JP3168107B2 - Cationic dyeable flame retardant polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to flame-retardant polyester fibers which are well dyed with cationic dyes.

[Prior art]

[0002] Aromatic polyesters represented by polyethylene terephthalate have excellent mechanical properties and therefore are widely used as fibers, films and other plastic molded products and are extremely useful materials. At the same time, however, it has a drawback that it is easy to burn, and in recent years, with increasing awareness of fire, there is a strong demand for flame retardancy. In particular, the generation of toxic gases (cyan and halogen) during combustion has been regarded as a problem, and there is therefore a need for the development of flame-retardant products that do not generate toxic gases.

Various attempts have been made to make polyester flame-retardant. For example, a method of post-treating a flame retardant to a molded product such as a fiber or a film, and a method of kneading the flame retardant during molding are known. However, the post-treatment method has various drawbacks such as complicated or non-uniform treatment, roughening of the texture of the molded product, and reduction in flame retardancy due to washing or the like. In the kneading method, the flame retardant is sublimated or colored during molding, or the mechanical properties of the molded product are significantly reduced. Further, when a molded article such as a fiber product is dry-cleaned, the flame retardant is dropped off or bleeds out, resulting in a number of drawbacks such as deterioration in performance and hygiene problems due to contamination.

As a method for remedying such a defect, a so-called copolymerization method for introducing a phosphorus atom, which is one of the atoms imparting flame retardancy, in the molecular main chain of polyester is effective, and various studies have been made in recent years. There are many suggestions. For example, JP-B-36-21050 and JP-B-38-9947 disclose methods of adding phosphonic acids or phosphonic acid esters. However, these phosphonic esters generally have a low boiling point, and thus have drawbacks such as being distilled out of the system during polymerization or causing a three-dimensional side reaction during the production of polyester, making molding difficult or impossible. Tokunosho 3
JP-A-6-20771 discloses a method of adding and copolymerizing bisglycol phosphonate having a relatively high boiling point. However, despite the high boiling point, there is a drawback that cyclic low-boiling substances are generated by self-condensation during polymerization, and many of them are volatilized out of the system.

JP-B-53-13479 and JP-A-50-53354 disclose copolymerization of carboxyphosphinic acid. Such phosphine compounds have no volatility and have excellent flame resistance. However, since the ester-forming functional group is a carboxyl group and a P-OH group of a phosphoric acid bond, the reaction rate is slightly different and the uniformity is somewhat lacking. Further, in terms of heat resistance, the P—O—C bond is inferior to the P—C bond. Also, it is derived from oxaphosphane oxide and itaconic acid in Japanese Patent Publication No. 55-41610. A method for copolymerizing a phosphorus-containing dicarboxylic acid compound is disclosed. This method also has excellent flame resistance.
However, since it is a complex compound having a polycyclic structure, it has a drawback that crystallinity, melting point, physical properties and the like are reduced due to steric hindrance, or molecular cleavage is easily caused by slight light or heat.

[0006] German Patent Application Publication No. 1232348
Discloses a polyester obtained by copolymerizing bis- (p-carboxyphenyl) -phosphinic acid, which is intended for polyester modification such as improvement of dyeing and has a low phosphorus content and almost imparts flame retardancy. Not done. On the other hand, U.S. Pat. No. 4,127,566 discloses a polyester obtained by copolymerizing bis- (carboxyethyl) -methylphosphine oxide. This shows good flame retardancy, but has the drawback that the melting point of the copolymer is greatly reduced and the heat resistance is slightly low.

Aromatic polyesters are difficult to be dyed, have economical and operational problems such as having to be dyed under high temperature and high pressure conditions or dyeing with a carrier. It has the disadvantage of being difficult. In order to improve these disadvantages, Japanese Patent Application Laid-Open No.
-22193, 48-66650, 4
Nos. 8-96643, 50-4193, and 4
Numerous proposals have been made, including Japanese Patent Application Laid-Open No. 9-90344.

[0008] However, these cationic dyeable polyesters also have the drawback that they are easily burnable, similar to or rather than ordinary polyesters, and their use in fields where flame retardancy is required is limited. is the current situation.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to improve the drawbacks of the prior art and to provide a polyester which has a small amount of effective and non-polluting flame-retardant polyester and can be dyed well with a cationic dye. It is intended to be given at the same time.

An object of the present invention is to form a fiber, a film or a resin molded article without deteriorating the mechanical properties and thermal properties inherent in polyester, and to have excellent whiteness, light resistance and washing resistance. Another object of the present invention is to provide a flame-retardant polyester copolymer excellent in cationic dyeability.

[0011]

Means for Solving the Problems The present inventors have conducted various studies on the flame-retardant copolymerization component and made intensive studies. As a result, from the viewpoint of flame-retardant performance, phosphine oxide having a PC bond was converted to an ester. The dicarboxylic acid group is formed from the viewpoint that the forming functional group has two symmetrical shapes in order to form a linear polymer, that the two functional groups have the same reaction rate, and that the boiling point is high and does not volatilize. Further, it has been found that the heat resistance is remarkably improved when the P-substituent is an aryl group. Further, from the viewpoint of dyeability, it has been found that cationic copolymerization can be imparted by copolymerizing a metal salt of sulfonic acid copolymerizable with a flame retardant copolymerization component as a copolymerization component in the polyester, and the present invention. completed.

That is , the first cationic dyeable dye of the present invention.
The flame-retardant polyester fiber has the general formula shown in Chemical Formula 3 below.
Phosphorus-containing dicarboxylic acid represented by (1) or a derivative thereof
And a monomer containing a metal salt of a copolymerizable sulfonic acid and
Dyeable Flame Retardant Polyester Using a Copolymer of
A polyester fiber, wherein the copolymer
Possible polymerization components of monomers containing sulfonic acid metal salts
At least 1.0% by weight and a small amount of P atoms
Characterized by at least 0.2% by weight
It is a cationic dyeable flame retardant polyester fiber.

Embedded image (Wherein X is an aryl group, an aralkyl group or a saturated alicyclic
Compound, Y is a hydrogen atom or a methyl group, Z is a hydrogen atom or
It represents an alkyl group having 1 to 4 carbon atoms. )

[0013] The second cationic dyeable dye of the present invention.
The flame-retardant polyester fiber has the general formula shown in Chemical Formula 4 below.
Phosphorus-containing dicarboxylic acid represented by (2) or a derivative thereof
And a monomer containing a metal salt of a copolymerizable sulfonic acid and
Dyeable Flame Retardant Polyester Using a Copolymer of
A polyester fiber, wherein the copolymer
Possible polymerization components of monomers containing sulfonic acid metal salts
At least 1.0% by weight and a small amount of P atoms
Characterized by at least 0.2% by weight
It is a cationic dyeable flame retardant polyester fiber.

Embedded image (Wherein X is an aryl group, an aralkyl group or a saturated alicyclic
Compound, Y is a hydrogen atom or a methyl group, Z is a hydrogen atom or
It represents an alkyl group having 1 to 4 carbon atoms. )

The dicarboxylic acid component used in the polyester copolymer of the present invention includes terephthalic acid, isophthalic acid, 2.6-naphthalenedicarboxylic acid, 1.5-naphthalenedicarboxylic acid, 4.4-diphenyldicarboxylic acid,
Bis- (4-carboxyphenyl) ether, bis-
(4-carboxyphenyl) sulfone, 1.2-bis (4-carboxyphenoxy) ethane, 5-sulfopropoxyisophthalic acid, diphenyl p. p'-dicarboxylic acid, p-phenylenediacetic acid, diphenyl oxide-p.
p'-Dicarboxylic acid, trans-hexahydroterephthalic acid, and their ester-forming derivatives such as alkyl esters, aryl esters, and ethylene glycol esters. Among them, particularly useful are terephthalic acid and 2.6-naphthalenedicarboxylic acid as main components, and aromatic dicarboxylic acids and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and decamethylene dicarboxylic acid. One or more of the other ester-forming derivatives may be used in a small mixture up to 10 mol%.

On the other hand, the glycol components include ethylene glycol, 1.2-propylene glycol, 1.4-butanediol, trimethylene glycol, 1.6-hexanediol, 1.4-cyclohexanediol, neopentyl glycol, and 1. 4-cyclohexanedimethanol, bisphenol A, bisphenol S, diethylene glycol, polyethylene glycol, polypropylene glycol and the like. Among them, useful ethylene glycol and 1.4-butanediol are used as main components, and one or more other glycol components and ester- forming derivatives can be used by mixing a small amount of up to 10 mol% of the diol component. it can.

As the oxycarboxylic acid component, 4-
Oxybenzoic acid, 4-hydroxyethoxybenzoic acid, oxypivalic acid and the like can be mentioned, and these can also be added in small amounts as needed.

The monomer containing a metal salt of a copolymerizable sulfonic acid used in the present invention is not particularly limited as long as it has two carboxyl groups at the terminal and has a sulfonic acid group. It is preferable to use a skeleton having a sulfonic acid group directly bonded to a benzene ring or a naphthalene ring in the skeleton because the deterioration of the physical and chemical properties of the polymer itself is suppressed as much as possible. As the kind of metal, lithium, sodium, potassium, quaternary phosphonium salt or the like is used.

Examples of the monomer containing a sulfonic acid metal salt used in the present invention include lithium 3,5-biscarboxybenzenesulfonate, sodium 3,5-biscarboxybenzenesulfonate, and 3,5-biscarboxybenzenesulfonic acid. Potassium carboxybenzenesulfonate, lithium 2,6-biscarboxybenzenesulfonate, sodium 2,6-biscarboxybenzenesulfonate, 2,6-biscarboxybenzenesulfonate
Biscarboxybenzenesulfonic acid potassium salt, 2,5
-Lithium biscarboxybenzenesulfonate, 2,
5-biscarboxybenzenesulfonic acid sodium salt,
2,5-biscarboxybenzenesulfonic acid potassium salt, 3,5-dicarbomethoxybenzenesulfonic acid lithium salt, 3,5-dicarbomethoxybenzenesulfonic acid sodium salt, 3,5-dicarbomethoxybenzenesulfonic acid potassium salt Or their isomers, or 3,5-
Lithium di (β-hydroxyethoxycarbonyl) benzenesulfonate, sodium 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonate, 3,
5-di (β-hydroxyethoxycarbonyl) benzenesulfonic acid potassium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid lithium salt, 2,6-dicarboxynaphthalene-4-sulfonic acid sodium salt, 2,6- Dicarboxynaphthalene-4-sulfonic acid potassium salt, etc.
Alternatively, quaternary phosphonium salt compounds thereof may be mentioned. The sulfonic phon acid metal salt may be used or two or more of them may be used alone in combination.

The content of the above-mentioned metal sulfonic acid salt in the polymer is at least 1.0% by weight, preferably 1.5% by weight.
-5% by weight, more preferably 2.0-4% by weight.
If the content of the metal sulfonic acid salt in the polymer is less than 1.0% by weight, the dyeing effect is not sufficient, and if it exceeds 5% by weight, the physical properties of the polymer itself are reduced, the melt viscosity is increased, or spinning is performed. Operability deteriorates.

The polyester copolymer of the present invention may contain a small amount of a monofunctional compound, if necessary, such as benzoic acid, benzoylbenzoic acid, acetic acid, or methoxypolyethylene glycol, or a compound having three or more functionalities, such as glycerin.
Pentaerythritol, phosphate compounds and their ester-forming derivatives can also be added.

The polyester according to the invention comprises such a dicarboxylic acid and diol component and a phosphorus-containing chain member, and the phosphorus-containing chain member has the general formula

Embedded image (In the formula, X represents an aryl group, an aralkyl group or a saturated alicyclic compound, and Y represents a hydrogen atom or a methyl group.)

Embedded image (Wherein, X represents an aryl group, an aralkyl group or a saturated alicyclic compound, and Y represents a hydrogen atom or a methyl group).

As can be seen from the above formula, the molecular structure is symmetrical with a phosphine oxide skeleton of a PC bond, and the two ester-forming functional groups are carboxyl groups at the same reaction rate. The residue X is an aryl group such as C ₆ H ₅ , C ₆ H ₄ -Me, C ₆ H _3- (M
e) ₂ , C ₆ H ₄ —Et, aralkyl groups include, for example, C ₆ H ₅ —CH ₂ , C ₆ H ₄ (Me) —CH ₂ , C _{6
H 5 -CH 2 CH 2, C} 6 H 3 - (Me) 2 , etc. -CH ₂ and the like. Among them, useful ones are a phenyl group and a toluyl group, and a phenyl group having particularly excellent heat resistance is most preferable. Residue Y is H, it is CH _3. C ₂ H ₅ or more is not preferred because it causes steric hindrance, and H is particularly preferred.

The polyester copolymer containing the above-mentioned special structural unit as a chain member can be prepared, for example, from a dicarboxylic acid component containing terephthalic acid as a main component and a glycol component containing ethylene glycol as a main component by a known method. In the production, it is obtained by adding and copolymerizing the phosphorus-containing dicarboxylic acid represented by the general formulas (1) and (2). The phosphorus-containing dicarboxylic acid may be a free dicarboxylic acid or a cyclic acid anhydride, or may be an alkyl ester or a glycol ester. The timing of the addition is selected and added as needed before the transesterification reaction step, or before the polycondensation, in the middle of the polycondensation or just before the completion of the polycondensation. The timing of such addition does not restrict the product of the present invention, but it is preferable to add it by mid-polycondensation in order to obtain a homogeneous copolymer. As a matter of course,
The transesterification reaction and the polycondensation reaction can be performed using a known catalyst.

During the production or molding of such a copolyester, pigments, matting agents, optical brighteners, heat stabilizers,
Various agents may be used as necessary, such as ultraviolet absorbers, antioxidants, antistatic agents, and ether bond inhibitors such as organic amines and organic carboxamides.

The amount of the phosphorus-containing dicarboxylic acid component represented by the general formulas (1) and (2) is such that the P (phosphorus atom) content in the obtained polyester is at least 0.2% by weight, preferably 0.3% by weight. To 3.0% by weight, more preferably 0.5%
１．５1.5% by weight. Of course, depending on the composition of the dicarboxylic acid and glycol components used, it is generally in the range of 2 to 20 mol% of the total acid components. P
Is less than 0.2% by weight, the flame retardancy is poor. On the other hand, if the content is more than 3.0% by weight, the flame retardant effect is saturated, and various properties inherent in the polyester are deteriorated. Of course, it is also possible to once produce a high-content polyester copolymer, mix it with ordinary polyester so as to obtain the desired phosphorus content, and process it. At the time of mixing, either the ordinary polyester polymerization step or the molding processing step may be used.

Examples of the phosphorus-containing dicarboxylic acid compound represented by the general formula (1) of the present invention include bis- (2-carboxyethyl) phenylphosphine oxide, bis- (2-carboxyethyl) m-toluylphosphine oxide, -(2-carboxyethyl) p-toluylphosphine oxide, bis- (2-carboxyethyl) xylylphosphine oxide, bis- (2-carboxyethyl) benzylphosphine oxide, bis- (2-carboxyethyl) m-ethylbenzyl Examples include phosphine oxides and their cyclic anhydrides, or their methyl esters, ethyl esters, propyl esters, butyl esters, ethylene glycol esters, propylene glycol esters, and esters with butanediol.

Examples of the phosphorus-containing dicarboxylic acid compound represented by the general formula (2) of the present invention include bis- (2-carboxymethyl) phenylphosphine oxide, bis- (2-carboxymethyl) m-toluylphosphine oxide, -(2-carboxymethyl) p-toluylphosphine oxide, bis- (2-carboxymethyl) xylylphosphine oxide, bis- (2-carboxymethyl) benzylphosphine oxide, bis- (2-carboxymethyl) m-ethylbenzyl Examples include phosphine oxides and their cyclic anhydrides, or their methyl esters, ethyl esters, propyl esters, butyl esters, ethylene glycol esters, propylene glycol esters, and esters with butanediol.

As a method for producing the fiber, a conventionally known method can be used. For example, the cation-dyeable flame-retardant polyester copolymer obtained in the present invention is melt-spun at a spinning temperature of 250 to 350 ° C. and a winding speed of 500 to 3000 m / min, and then polymerized. It is stretched about 2.5 to 5 times at a temperature near the glass transition point to make a drawn yarn. Alternatively, a drawn yarn is produced in one step by ultra-high-speed spinning at a winding speed of 3000 to 10000 m / min. The drawn yarn can be used as it is, or it can be made into a woven or knitted fabric by passing through false twisting, blending, and the like. Woven knitting may be performed by a usual method, and then scouring, alkali reduction, dyeing and the like are performed. The present invention can be dyed with a basic dye, and if necessary, can be subjected to hydrophilic processing, water repellent processing and the like. A known technique such as spinning mixed with ordinary polyester or the like, or composite spinning, or forming a multi-layer woven or knitted fabric using a yarn mixed with other fibers such as the polyester cotton and acrylic or other fiber yarns. Thus, polyester fiber products having excellent cationic dyeability and flame retardancy can be obtained.

[0029]

The cationically dyeable flame-retardant polyester fiber of the present invention has a phosphorus atom imparting flame retardancy introduced into the main chain of the polyester. In addition, there is no elution or falling off during use such as in the consumer stage or processing such as washing, and the flame retardant performance does not decrease. Further, the atom imparting flame retardancy is only a phosphorus atom, and no gas harmful to the human body is generated even when the molded article comes into contact with a flame. In addition, by including a metal salt of sulfonic acid together with a flame-retardant phosphorus atom in the polyester main chain, it is possible to impart a cationic dyeing property which cannot be obtained with a conventional flame-retardant polyester or the like.

The flame-retardant polyester of the present invention has excellent dyeability and can be applied to a wider range of uses than conventional products. Examples of such textile products and molded articles include thick fabrics, clothing, carpets, curtains, nonwoven fabrics, bottles, films, structural parts, mechanically conductive parts, and the like.

In particular, in the case of light-shielding curtains, tent fabrics, canvas fabrics, and clothing materials produced by sandwiching the fiber of the present invention between ordinary fibers and ordinary flame-retardant fibers, the flame retardancy and the dyeability are poor. It can be said that functions that have been difficult to achieve at the same time can be provided, and there are some that have great industrial value.

[0032]

The present invention will be described in detail with reference to the following examples. In the examples, “parts” means “parts by weight”. The intrinsic viscosity “η” was measured by a conventional method at 20 ° C. in a mixed solvent of phenol / tetrachloroethane = 6/4.
The melting point was determined from the endothermic peak of DSC. The evaluation of the flame retardancy is based on the number of times of flame contact by the 45 ° coil method (JIS L-10).
91 D) or the limiting oxygen index (JIS K-720)
1) Measured and shown according to the method.

Reaction Example 1 A 1-liter four-necked flask equipped with a stirrer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser was placed in an ice-water bath, and 220 g of phenylphosphine was added to 250 c while flowing nitrogen gas.
Dissolve in acrylonitrile c and pour into flask. Next, a 10 N potassium hydroxide solution is added with stirring, and the mixture is cooled with ice water so that the internal temperature becomes 22 ° C. Next, 220 g of acrylonitrile is dropped from the dropping funnel over 45 minutes while adjusting the dropping speed so that the internal temperature is maintained at 25 to 28 ° C. After the completion of the dropwise addition,
Perform a time reaction. After the completion of the reaction, liquid separation was performed and saturated saline 100c was used.
Washed 3 times with c and dried with anhydrous nitrite. Distill the reaction solution,
The fraction at 215 ° -223 ° C./0.2 mmHg was crystallized and recrystallized from ethanol to give 255 g of bis- (2-
(Cyanoethyl) -phenylphosphine was obtained.

250 g of bis- (2-cyanoethyl) phenylphosphine obtained by the above-mentioned method was dissolved in 2.5-fold acetic acid, and uniformly dissolved while maintaining the internal temperature at 60 ° C. Under stirring, 204 g of 30% hydrogen peroxide was heated to an internal temperature of 60-
About 1 hour was added dropwise while maintaining the temperature at 70 ° C. afterwards,
Activated carbon was further added at 75 ° C. for 15 minutes, and the mixture was heated to 100 ° C. and heated and stirred for 15 minutes. After cooling, acetic acid was distilled off using an evaporator, and 265 g of bis- (2-cyanoethyl) was removed.
Phenylphosphine oxide was obtained. 2 if necessary
-Recrystallize with propanol.

280 g of bis- (2-cyanoethyl) phenylphosphine oxide obtained by the above-mentioned method were dissolved in 1300 ml of methanol, and 541 g of the same were dissolved.
(Bis- (2-cyanoethyl) phenylphosphine oxo
A mixture of potassium hydroxide (8 equivalents of Sid ) in 560 ml of water was mixed, and the mixture was mixed at a reflux temperature of methanol of 5.5.
Reacted for hours. After the completion of the reaction, the reaction mixture was diluted with
It was prepared so that H = 1. White crystals gradually precipitated under stirring, and the precipitated crystals were collected by filtration, and 296 g of bis- (2
-Carboxyethyl) phenylphosphine oxide was obtained.

Example 1 Dimethyl terephthalate, ethylene glycol, and bis- (2-carboxyethyl) phenylphosphine oxide obtained in the above reaction example are shown in Table 1, and 0.04 part of zinc acetate is used as a transesterification catalyst in a reaction vessel. And the resulting mixture was heated from 150 ° C. to 220 ° C., and transesterification was carried out for 3 hours while continuously distilling off the methanol produced outside the system. Next, 0.03 parts of antimony trioxide as a polymerization catalyst and ethylene glycol ester of 5-sodium isophthalic acid as a sulfonic acid-containing monomer were added so as to have a composition shown in Table 1, and the internal pressure was reduced while gradually increasing the temperature. Finally, polycondensation was performed at 275 ° C. and 0.3 mmHg for 2 hours. Next, the polymer was extruded into water into a cord shape and cut into pellets of 2.5 mmφ and 3 mm in size. The resulting polymer had an intrinsic viscosity “η” of 0.52 and a melting point of 243 ° C.

After the pellets were dried to a moisture content of 0.005%, they were melt-spun with an extruder at a spinning temperature of 280 ° C. and a take-up speed of 800 m / min, followed by a magnification of 3.9.
The film is stretched by a roller heater at 75 ° C. at a stretching speed of 1000 m / min and set by a plate heater at 140 ° C.
A d / 24f drawn yarn was obtained. Yarn quality is 4.3 ~
4.8 g / d and elongation of 25 to 35% were favorable.

Two drawn yarns were combined, knitted in a tube knitting machine, scoured, and tested for dyeability and flame retardancy. still,
Staining is Kayacryl Blue GSL-ED 5% owf acetic acid 0.2g / L
In a dye bath at a bath ratio of 1:50 at 100 ° C. for 60 minutes. Next, it was washed in a soaping bath containing 1 g / L of a neutral detergent and 0.2 g / L of acetic acid. In the flame retardancy test, a tube knit was weighed 1 g and length 1
It was cut off to a thickness of 00 mm, and the number of flame contacts by the 45 ° coil method was determined. Table 1 shows the results.

[0039]

[Table 1]

Reaction Example 2 A 1-liter four-necked flask equipped with a stirrer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser was placed in an ice-water bath, and hydrogenated with dehydrated tetrahydrofuran (hereinafter referred to as THF) while flowing nitrogen gas. 46.08 g of sodium are added. Thereafter, while cooling, 184.5 g of ethyl malonate is added dropwise for about 1 hour. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. When the solution became transparent, dichlorophenylphosphine dichloride was added dropwise for about 30 minutes under ice-cooling, and the mixture was reacted at a reflux temperature for 3 hours. After completion of the reaction, THF was distilled off, chloroform and water were added to the residue, the chloroform layer was separated, washed with water and dried over anhydrous sodium sulfate. Chloroform was distilled off, ethanol was added to the residue, and the mixture was allowed to stand, and yellow crystals precipitated.

To 100 g of the above yellow crystals, 760 m of hydrochloric acid was added.
l, 760 ml of water was added, and the mixture was heated at reflux temperature for 5 hours.
After completion of the reaction, water was distilled off, and dried at 60 ° C. in vacuo. The product was reacted at 130 ° C. for 6 hours, washed with ethanol,
86 g of bis- (2-carboxymethyl) -phenylphosphine oxide were obtained.

Example 2 The compound obtained in Reaction Example 2 was used in Example 1 Polymerization, spinning and stretching were performed in the same manner as in Example 8, and a flame retardancy test was performed. The dyeability was good, and the flame retardancy was good, with an LOI value of 24.7. The yarn had a strength of 4.3 g / d and an elongation of 28%.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-234782 (JP, A) JP-A-6-158426 (JP, A) JP-A-5-51440 (JP, A) JP-A-50- 82149 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) D01F 6/84 305-306 C08G 63/688-63/692

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (1):
With a phosphorus-containing carboxylic acid or a derivative thereof,
Copolymerized with a monomer containing a metal salt of sulfonic acid
With cationic dyeable flame-retardant polyester fiber using polymer
In the above copolymer, a copolymerizable sulfonic acid
The polymerization component of the metal salt-containing monomer is at least 1.0
% By weight and at least 0.2 P
% Cationic dyeability, characterized by containing
Burning polyester fiber. Embedded image (Wherein X is an aryl group, an aralkyl group or a saturated alicyclic
Compound, Y is a hydrogen atom or a methyl group, Z is a hydrogen atom or
It represents an alkyl group having 1 to 4 carbon atoms. ) 2. A compound represented by the following general formula (2):
With a phosphorus-containing carboxylic acid or a derivative thereof,
Copolymerized with a monomer containing a metal salt of sulfonic acid
With cationic dyeable flame-retardant polyester fiber using polymer
In the above copolymer, a copolymerizable sulfonic acid
The polymerization component of the metal salt-containing monomer is at least 1.0
% By weight and at least 0.2 P
% Cationic dyeability, characterized by containing
Burning polyester fiber. Embedded image (Wherein X is an aryl group, an aralkyl group or a saturated alicyclic
Compound, Y is a hydrogen atom or a methyl group, Z is a hydrogen atom or
It represents an alkyl group having 1 to 4 carbon atoms. )