dispersing TDPIC in the emulsified dispersion of the polyester resin, but the self-emulsifying dispersible polyester resin has a function of improving the emulsification and dispersion stability of TDPIC. The amount of surfactant used when emulsifying and dispersing TDBPIC is determined by carrying out emulsification and dispersion of TDBPIC in an emulsified dispersion of a self-emulsifying and dispersing polyester resin. It can be reduced to about 0.5 to 0.75 times the amount of the surfactant used when emulsifying and dispersing. That is, when emulsifying and dispersing TDPIC in the presence of the self-emulsifying and dispersing polyester resin, the amount of surfactant used is preferably 0.05 to 22.5 parts by mass with respect to 100 parts by mass of TDPIC. More preferably, it can be reduced to 0.25 to 7.5 parts by mass. Thus, according to the method of obtaining the TDBPIC emulsified dispersion in the emulsified dispersion of the self-emulsifiable dispersible polyester resin by utilizing the stabilizing effect of the self-emulsifiable dispersible polyester resin on the TDBPIC, the inhibiting factor of the TDBPIC exhaustion is obtained. Accordingly, it is possible to obtain a polyester fiber having a high TDBPIC exhaustion rate. As the self-emulsifying dispersible polyester resin, those having an oxyethylene group as a hydrophilic group are preferred, and those having a sulfonic acid group are particularly preferred.

  In the flame retardant processing agent of the present invention, protective colloid agents such as polyvinyl alcohol, carboxymethyl cellulose, and starch can be added. Thereby, separation and sedimentation of each component in the flame retardant processing agent can be suppressed, and the emulsified dispersion state of the flame retardant processing agent can be kept stable.

<Flame retardant polyester fiber products>
The flame-retardant polyester fiber product of the present invention can be produced by treating polyester fiber with the flame-retardant processing agent of the present invention. Thus, by treating the polyester fiber with the flame retardant processing agent of the present invention, TDPIC and the polyester resin are adsorbed and / or absorbed into the polyester fiber, and the polyester fiber is imparted with excellent flame retardancy. In addition, it is possible to suppress the texture hardening of the polyester fiber product.

  There is no restriction | limiting in particular as a polyester fiber used for this invention, For example, a regular polyester fiber, a cationic dyeable polyester fiber, a reproduction | regeneration polyester fiber, or the thread | yarn with the polyester fiber which consists of these 2 or more types, a tow, a top, a casket, textile Knitting, non-woven fabric and rope. In addition, these polyester fibers and natural fibers such as cotton, hemp, silk and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, acrylic and polyamide; inorganics such as carbon, glass, ceramics, asbestos and metals Fibers; or yarns obtained by blending them, tows, tops, casks, woven fabrics, knitted fabrics, nonwoven fabrics, ropes, and the like.

  In the flame-retardant polyester fiber product of the present invention, the amount of TDBPIC attached (exhaust amount) is not particularly limited, but is 0.1 to 20% o. w. f. (% By mass with respect to the mass of the fiber), preferably 0.2 to 15% o.d. w. f. More preferably, 0.3 to 10% o. w. f. It is particularly preferred that When the adhesion amount (exhaust amount) of TDBPIC is less than the lower limit, it may be impossible to obtain a sufficient flame retardant effect. On the other hand, the flame retardant effect becomes stronger as the amount of TDBPIC attached increases, but if the upper limit is exceeded, the texture tends to harden significantly or cause powdering.

  The amount of the polyester resin used is not particularly limited, but is 1 to 10% o. w. f. 2 to 8% o. w. f. It is more preferable that When the usage-amount of the said polyester resin will be less than the said minimum, there exists a possibility that the texture hardening of a polyester fiber product cannot fully be prevented. On the other hand, the effect of preventing texture hardening becomes stronger as the amount of the polyester resin used increases, but if the upper limit is exceeded, the texture tends to be too soft or cause powdering.

  There are no particular restrictions on the method of applying a flame retardant treatment to the polyester fiber using the flame retardant processing agent of the present invention. For example, a thermosol such as a high pressure exhaust method, a padding method, a spray method, a coating method, or a printing method is used. Law.

  When the flame retardant processing is performed by the high pressure exhaustion method, the polyester fiber is usually 110 to 150 ° C., preferably 120 to 140 ° C. and 20 to 20 ° C. in the flame retardant processing liquid containing the flame retardant processing agent of the present invention. What is necessary is just to immerse about 60 minutes and to adsorb | suck and / or absorb a flame retardant processing agent to a polyester fiber. When the flame-retardant processing temperature is less than the lower limit, TDPIC is difficult to melt, the flame-retardant processing agent is not sufficiently adsorbed and / or absorbed in the polyester fiber, and the flame resistance tends not to be sufficiently imparted to the polyester fiber. is there. On the other hand, when the upper limit is exceeded, discoloration or embrittlement of the polyester fibers tends to occur. Moreover, the flame retardant processing agent of this invention, the process liquid containing a disperse dye and a fluorescent dye can be prepared, and a flame retardant processing process and a dyeing | staining process can also be implemented simultaneously. Examples of the equipment used for the high pressure exhaustion method include a liquid dyeing machine, a beam dyeing machine, and a cheese dyeing machine.

  When flame retardant processing is performed by the thermosol method, after applying the flame retardant processing agent of the present invention to the polyester fiber by padding, spraying, coating or printing, dry heat treatment, saturated normal pressure steam treatment, heating steam treatment The flame retardant can be adsorbed and / or absorbed by the polyester fiber by performing steaming such as high-pressure steam treatment. The temperature of the dry heat treatment and the steam heat treatment is usually 110 to 210 ° C, preferably 160 to 210 ° C. When the temperature of the dry heat treatment and the steam heat treatment is less than the lower limit, the TDBPIC becomes difficult to melt, the flame retardant processing agent is not sufficiently adsorbed and / or absorbed in the polyester fiber, and the flame retardancy cannot be sufficiently imparted to the polyester fiber. There is a tendency. On the other hand, when the upper limit is exceeded, discoloration or embrittlement of the polyester fibers tends to occur.

  Examples of the spray used in the spray method include an air spray that sprays a flame-retardant processing liquid in a mist state using compressed air, and a hydraulic atomization type air spray. Examples of the coater used in the coating method include air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse coater, transfer coater, gravure coater, kiss roll coater, cast coater, curtain coater, and calendar coater. It is done. Examples of the printing machine used in the printing method include a roller printing machine, a flat screen printing machine, and a rotary screen printing machine.

  In addition, when performing a flame retardant processing treatment by a coating method, a foaming agent comprising an anionic surfactant or a nonionic surfactant is added to the flame retardant processing solution containing the flame retardant processing agent of the present invention. A foam processing coating method in which a foam-like treatment liquid is prepared and adhered to the polyester fiber, and a viscosity modifier is added to the flame retardant processing liquid containing the flame retardant processing agent of the present invention to adjust the viscosity to be suitable for processing. A coating method using a treatment liquid can be applied.

  In addition, according to the foam processing coating method, the necessary amount of the flame retardant processing agent can be adhered to the polyester fiber, and the entire amount of the flame retardant processing solution can be used without waste. Although it can be significantly shortened, it is important to minimize the amount of foaming agent used because the exhaustion rate of the flame retardant finish may be reduced by the action of the foaming agent. The viscosity modifier is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, propyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, xanthan gum, and starch paste.

  Further, in the method for producing a flame-retardant polyester fiber product of the present invention, after performing the flame-retardant treatment, the polyester fiber is soaped by an ordinary known method so that the surface does not penetrate or adhere to the polyester fiber. It is preferable to remove TDBPIC that is only attached to the surface. Examples of the cleaning agent used in such a soaping process include ordinary anionic, nonionic and amphoteric surfactants and detergents containing these.

  Furthermore, in the method for producing a flame retardant polyester fiber product of the present invention, other conventionally used fiber processing agents are combined with a flame retardant processing agent to such an extent that the flame retardancy and the effect of preventing texture hardening are not impaired. It can also be used together. Examples of such fiber processing agents include antistatic agents, water and oil repellents, antifouling agents, hard finishes, texture modifiers, softeners, antibacterial agents, water absorbing agents, antislip agents, and light fastness. An improver is mentioned.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, measurement of weight average molecular weight of polyester resin, flame retardancy of polyester fiber product, texture, friction fastness, fastness to light fastness, exhaustion rate of flame retardant component, average particle diameter of flame retardant and 90% Measurement of the particle size and appearance observation of the flame retardant in the emulsified dispersion state were carried out by the following methods.

(1) Weight average molecular weight It measured using the gel permeation chromatography (High-speed GPC "HLC-8120 type | mold" by Tosoh Corp., a measurement standard substance: Polyethylene glycol).

(2) Flame retardancy The obtained flame retardant polyester fiber product was used as it was as a sample before washing and washing. In addition, as a sample after washing and washing, the obtained flame-retardant polyester fiber product was washed and washed five times according to the method described in JIS L 1091: 1999. Further, as a sample after dry cleaning, a product obtained by dry-cleaning the obtained flame-retardant polyester fiber product 5 times according to the method described in JIS L 1018: 1999 was used. Using these samples, the flame retardancy of the polyester fibers was evaluated by the following method.

(I) 45 ° Micro Burner Method After flame time and combustion area were measured using the A-1 method described in JIS L 1091: 1999. In addition, the case where afterflame time was less than 3 second and a combustion area was 30 cm < ² > or less was determined to be acceptable, and other cases were determined to be unacceptable.

(Ii) Coil method (flame contact test)
The number of flame contact was measured using the D method described in JIS L 1091: 1999. In addition, the case where the number of times of flame contact was 3 times or more was determined to be acceptable, and the other cases were determined to be unacceptable.

(3) Texture 10 (soft) of the polyester raw fabric used in the examples and comparative examples, and 1 (hard) the hardest texture among the flame-retardant polyester fiber products obtained in the examples and comparative examples As above, the texture of each flame-retardant polyester fiber product was evaluated in 10 stages.

(4) Friction fastness In accordance with the dyeing fastness test method for friction described in JIS L 0849: 2004, using a device conforming to the friction tester type II (Gakushoku) specified in this, The series was determined by rubbing 100 times at a load of 200 g.

(5) Light fastness It processed at 63 degreeC and 40 hours using the carbon fade o meter, and the series was determined.

(6) Exhaust rate of flame retardant component First, a 6% by mass dispersion of TDBPIC was prepared, and this was placed on a 100% by mass undyed fabric of regular polyester weft with a basis weight of 220 g / m ² and pick-up rate 60 %, And TDBPIC is 3.6% o. w. f. The ratio was applied. This was dried at 130 ° C. for 2 minutes and further cured at 170 ° C. for 1 minute. The fluorescent X-ray intensity I ₀ caused by Br in TDBPIC exhausted by the polyester fiber product by this padding treatment was measured using a fluorescent X-ray analyzer (manufactured by SPECTRO Analytical instrument).

Next, with respect to the flame retardant polyester fiber products obtained in Examples and Comparative Examples, the fluorescent X-ray intensity I caused by Br is measured using the fluorescent X-ray analyzer, and the flame retardant polyester fiber products absorb the flame retardant polyester fiber products. The exhausted flame retardant component amount M _FR (unit:% ow f) is expressed by the following formula (i):
M _FR = 3.6 × I / I ₀ (i)
Further, the amount when the flame retardant component in the flame retardant processing solution (flame retardant / dyeing processing solution) is _exhausted 100% is calculated as the theoretical exhaust amount M _FR0 (unit:% owf. ), The exhaust rate of the flame retardant component is represented by the following formula (ii):
_Exhaust rate of flame retardant component (%) = M _FR / M _FR0 × 100 (ii)
Determined by

However, since resorcinol bis (diphenyl phosphate) does not contain Br, in Comparative Example 4, the amount of flame retardant component M _FR exhausted by the flame retardant polyester fiber product (unit:% owf) is used. Formula (iii) below:
M _FR = [(W _R1 −W _R0 ) / W _R0 − (W ₁ −W ₀ ) / W ₀ ] × 100 (ii)
(W _R1 represents the mass of the fiber product after treatment with the flame retardant / dyeing treatment liquid, W _R0 represents the mass of the fiber product before treatment with the flame retardant / dyeing treatment liquid, and W ₁ is difficult. This represents the mass of the textile product after the treatment with the dyeing treatment liquid not containing the flame retardant, and W ₀ represents the mass of the textile product before the treatment with the dyeing treatment liquid containing no flame retardant)
And the exhaustion rate of the flame retardant component was determined by the formula (ii).

(7) Average particle size, 90% particle size, and appearance Measure the cumulative volume particle size distribution of the flame retardant using a laser diffraction / scattering particle size distribution analyzer ("LA-920" manufactured by HORIBA), and measure the integrated volume. The particle diameter of 50% and the particle diameter of 90% were determined from the small particle diameter side, and the average particle diameter (d50) and 90% particle diameter (d90) were obtained, respectively. Further, the appearance of the emulsified and dispersed flame retardant was visually observed.

(Preparation Example 1)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 77.6 g (0.4 mol) of dimethyl terephthalate, 19.4 g (0.1 mol) of dimethyl isophthalate, polyethylene glycol (average molecular weight) : 3100) 387.5 g (0.125 mol), monoethylene glycol 68.2 g (1.1 mol), antimony trioxide 0.1 g, and zinc acetate 0.1 g were charged, and N ₂ gas was introduced. Next, this mixture was heated to 130 ° C., and then slowly heated from 130 ° C. to 180 ° C. over 2 hours to conduct a transesterification reaction. Methanol outflow began at 140 ° C. Further, after slowly raising the temperature from 180 ° C. to 250 ° C. over 2 hours, the introduction of N ₂ gas was stopped. Then, after reducing the pressure and reacting at 250 to 260 ° C. under a pressure of 0.7 kPa for 2 hours, further reducing the pressure and reacting at a pressure of 0.3 kPa at 260 ° C. for 30 minutes to perform a transesterification reaction. 500 g of resin was obtained. The weight average molecular weight of this polyester resin was 36,000. Next, after dissolving 100 g of this polyester resin in 50 g of N, N-dimethylformamide, 850 g of hot water was added and emulsified to obtain a self-emulsifying dispersible polyester resin liquid A (polyester resin concentration: 10% by mass). It was.

(Preparation Example 2)
In a reaction vessel equipped with a stirrer, a thermometer, a methanol outflow tube, and a rectifying tube, dimethyl terephthalate 87.3 g (0.45 mol), 5-sulfoisophthalic acid dimethyl sodium salt 14.8 g (0.05 mol), Charged with 310 g (0.1 mol) of polyethylene glycol (average molecular weight: 3100), 68.2 g (1.1 mol) of monoethylene glycol, 0.1 g of antimony trioxide and 0.1 g of zinc acetate, and N ₂ gas was introduced. did. Thereafter, a transesterification reaction was carried out in the same manner as in Preparation Example 1 to obtain 425 g of a polyester resin. The weight average molecular weight of this polyester resin was 15,000. Next, after dissolving 100 g of this polyester resin in 50 g of N, N-dimethylformamide, 850 g of hot water was added and emulsified to obtain a self-emulsifying dispersible polyester resin liquid B (polyester resin concentration: 10% by mass). It was.

(Preparation Example 3)
In a reaction vessel equipped with a stirrer, thermometer, methanol outflow tube, and rectification tube, 67.9 g (0.35 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of dimethyl sodium 5-sulfoisophthalate, Dimethyl isophthalate 29.1 g (0.15 mol), polyethylene glycol (average molecular weight: 1000) 200 g (0.2 mol), monoethylene glycol 136.4 g (2.2 mol) and antimony trioxide 0.1 g, acetic acid Zinc 0.1 g was charged and N2 gas was introduced. Thereafter, a transesterification reaction was carried out in the same manner as in Preparation Example 1 to obtain 900 g of a polyester resin. The weight average molecular weight of this polyester resin was 24,000. Next, 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide and then emulsified by adding 850 g of hot water to obtain a self-emulsifying and dispersing polyester resin liquid C (polyester resin concentration: 10% by mass). It was.

(Preparation Example 4)
The amount of 97 g of dimethyl terephthalate is 0.5 mol, the amount of dimethyl isophthalate is 97 g (0.5 mol), and the amount of polyethylene glycol (average molecular weight: 1000) is 100 g (0.1 mol). 400 g of polyester resin was obtained in the same manner as in Preparation Example 1, except that the change was made. The weight average molecular weight of this polyester resin was 2,500. Next, after 100 g of this polyester resin was dissolved in 50 g of N, N-dimethylformamide, 850 g of hot water was added to emulsify, and a self-emulsifying dispersible polyester resin liquid D for comparison (polyester resin concentration: 10% by mass). )

Example 1
TDPIC (40 parts by mass) was added to a 20% adduct of tristyrenated phenol ethylene oxide 20 mol (3 parts by mass) and 50 wt% aqueous solution of ammonium sulfate 10 mol adduct of tristyrenated phenol (2 parts by mass). ), Water (35 parts by mass), preliminarily dispersed using a milder, and then emulsified and dispersed using a bead mill to obtain an emulsified dispersion of TDBPIC. To this, the self-emulsifying dispersible polyester resin liquid A (20 parts by mass) obtained in Preparation Example 1 was added to prepare a flame retardant processing agent. The blending ratio of this flame retardant finish is shown in Table 1.

  Next, 12% o. w. f. Of disperse dye (CI Disperse Blue 56) at 1% o. w. f. Flame retardant / dyeing containing a dispersion leveling agent (“Nikkasan Salt RM-340E” manufactured by Nikka Chemical Co., Ltd.) at 0.5 g / L and 80% by mass acetic acid at 0.3 mL / L A processing solution was prepared.

Next, the flame retardant / dyeing treatment solution was charged into a 100% by mass undyed fabric of weft original regular polyester having a basis weight of 220 g / m ^{2 using} a mini-color dyeing machine (manufactured by Tecsum Giken Co., Ltd.). In a dyeing bath, a flame retardant / dyeing treatment was performed for 30 minutes under conditions of a bath ratio of 1:15 and a temperature of 130 ° C. The polyester fabric after the flame retardant treatment is subjected to a soaping treatment at 80 ° C. for 20 minutes using an aqueous solution containing 2 g / L of a soaping agent (“Escudo FRN” manufactured by Nikka Chemical Co., Ltd.) and 1 g / L of caustic soda. And dried at 170 ° C. for 1 minute to obtain a flame-retardant polyester fiber product.

  The flame retardant evaluation results of this flame retardant polyester fiber product are shown in Table 2. The average particle size and 90% particle size of the flame retardant finishing agent, the appearance observation results, and the measurement results of the exhaust rate of the flame retardant components Table 3 shows the evaluation results of the texture, friction fastness and light fastness of the flame-retardant polyester fiber product.

(Example 2)
TDPIC (40 parts by mass) is mixed with 50 mass% aqueous solution of ammonium ester of 10 mol of tristyrenated phenol ethylene oxide adduct (8 parts by mass) and 32 parts by mass of water, and predispersed using a milder. After that, an emulsified dispersion treatment was performed using a bead mill to obtain an emulsified dispersion of TDBPIC. To this, the self-emulsifying dispersible polyester resin liquid B (20 parts by mass) obtained in Preparation Example 2 was added to prepare a flame retardant processing agent. The blending ratio of this flame retardant finish is shown in Table 1. Next, a flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame-retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Example 3)
As shown in Table 1, it was difficult in the same manner as in Example 2 except that instead of the self-emulsifying / dispersing polyester resin liquid B, the self-emulsifying / dispersing polyester resin liquid C (20 parts by mass) obtained in Preparation Example 3 was used. A flame retardant was prepared. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

Example 4
TDBPIC (40 parts by mass) was mixed with 50 mass% aqueous solution (8 parts by mass) of an ammonium sulfate sulfate adduct of 10 moles of ethylene oxide of tristyrenated phenol, self-emulsifying dispersible polyester resin liquid B (prepared in Preparation Example 2) 20 parts by mass) and water (32 parts by mass), preliminarily dispersed using a milder, and then emulsified and dispersed using a bead mill to prepare a flame retardant processing agent. The blending ratio of this flame retardant finish is shown in Table 1. Next, a flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame-retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Example 5)
As shown in Table 1, Example 4 was carried out except that the amount of 50 mass% aqueous solution of ammonium sulfate 10 mol adduct of tristyrenated phenol was changed to 5 parts by mass and the amount of water was changed to 35 parts by mass. In the same manner as above, a flame retardant finish was prepared. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Example 6)
As shown in Table 1, flame retardant processing was carried out in the same manner as in Example 5 except that the amount of the self-emulsifiable dispersible polyester resin liquid B obtained in Preparation Example 2 was changed to 50 parts by mass and the amount of water was changed to 5 parts by mass. An agent was prepared. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Example 7)
As shown in Table 1, flame retardant in the same manner as in Example 6 except that the self-emulsifying / dispersing polyester resin liquid C (50 parts by mass) obtained in Preparation Example 3 was used instead of the self-emulsifying / dispersing polyester resin liquid B. A processing agent was prepared. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Comparative Example 1)
As shown in Table 1, a flame retardant finish was prepared in the same manner as in Example 1 except that water (20 parts by mass) was added instead of the self-emulsifying / dispersing polyester resin liquid A. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Comparative Example 2)
As shown in Table 1, the same procedure as in Example 1 was conducted except that the comparative self-emulsifiable dispersible polyester resin liquid D (20 parts by mass) obtained in Preparation Example 4 was used instead of the self-emulsifiable dispersible polyester resin liquid A. A flame retardant finish was prepared. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Comparative Example 3)
HBCD (40 parts by mass) is mixed with a 50% by mass aqueous solution (10 parts by mass) of an ammonium sulfate sulfate salt of 10 mol of an adduct of ethylene oxide of tristyrenated phenol, and water (50 parts by mass). After the dispersion, a flame retardant processing agent was prepared by emulsifying and dispersing using a bead mill. The blending ratio of this flame retardant finish is shown in Table 1. Next, a flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame-retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Comparative Example 4)
Resorcinol bis (diphenyl phosphate) [Formula (4) below:

A mixture of t = 1 and t = 2] (50 parts by mass), polyoxyethylene (10 mol addition) tristyrylphenyl ether phosphate ammonia salt 50% by mass aqueous solution (16 parts by mass), water (34 parts by mass) And pre-dispersed using a milder, and then emulsified and dispersed using a bead mill to prepare a flame retardant. The blending ratio of this flame retardant finish is shown in Table 1. Next, a flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that this flame-retardant finish was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Comparative Example 5)
TDPIC (40 parts by mass) was mixed with 50 mass% aqueous solution (30 parts by mass) of an ammonium sulfate sulfate salt of tristyrenated phenol ethylene oxide 10 mol adduct, and water (30 parts by mass). After the dispersion, a flame retardant processing agent was prepared by emulsifying and dispersing using a bead mill. 15% o. w. f. A flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that the above-mentioned ratio was used. The results of measurement and evaluation of this flame-retardant polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

(Comparative Example 6)
A polyester fiber product subjected to only a dyeing process was obtained in the same manner as in Example 1 except that the flame retardant was not used. The results of measurement and evaluation for this polyester fiber product in the same manner as in Example 1 are shown in Tables 2-3.

  As is apparent from the results shown in Table 2, a flame retardant polyester fiber obtained by treating the flame retardant processing agent of the present invention containing TDBPIC and a self-emulsifying dispersible polyester resin in the same bath as a dyeing bath containing a dye ( In Examples 1 to 7), compared with the case where no flame retardant was used (Comparative Example 6) and the case where a phosphorus compound was used as the flame retardant (Comparative Example 4), before washing with water and after washing with water In addition, a good flame retardant effect was confirmed both after dry cleaning. Therefore, it was confirmed that flame resistance excellent in durability can be imparted to the polyester fiber by treating the polyester fiber with the flame retardant processing agent of the present invention. In particular, it was confirmed that the flame retardant polyester fibers obtained in Examples 3 to 7 have a flame retardant effect comparable to that obtained when HBCD was used as a flame retardant processing agent (Comparative Example 3).

  Furthermore, when Examples 2 and 3 were compared, it was confirmed that the flame retardancy of the polyester fiber was improved as the proportion of the sulfonic acid group in the self-emulsifying and dispersing polyester resin increased. Moreover, when Example 2 and 5 were compared, it was confirmed that the flame retardance of a polyester fiber improves, so that there is little quantity of surfactant.

  As is apparent from the results shown in Table 3, the flame retardant processing agents of the present invention (Examples 1 to 7) all have an average particle diameter regardless of the amount of the self-emulsifying / dispersing polyester resin and the surfactant used. This was a 0.4 to 0.5 μm white liquid emulsified dispersion, which was equivalent to the average particle diameter and appearance of the HBCD of Comparative Example 3 emulsified and dispersed under the same conditions. Moreover, it was confirmed that TDPIC (Examples 1-7 and Comparative Examples 1-2) concerning this invention has high exhaustibility with respect to a polyester fiber compared with HBCD (Comparative Example 3) and RDP (Comparative Example 4). It was. Further, when the flame retardant treatment was performed using TDBPIC in the presence of the self-emulsifying dispersible polyester resin (Example 1 and Comparative Example 2), the case of not using the self-emulsifying dispersible polyester resin (Comparative Example) When the self-emulsifying dispersible polyester resin having a predetermined weight average molecular weight is used (Example 1), the self-emulsification dispersion having a small weight average molecular weight is obtained. It was confirmed that the exhaustion rate of TDBPIC was increased as compared with the case where the conductive polyester resin was used (Comparative Example 2). Thus, by increasing the exhaustion rate of the flame retardant component, it is possible to impart an excellent flame retardant effect to the polyester fiber. In addition, since the amount of TDBPIC remaining in the bath at the end of the flame-retardant processing is relatively reduced, it is possible to reduce the amount of halogen discharged to the environment together with the waste water.

  Further, when TDBPIC is exhausted without using a self-emulsifying dispersible polyester resin (Comparative Examples 1 and 5), or when TDBPIC is exhausted using a low molecular weight self-emulsifying dispersible polyester resin (Comparative Example 2). ), The texture of the flame-retardant polyester fiber product was cured, but when TDBPIC was exhausted using the self-emulsifying dispersible polyester resin according to the present invention (Examples 1 to 7), the texture was cured. It tended to be difficult. That is, it was confirmed that the texture hardening of the flame retardant polyester fiber product can be suppressed by treating the polyester fiber with the flame retardant processing agent of the present invention. It has also been confirmed that the use of the self-emulsifying dispersible polyester resin according to the present invention does not affect the fastness to friction and light fastness.

<Stability of flame retardant processing bath>
The flame retardant finishing agents prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were mixed with 15% o. w. f. Of disperse dye (BLACK BL-2001) at 8% o. w. f. Flame retardant / dyeing containing a dispersion leveling agent (“Nikkasan Salt RM-340E” manufactured by Nikka Chemical Co., Ltd.) at 0.5 g / L and 80% by mass acetic acid at 0.5 mL / L A processing solution was prepared.

  This flame-retardant / dyeing treatment solution is charged into a pot of a color pet (manufactured by Nippon Dyeing Machinery Co., Ltd.), and a polyester-processed yarn knit is wrapped around a holder and both ends are fastened with rubber bands. The temperature was rapidly raised and immediately cooled. Thereafter, the knit was washed with water and dried.

(A) Stability of flame retardant processing bath For the obtained knit, measure the amount of casing spot generated by agglomeration of dye and powdering of flame retardant components, and stability of flame retardant processing bath according to the following criteria (Dispersibility) was determined. The results are shown in Table 4.
1: There are a lot of casing spots.
2: There is a medium casing spot.
3: There is a small amount of casing spot.
4: There is a trace amount of casing spot.
5: No casing spot.

(B) Texture Evaluate the texture of each flame-retardant polyester fiber product in 10 grades, with the texture of the unprocessed polyester yarn knit as 10 (flexible) and the hardest texture among the obtained knit as 1 (hard). did. The results are shown in Table 4.

  As is apparent from the results shown in Table 4, a flame retardant polyester fiber obtained by treating the flame retardant processing agent of the present invention containing TDBPIC and a self-emulsifying dispersible polyester resin in the same bath as a dyeing bath containing a dye ( In Examples 1 to 7), the texture hardening is sufficiently suppressed, and there is more flexibility than when the self-emulsifying dispersible polyester resin is not used (Comparative Example 1), and when HBCD is used (Comparison) Compared to Example 3), the texture was inferior.

  When the self-emulsifying dispersible polyester resin into which sulfonic acid groups are not introduced (Example 1) is used, the stability of the flame-retardant processing bath is not using the self-emulsifying dispersible polyester resin (Comparative Example 1). ). On the other hand, when the self-emulsifying dispersible polyester resin having a sulfonic acid group is used (Examples 2 to 7), the occurrence of casing spots is suppressed as compared with Example 1 and Comparative Example 1, and the flame retardant processing is performed. It was confirmed that the bath was stable. When the amount of the surfactant used was increased without using the self-emulsifying dispersible polyester resin (Comparative Example 5), the stability of the flame retardant processing bath was improved, but the texture was slightly soft. It was about.

  As described above, according to the present invention, the polyester fiber can sufficiently exhaust the flame retardant processing agent containing TDBPIC as a flame retardant component, and the polyester fiber has excellent durability. It becomes possible to grant. In addition, it is possible to suppress the texture hardening of the polyester fiber product. Therefore, the flame retardant processing agent of the present invention containing TDPIC and a specific polyester resin is useful as an alternative to the conventional flame retardant processing agent HBCD.

  Moreover, when flame-retardant polyester fiber is produced using the flame-retardant processing agent of the present invention, the residual concentration of TDPIC in the flame-retardant processing bath decreases due to the improvement of exhaustion of TDPIC, so that it can be used as wastewater in the environment. The amount of halogen flowing out can be reduced. Therefore, the method for producing a flame-retardant polyester fiber of the present invention is useful as a production method corresponding to environmental protection and ecology.

Claims (5)

Tris (2,3-dibromopropyl) isocyanurate and the following formula (1):

In [formula (1), ^{R 1} is HO- group or HO ^(R 2 _{O) a} - represents a group, ^{R 2} represents an alkylene group having 2 to 4 carbon atoms, a is an integer of 1 to 200, When a is 2 or more, R ² O may be the same or different, and when R ² O is 2 or more, R ² O may be random addition or block addition, and b is R ⁴ is an integer of 2 to 100, and a plurality of R ^{4 s} in a molecule each independently represent a hydrogen atom or a —SO ₃ X group (X represents a hydrogen atom, an alkali metal or an amine), A may be the same or different, and R ³ is a hydrogen atom or the following formula (2):

(Equation (2) ^{R 4} in has the same meaning as ^{R 4} in the formula (1))
Represents a group represented by
And a polyester resin having a weight average molecular weight of 5,000 to 200,000.   2. The difficulty for polyester fiber according to claim 1, wherein the tris (2,3-dibromopropyl) isocyanurate is present in an emulsified and dispersed state, and the polyester resin is a self-emulsifying and dispersing polyester resin. Burning agent. The flame retardant for a polyester fiber according to claim 1 or 2, wherein R ⁴ in the formulas (1) and (2) is a -SO ₃ X group, and the X is an alkali metal.   The manufacturing method of a flame-retardant polyester fiber product characterized by processing a polyester fiber using the flame-retardant processing agent for polyester fibers as described in any one of Claims 1-3.   A flame-retardant polyester fiber product obtained by the production method according to claim 4.