JPH07109621A - Flame-retardant polyester fiber dyeable with cationic dye - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant polyester fiber dyeable with a cationic dye, which contains a specific phosphorus-containing dicarboxylic acid and a copolymerizable sulfonate metal salt, shows washing fastness and emits no toxic gas. CONSTITUTION:A polyester containing at least 0.2wt.%, preferably 0.5 to 1.5wt.%, based on the phosphorus atom, of a phosphorus-containing dicarboxylic acid or its derivative of formula I or formula II (X is an aryl, an aralkyl or a saturated alicyclic compound; Y is H, methyl; Z is H, a 1-4 C alkyl) and at least 1.0wt.% preferably 2.0 to 4wt.% of a copolymerizable sulfonate metal salt-containing monomer such as 5-sodium sulfoisophthalic acid is spun by melt extrusion and drawn to give the objective flame-retardant polyester fiber dyeable with a cationic dye.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to flame-retardant polyester fibers which are well dyed with cationic dyes.

[Prior art]

Aromatic polyesters typified by polyethylene terephthalate have excellent mechanical properties and 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 easily burns, and with the recent increase in awareness of fire, there is a strong demand for flame retardancy. In particular, the generation of toxic gases (cyan, halogen) at the time of combustion is regarded as a problem, and therefore development of flame-retardant products that do not generate toxic gas is under much demand.

Various attempts have been hitherto made to make polyester flame-retardant. For example, a method of post-treating a flame-retardant agent on a molded article such as fiber or film, and a method of kneading the flame-retardant agent at the time of molding are known. However, the post-treatment method has various drawbacks such as complicated and non-uniform treatment, rough texture of the molded product, and reduced flame retardancy due to washing and the like. Further, in the kneading method, the flame retardant is sublimated or colored during molding, or the mechanical properties of the molded product are remarkably deteriorated. Furthermore, when a molded product such as a textile product is dry-cleaned, the flame retardant may come off or bleed out, resulting in a number of drawbacks such as deterioration in performance and hygiene due to contamination.

A so-called copolymerization method in which a phosphorus atom, which is one of the flame-retarding atoms in the main chain of the polyester molecule, is introduced is effective as a method for improving such drawbacks, and various studies have been made in recent years. There are many suggestions. For example, Japanese Patent Publication No. 36-21050 and Japanese Patent Publication No. 38-9447 disclose methods of adding phosphonic acid or phosphonic acid esters. However, since these phosphonates generally have a low boiling point, they have the drawbacks that they are distilled out of the system during polymerization, or three-dimensional side reactions occur during the production of polyester, making molding difficult or impossible. Tokusho Sho 3
Japanese Unexamined Patent Publication No. 6-20771 discloses a method in which a phosphonic acid bisglycol ester having a relatively high boiling point is added and copolymerized. However, despite the high boiling point, there is a drawback in that a large amount of cyclic low-boiling substances are generated by self-condensation during the polymerization and volatilize out of the system.

Japanese Patent Publication No. 53-13479 and Japanese Patent Laid-Open No. 50-53354 disclose copolymerizing carboxyphosphinic acid. Such a phosphine compound has no volatility and has 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 poor. Furthermore, in terms of heat resistance, the P-O-C bond is inferior to the P-C bond. Further, it is derived from oxaphosphane oxide and itaconic acid in JP-B-55-41610. A method of copolymerizing a phosphorus-containing dicarboxylic acid compound is disclosed. This method also has excellent flame resistance.
However, since it is a complex polycyclic compound, it has a drawback that crystallinity, melting point, physical properties, etc. are deteriorated due to steric hindrance, or molecular scission is easily caused by slight light or heat.

German Patent Application Publication No. 12232348
JP-A No. 1989-187 discloses a polyester copolymerized with bis- (p-carboxyphenyl) -phosphinic acid, but it is intended for polyester modification such as dyeing improvement, and has a low phosphorus content and imparts almost no flame retardancy. Not done. On the other hand, US Pat. No. 4,127,566 discloses a polyester copolymerized with bis- (carboxyethyl) -methylphosphine oxide. Although this compound exhibits good flame retardancy, it has the drawbacks that the melting point of the copolymer polymer is largely lowered and the heat resistance thereof is rather low.

Aromatic polyesters are difficult to be dyed and have economical and operational problems such as dyeing under conditions of high temperature and high pressure, or having to be dyed with a carrier. It has the drawback of being difficult. In order to improve these drawbacks, JP-A-4848
No. 22193, No. 48-66650, No. 4
No. 8-96643, No. 50-4193, No. 4
A number of proposals have been made including the publication of 9-90344.

However, these cationic dyeable polyesters also have the drawback that they are easily burned as in the case of ordinary polyesters, and their use in fields requiring flame retardancy is limited. is the current situation.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to improve the above-mentioned drawbacks of the prior art, to provide a polyester which has a flame-retardant property which is effective and harmless in a small amount, and which is capable of dyeing a cationic dye well. It is intended to be given at the same time.

The object of the present invention is to form into fibers, films and resin moldings without deteriorating the mechanical properties and thermal properties inherent in polyester, which are excellent in whiteness, light resistance and washing resistance, Another object of the present invention is to provide a flame-retardant polyester copolymer having excellent cationic dyeability.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted various studies on the flame-retardant copolymerization component, and as a result, have conducted extensive studies. The forming functional group has two symmetrical groups to form a linear polymer, the two functional groups have the same reaction rate, and the boiling point is high and the dicarboxylic acid group does not volatilize. Furthermore, 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 was found that cationic dyeability can be imparted by copolymerizing a metal salt of a sulfonic acid copolymerizable with a flame retardant copolymerization component as a copolymerization component in polyester. completed.

That is, the first aspect of the present invention is the general formula

[Chemical 3] (Wherein X represents an aryl group, an aralkyl group or a saturated alicyclic compound, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). An acid compound or its derivative is contained so that the weight of P atoms in the fiber is at least 0.2% by weight, and a monomer containing a copolymerizable metal salt of sulfonic acid is contained in the fiber in an amount of at least 1.0% by weight. % Of the polyester fiber.

The second aspect of the present invention is the general formula

[Chemical 4] (Wherein X represents an aryl group, an aralkyl group or a saturated alicyclic compound, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). An acid compound or its derivative is contained so that the weight of P atoms in the fiber is at least 0.2% by weight, and a monomer containing a copolymerizable metal salt of sulfonic acid is contained in the fiber in an amount of at least 1.0% by weight. % Of the polyester fiber.

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.
Examples thereof include p'-dicarboxylic acid, trans-hexahydroterephthalic acid, and ester-forming derivatives thereof such as alkyl ester, aryl ester and ethylene glycol ester. Among them, particularly useful are those containing terephthalic acid and 2.6-naphthalenedicarboxylic acid as main components, and aromatic dicarboxylic acids thereof and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and decamethylenedicarboxylic acid, and One or more of the other ester-forming derivatives may be mixed in a small amount up to 10 mol% and used.

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

Further, as the oxycarboxylic acid component, 4-
Examples thereof include oxybenzoic acid, 4-hydroxyethoxybenzoic acid and oxypivalic acid, and these may be added in a small amount as necessary.

The copolymerizable sulfonic acid metal salt-containing monomer 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, but is preferable. It is preferable to use a polymer 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. Further, as the kind of metal, lithium, sodium, potassium, quaternary phosphonium salt, or the like is used.

Examples of the metal salt-containing monomer of sulfonic acid used in the present invention include 3,5-biscarboxybenzenesulfonic acid lithium salt, 3,5-biscarboxybenzenesulfonic acid sodium salt, and 3,5-biscarboxybenzenesulfonic acid sodium salt. Biscarboxybenzenesulfonic acid potassium salt, 2,6-biscarboxybenzenesulfonic acid lithium salt, 2,6-biscarboxybenzenesulfonic acid natrium salt, 2,6
-Biscarboxybenzenesulfonic acid potassium salt, 2,
5-biscarboxybenzenesulfonic acid lithium salt,
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 isomers thereof, or 3,5
-Di (β-hydroxyethoxycarbonyl) benzenesulfonic acid lithium salt, 3,5-di (β-hydroxyethoxycarbonyl) benzenesulfonic acid sodium salt,
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 and the like, or quaternary phosphonium salt compounds thereof can be mentioned. The metal sulfonates may be used alone or in combination of two or more.

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

The polyester copolymer of the present invention may optionally contain a small amount of a monofunctional compound such as benzoic acid, benzoylbenzoic acid, acetic acid, methoxypolyethylene glycol, or a trifunctional or higher functional compound such as glycerin,
It is also possible to add pentaerythritol, phosphoric acid compounds and their ester-forming derivatives.

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

[Chemical 5] (Wherein X represents an aryl group, an aralkyl group or a saturated alicyclic compound, and Y represents a hydrogen atom or a methyl group), or has a general formula

[Chemical 6] (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.).

As can be seen from the above formula, the molecular structure is bilaterally symmetrical with a P--C bond phosphine oxide skeleton, and the two ester-forming functional groups are both carboxyl groups and the reaction rates are the same. Residues X Ali - The group, for example _{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, the useful ones are phenyl group and toluyl group, and phenyl group having excellent heat resistance is most preferable. Residue Y is H, CH ₃ . C ₂ H ₅ or more is not preferable because it causes steric hindrance, and H is particularly preferable.

The polyester copolymer containing the above-mentioned special structural unit as a chain member is obtained by a known method 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. It is obtained by adding and copolymerizing the phosphorus-containing dicarboxylic acid represented by the general formula (1) or (2) at the time of production. The phosphorus-containing dicarboxylic acid may be a free dicarboxylic acid or a cyclic acid anhydride, or may be an alkyl ester or glycol ester. The timing of the addition is selected and added, if necessary, before the transesterification reaction step or before the polycondensation, in the middle of the polycondensation, or just before the completion of the polycondensation. Although the product of the present invention is not restricted by the timing of addition, it is preferable to add it by the middle of polycondensation in order to obtain a homogeneous copolymer. As a matter of course,
The transesterification reaction and polycondensation reaction can be carried out using a known catalyst.

Pigments, matting agents, optical brighteners, heat stabilizers,
If necessary, various kinds of ultraviolet absorbers, antioxidants, antistatic agents, and ether bond inhibitors such as organic amines and organic carboxylic acid amides may be used.

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. To 3.0% by weight, more preferably 0.5
Add to be ~ 1.5 wt%. Of course, it varies depending on the composition of the dicarboxylic acid and glycol components used, but is generally within the range of 2 to 20 mol% of all the acid components. P
If the content of is less than 0.2% by weight, flame retardancy is poor. On the other hand, if the amount is more than 3.0% by weight, the flame retardant effect is saturated and various properties inherent to polyester are deteriorated, which is not preferable. Of course, it is also possible to once produce a high content polyester copolymer, mix it with a normal polyester so as to obtain a desired phosphorus content, and perform molding. The mixing may be carried out at the usual polyester polymerization step or molding step.

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 and bis. -(2-carboxyethyl) p-toluylphosphine oxide, bis- (2-carboxyethyl) xylylphosphine oxide, bis- (2-carboxyethyl) benzylphosphine oxide, bis- (2-carboxyethyl) m-ethylbenzyl Examples thereof include phosphine oxide, and cyclic acid anhydrides thereof, or their methyl esters, ethyl esters, propyl esters, butyl esters, ethylene glycol esters, propylene glycol esters, esters with butanediol, and the like.

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 and bis. -(2-carboxymethyl) p-toluylphosphine oxide, bis- (2-carboxymethyl) xylylphosphine oxide, bis- (2-carboxymethyl) benzylphosphine oxide, bis- (2-carboxymethyl) m-ethylbenzyl Examples thereof include phosphine oxide, and cyclic acid anhydrides thereof, or their methyl esters, ethyl esters, propyl esters, butyl esters, ethylene glycol esters, propylene glycol esters, esters with butanediol, and the like.

As the 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 by a conventional method, for example, a spinning temperature of 250 to 350 ° C. and a winding speed of 500 to 3000 m / min, and then polymerized. Stretching is performed at a temperature near the glass transition point by about 2.5 to 5 times to make a stretched yarn. Alternatively, in the spinning, the drawn yarn is made in one stage by ultra-high speed spinning at a winding speed of 3000 to 10000 m / min. The drawn yarn can be used as it is as a raw yarn, or a woven or knitted fabric can be made by changing the process such as false twisting and blending. Woven knitting may be carried out by an ordinary 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, hydrophilic processing, water repellent processing and the like can be carried out. Known techniques such as mixed spinning with ordinary polyester or composite spinning, or yarns mixed with other fibers such as polyester cotton and acrylic or other fiber yarns to form a multi-layered woven or knitted fabric Thus, it is possible to obtain a flame-retardant polyester fiber product having various cation dyeability.

[0029]

INDUSTRIAL APPLICABILITY The cationic dyeable flame-retardant polyester fiber of the present invention has a phosphorus atom which imparts flame retardancy introduced into the main chain of polyester, so that it can be used for manufacturing processes such as spinning, weaving and dyeing. In addition, the flame-retardant performance is not deteriorated due to neither elution nor dropping even during use such as washing or washing at the consumer stage. Further, since the atom imparting flame retardancy is only the phosphorus atom, no harmful gas is generated in the human body even when the molded product comes into contact with the flame, and it is extremely safe and useful. Further, by incorporating a metal salt of sulfonic acid in addition to a phosphorus atom having flame retardancy in the polyester main chain, it is possible to impart a cationic dyeing property, which cannot be obtained by 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 applications than conventional products. Examples of such fiber products and molded articles include thick fabrics, clothing, carpets, curtains, non-woven fabrics, bottles, films, structural parts, mechanically conductive parts and the like.

In particular, in the case of light-shielding curtains, tents, canvases, and clothing materials produced by sandwiching the fiber of the present invention between ordinary fibers and ordinary flame-retardant fibers, flame retardancy and dyeability are It can be said that functions that were difficult to achieve at the same time can be added, and there is a great industrial value.

[0032]

The present invention will be described in detail with reference to the following examples. All "parts" in the examples mean "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 by the endothermic peak of DSC. The flame retardancy was evaluated by 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 according to the method and shown.

Reaction Example 1 A 1-liter four-necked flask equipped with a stirrer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser was installed in an ice water bath, and 220 g of phenylphosphine was added to 250 c while flowing nitrogen gas.
Dissolve in acrylonitrile of c and pour into a flask. Then, 10N potassium hydroxide solution is added with stirring, and the mixture is cooled with ice water so that the internal temperature becomes 22 ° C. Then, 220 g of acrylonitrile is dropped from the dropping funnel over 45 minutes while adjusting the dropping rate so that the internal temperature is kept at 25 to 28 ° C. 3 at 28-35 ° C after completion of dropping
React for time. After completion of the reaction, the solution is separated and saturated saline 100c
It was washed 3 times with c, and dried with anhydrous sodium sulfate. Distill the reaction solution,
215-223 ° C./0.2 mmHg fraction 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 added to 2.5 g.
It was dissolved in twice the amount of acetic acid, and the internal temperature was kept at 60 ° C. to dissolve it uniformly. While stirring, 204 g of 30% hydrogen peroxide was used at an internal temperature of 60-
While maintaining the temperature at 70 ° C., the solution was dropped for about 1 hour. afterwards,
Activated carbon was further added at 75 ° C for 15 minutes, the temperature was raised to 100 ° C, and the mixture was heated with stirring for 15 minutes. After cooling, acetic acid was distilled off with an evaporator to obtain 265 g of bis- (2-cyanoethyl).
-Phenylphosphine oxide was obtained. If necessary,
Recrystallize with 2-propanol.

280 g of bis- (2-cyanoethyl) -phenylphosphine oxide obtained by the above method dissolved in 1300 ml of methanol, 541
A mixture of g (8 times equivalent of bis- (2-cyanoethyl) -phenylphosphine oxide) potassium hydroxide dissolved in 560 ml of water was mixed and reacted at the reflux temperature of methanol for 5.5 hours. After completion of the reaction, the reaction solution was adjusted to pH = 1 with diluted hydrochloric acid. White crystals gradually precipitated under stirring, and the precipitated crystals were collected by filtration to obtain 296 g of bis- (2-carboxyethyl) -phenylphosphine oxide.

Example 1 Composition of dimethyl terephthalate, ethylene glycol, and bis- (2-carboxyethyl) phenylphosphine oxide obtained by the above reaction example shown in Table 1, and 0.04 parts of zinc acetate as a transesterification catalyst in a reaction vessel. Then, the ester exchange reaction was carried out for 3 hours while continuously distilling out the methanol produced by heating from 150 ° C. to 220 ° C. to the outside of the system. Next, 0.03 part 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 the 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 in a cord shape and cut into pellets having a size of 2.5 mmφ and 3 mm. The obtained polymer had an intrinsic viscosity “η” of 0.52 and a melting point of 243 ° C.

After drying the pellets to a moisture content of 0.005%, they were melt-spun in an extruder at a spinning temperature of 280 ° C. and a winding speed of 800 m / min, and subsequently a draw ratio of 3.9.
Double, draw speed 1000m / min, draw with roller heater at 75 ℃, set with plate heater at 140 ℃,
A drawn yarn of d / 24f was obtained. The yarn quality is tensile strength 4.3-
The result was 4.8 g / d and the elongation was 25 to 35%, which were good.

Two drawn yarns were combined, knitted by a knitting machine and scoured, and then dyeability and flame retardancy tests were conducted. still,
Staining is Kayacryl Blue GSL-ED 5% owf acetic acid 0.2g / L
In the dyebath, the dyeing was carried out at a bath ratio of 1:50 at 100 ° C. for 60 minutes. Then, it was washed in a soaping bath of 1 g / L of neutral detergent and 0.2 g / L of acetic acid. The flame retardancy test weighs 1 g of cylinder knit and 1 length.
It was cut so as to be 00 mm, and the number of times of flame contact by the 45 ° coil method was obtained. The results are shown in Table 1.

[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 installed in an ice-water bath, and hydrogenated with dehydrated tetrahydrofuran (hereinafter referred to as THF) while flowing nitrogen gas. Add 46.08 g of sodium. Then, 184.5 g of ethyl malonate is added dropwise while cooling for about 1 hour. After completion of the dropping, the mixture was stirred at room temperature for 2 hours, and when the solution became transparent, dichlorophenylphosphine dichloride was added dropwise over about 30 minutes under ice cooling, and the mixture was reacted at 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, whereby yellow crystals were precipitated.

100 g of the above yellow crystals and 760 m of hydrochloric acid
1, 760 ml of water were added, and the mixture was heated at reflux temperature for 5 hours.
After completion of the reaction, water was distilled off and the residue was vacuum dried at 60 ° C. The product was reacted at 130 ° C. for 6 hours, washed with ethanol,
86 g of bis- (2-carboxymethyl) -phenylphosphine oxide was obtained.

Example 2 The compound obtained in Reaction Example 2 was used in Example 1 No. Polymerization, spinning and drawing were performed in the same manner as in No. 8, and a flame retardancy test was performed. The dyeability was good, and the flame retardancy was also good with an LOI value of 24.7. The strength of the yarn was 4.3 g / d and the elongation was 28%.

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Claims (2)

[Claims] 1. A general formula: (Wherein X represents an aryl group, an aralkyl group or a saturated alicyclic compound, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). An acid compound or its derivative is contained so that the weight of P atoms in the fiber is at least 0.2% by weight, and a monomer containing a copolymerizable metal salt of sulfonic acid is contained in the fiber in an amount of at least 1.0% by weight. % Of polyester fiber. 2. A general formula: (Wherein X represents an aryl group, an aralkyl group or a saturated alicyclic compound, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). An acid compound or its derivative is contained so that the weight of P atoms in the fiber is at least 0.2% by weight, and a monomer containing a copolymerizable metal salt of sulfonic acid is contained in the fiber in an amount of at least 1.0% by weight. % Of polyester fiber.