JP3316333B2 - High flame retardant polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel flame-retardant polyester fiber.

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

[0003]

2. Description of the Related Art Various attempts have been made to make polyester polyester flame-retardant. For example, a method of post-treating a flame retardant to a molded product such as a fiber or a film, a method of kneading the flame retardant during molding, a method of adding and blending the flame retardant by a copolymerization method, and the like are known. .

[0004] The post-treatment method has various disadvantages such as complicated treatment, non-uniform treatment, roughening of the texture of the fiber, and deterioration in flame retardancy due to washing or the like.
In addition, in the kneading method, if the flame retardant is added in an excessive amount in order to improve the flame retardant effect, the flame retardant sublimates or is colored at the time of spinning, or the mechanical properties of the fiber are significantly reduced. Further, when the fiber product or the like is dry-cleaned, the flame retardant falls off or bleeds out, and as a result, there are many disadvantages such as deterioration in performance and hygiene problems due to contamination.

[0005] Many copolymerization methods have also been proposed.
For example, JP-B-36-21050, JP-B-38-9
No. 447 discloses a method of adding phosphonic acid or phosphonic acid esters. However, these phosphonic acids or phosphonic esters generally have a low boiling point, and thus have drawbacks such as distilling out of the system during polymerization or causing a three-dimensional side reaction during the production of polyester, making molding difficult or impossible. JP-B-36-2071 discloses a method of adding and copolymerizing bisglycol phosphonate having a relatively high boiling point. However, in spite of the high boiling point, there is a drawback in that cyclic low-boiling components are generated by self-condensation during polymerization and volatilized out of the system.

JP-B-53-13479 and JP-B-50-53354 disclose copolymerization of carboxyphosphinic acid. Such phosphine compounds have no volatility and have excellent flame retardancy. 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 different and the uniformity is somewhat lacking. Furthermore, in terms of heat resistance, the POC bond is
Inferior to C bond. Japanese Patent Publication No. 55-41610 discloses a method of copolymerizing a phosphorus-containing carboxylic acid compound derived from oxaphosphane oxide and itaconic acid. This compound also has excellent heat resistance,
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.

[0007] 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 dyeability, and has a low phosphorus content and almost no flame retardancy. Not done. On the other hand, U.S. Patent Application Publication No. 4127566 discloses a polyester obtained by copolymerizing bis (carboxyethyl) -methylphosphine oxide. Although this has good flame retardancy, the melting point of the copolymer is greatly reduced,
In addition, it has a drawback that the heat resistance is slightly low.

As described above, various attempts have been made to make the polyester flame-retardant. However, in order to impart excellent flame-retardancy, if too much phosphorus compound is added, the mechanical properties or light resistance of the fiber will be increased. Is greatly reduced. In addition, the method of copolymerization greatly reduces the melting point of the copolymerized polymer, and the method of kneading not only causes sublimation, falling off, and bleed out of the flame retardant, but also causes coloring of the fiber. It becomes remarkable. In other words, in any of the methods of adding and compounding a phosphorus-containing compound by copolymerization, or the method of adding and compounding a phosphorus-containing compound by kneading, the amount of the phosphorus-containing compound to be added is limited, and the amount of the phosphorus-containing compound by a single method is limited. With the addition and compounding method, it is not possible to satisfy the mechanical properties or light resistance of the fiber and to achieve the high flame retardancy required by us.

Conventionally, the reaction of phenylphosphonic acid dichloride with an ethylene glycol adduct of bisphenol S (hereinafter referred to as Bis-S (nEO)) is carried out by Bis-
The solubility of S (nEO) in a solvent is very poor, and the desired compound having a high degree of polymerization has not been obtained. The reaction of phenylphosphonic acid dichloride with bisphenol S gives the desired compound, but the bond is very easy to break due to the bond between phosphorus and phenolic oxygen. At present, not only the mechanical properties or thermal properties of the obtained fibers are remarkably reduced, but also sufficient flame retardancy or light resistance cannot be obtained.

On the other hand, if the reaction between phenylphosphonic acid dichloride and Bis-S (nEO) is carried out by melt polymerization, the desired compound can be obtained. However, Bis-S (n
Since EO) is excessively present, a polymer having a high degree of polymerization cannot be obtained. Further, since a large amount of unreacted Bis-S (nEO) is present, not only the mechanical or thermal properties of the fiber to which this is added and blended are significantly reduced, but also sufficient flame retardancy or light resistance is obtained. I can't.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to improve the drawbacks of the prior art, to be effective in a small amount, to be non-polluting, not to decrease the mechanical or thermal physical properties of polyester, and to provide light resistance. Another object of the present invention is to provide a highly flame-retardant polyester fiber having excellent properties.

[0012]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that after a predetermined amount of an organic phosphorus compound is added and blended into a polymer by copolymerization, an organic phosphorus-containing oligomer is further blended by kneading. This proved that high flame retardancy was obtained. In addition, it was found that in this method, despite the high phosphorus atom content in the polyester, there was almost no decrease in the mechanical properties or thermal properties of the polyester as compared with those added and blended by each method alone. did.

By mixing Bis-S (nEO) with a bishydroxy compound having a similar structure,
It was found that the solubility of Bis-S (nEO) in the solvent was improved.

If an epoxy compound is reacted with the reaction product and the terminal acid value in the reaction product is reduced, the mechanical properties or thermal properties inherent to the polyester are not reduced, and the degree of coloring is reduced. At the same time.

That is, the first aspect of the present invention is to hydrolyze the product after completion of the reaction in a polyester obtained by copolymerizing an organic phosphorus compound so that the phosphorus atom content in the polymer is at most 1.0% by weight. A general formula having a degree of polymerization (n) of 1 to 50, which is decomposed and reacted with an epoxy compound to reduce the terminal acid value to less than 10.

Embedded image (Wherein, R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxymethyl group having 1 to 6 carbon atoms, or a C 1 to C 4
An aryloxymethyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms; an aryl group having 6 to 18 carbon atoms; an aralkyl group having 7 to 20 carbon atoms;
A is a divalent aromatic organic residue (however, a halogen atom is not included), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l and m are 1 to 2 And at least 1 or more of the organic phosphorus-containing compounds represented by the following formula: wherein the phosphorus atom content of the whole fiber is 0.4 to 2. It is a highly flame-retardant polyester fiber characterized by being added and blended to be 0% by weight.

The second aspect of the present invention is to provide (a) a compound represented by the general formula which is a structural unit of one bishydroxy compound:

Embedded image (In the formula, B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, and even if l = m,
1 ≠ m. ) And other general formulas that are structural units of bishydroxy compounds

Embedded image (In the formula, A is a divalent aromatic organic residue (however, a halogen atom is not included), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l and m are integers of 1 to 2, at least one of the following formulas is randomly arranged: (b) the general formula

Embedded image 2. The highly flame-retardant polyester fiber according to claim 1, wherein at least one kind of an organic phosphorus-containing compound having a content of a structural unit of the bishydroxy compound represented by the formula below of 50 mol% or less is used.

The third aspect of the present invention is a compound represented by the general formula:

Embedded image (In the formula, B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, and even if l = m,
1 ≠ m. 2. The flame-retardant flame retardant according to claim 1, wherein one or more organic phosphorus-containing compounds comprising two or more structural units of a bishydroxy compound other than the structural units of the bishydroxy compound represented by the formula (1) are used. 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) sulfone,
1,2-bis (4-carboxyphenyl) ether,
1,2-bis (4-carboxyphenyl) sulfone,
1,2-bis (4-carboxyphenyl) ethane, 5-
Sodium sulfoisophthalic acid, diphenyl-p, p '
Dicarboxylic acid, p-phenylenediacetic acid, diphenyloxide-p, p'-dicarboxylic acid, trans-hexahydroterephthalic acid and their ester-forming derivatives such as alkyl esters, aryl esters, ethylene glycol esters. .

Among them, useful terephthalic acid and 2,6-naphthalenedicarboxylic acid as main components, and other monomers copolymerizable with these aromatic dicarboxylic acids include adipic acid, sebacic acid, azelaic acid and decamethylene dicarboxylic acid. One or more of aliphatic dicarboxylic acids and ester-forming derivatives thereof can be used up to 10 mol%.

On the other hand, the glycol components include ethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol,
Butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentylglycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol -S and its ethylene glycol, polyethylene glycol adduct, diethylene glycol, polyethylene glycol and the like.

Among the useful ethylene glycols, 1,4
-One or more other copolymerizable ester-forming derivatives containing butanediol as the main component,
Mole% can be used as a limit.

The organic phosphorus compound to be copolymerized with the polyester in the present invention is represented by the following general formula:

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
An aryl group having 8 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Write. ) Or a general formula

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
An aryl group having 8 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Write. ) Or a general formula

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
An aryl group having 8 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Write. ) Or a general formula

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
An aryl group having 8 to 8 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, Y represents a hydrogen atom or a methyl group, Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Write. ) Or a general formula

Embedded image (In the formula, R ′ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ″ represents a hydrogen atom or a methyl group, and two R ′s may be the same or different.) The compound represented by these is mentioned.

General formula

Embedded image As the compound represented by, for example, bis- (2-carboxyethyl) phenylphosphine oxide, bis- (2
-Carboxyethyl) m-toluylphosphine oxide, bis- (2-carboxyethyl) p-toluylphosphine oxide, bis- (2-carboxyethyl) xylylphosphine oxide, bis- (2-carboxyethyl) benzylphosphine oxide, bis -(2-carboxyethyl) m-ethylbenzylphosphine oxide and their cyclic acid anhydrides, or their methyl esters, ethyl esters, propyl esters, butyl esters, ethylene glycol esters, propylene glyco-
And esters with butanediol.

General formula

Embedded image As the compound represented by, for example, bis- (2-carboxymethyl) phenylphosphine oxide, bis- (2
-Carboxymethyl) m-toluylphosphine oxide, bis- (2-carboxymethyl) p-toluylphosphine oxide, bis- (2-carboxymethyl) xylylphosphine oxide, bis- (2-carboxymethyl) benzylphosphine oxide, bis -(2-carboxymethyl) m-ethylbenzylphosphine oxide and their cyclic acid anhydrides, or their methyl esters, ethyl esters, propyl esters, butyl esters, ethylene glycol esters, propylene glyco-
And esters with butanediol.

General formula

Embedded image Examples of the compound represented by are 2-carboxyethyl-methylphosphonic acid, 2-carboxyethyl-ethylphosphonic acid, 2-carboxyethyl-phenylphosphonic acid, 2-carboxyethyl-m-toluylphosphonic acid 2-carboxyethyl-p-toluylphosphonic acid, 2-carboxyethyl-xylylphosphonic acid,
2-carboxyethyl-benzylphosphonic acid, 2-carboxyethyl m-ethylbenzylphosphonic acid, and the like.

General formula

Embedded image Examples of the compound represented by are 2-carboxymethyl-methylphosphonic acid, 2-carboxymethyl-ethylphosphonic acid, 2-carboxymethyl-phenylphosphonic acid, 2-carboxymethyl-m-toluylphosphonic acid 2-carboxymethyl-p-toluylphosphonic acid, 2-carboxymethyl-xylylphosphonic acid,
2-carboxymethyl-benzylphosphonic acid, 2-carboxymethyl m-ethylbenzylphosphonic acid and the like.

These organic phosphorus halides have the general formula

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
8, an aryl group, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, and L represents a halogen atom. ) Is trivalent, such as dichlorophenylphosphine, dibromophenylphosphine, dichloromethylphosphine, dibromomethylphosphine, dichloroethylphosphine, dibromoethylphosphine, dichloro-m-toluylphosphine, Dibromo-m-toluylphosphine, dichloro-
p-toluylphosphine, dibromo-p-toluylphosphine, dichloroxylylphosphine, dibromoxylylphosphine, dichlorobenzylphosphine, dibromobenzylphosphine, dichloro-m-ethylbenzylphosphine, dibromo-m-ethylbenzylphosphine,
Compounds such as dichlorodimethylphenylphosphine and dibromodimethylphenylphosphine, or a general formula

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
8, an aryl group, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, and L represents a halogen atom. ) Wherein the phosphorus atom is pentavalent, such as dichlorophenylphosphine oxide, dibromophenylphosphine oxide, dichloromethylphosphine oxide, dibromomethylphosphine oxide,
Dichloroethyl phosphine oxide, dibromoethyl phosphine oxide, dichloro-m-toluyl phosphine oxide, dibromo-m-toluyl phosphine oxide, dichloro-p-toluyl phosphine oxide, dibromo-p-toluyl phosphine oxide, dichloroxylyl phosphine oxide, dichlorooxy phosphine oxide, dibromo 1 mol of a compound such as silylphosphine oxide, dichlorobenzylphosphine oxide, dibromobenzylphosphine oxide, dichloro-m-ethylbenzylphosphine oxide, dibromo-m-ethylbenzylphosphine oxide, dichlorodimethylphenylphosphine oxide, dibromodimethylphenylphosphine oxide and acrylonitrile 1
Mole or 2 moles, or 1 mole of the above-mentioned organophosphorus halide and 2 moles of malonic acid ester, followed by hydrolysis and decarboxylation, or 1 mole of the above-mentioned organophosphorus halide and an organometallic compound Alternatively, react with 1 mol or 2 mol of Grignard reagent, or react with general formula

Embedded image Is obtained by the reaction of oxaphosphane oxide with an itaconic acid derivative.

The polyester copolymers described above, for example, a dicarboxylic acid component containing terephthalic acid or 2,6-naphthalenedicarboxylic acid as a main component and ethylene glycol or 1,
In producing an aromatic polyester comprising a glycol component containing 4-butanediol as a main component by a known method, the above organic phosphorus compound is added and copolymerized. At this time, the timing of addition is selected and added as necessary, before the transesterification step, before the polycondensation, in the middle of the polycondensation, or just before the completion of the polycondensation. The time of addition does not restrict the product of the present invention, but it is preferable to add it by the middle of polycondensation in order to obtain a homogeneous copolymer. The transesterification reaction and the polycondensation reaction can be performed using a known catalyst.

During the production or molding of such a polyester copolymer, pigments, matting agents, fluorescent brighteners, ultraviolet absorbers, antioxidants, antistatic agents, and organic amines, organic carboxylic acid amides, etc. Various compounds such as a ter bond inhibitor may be used as necessary.

The amount of the organic phosphorus compound added to the polyester copolymer is such that the phosphorus atom content in the polyester copolymer is at most 1.0% by weight, preferably at most 0.9% by weight, more preferably at most 0.9% by weight. An organic phosphorus compound is added and blended so as to be 0.4 to 0.8% by weight. When the added amount of the organic phosphorus compound exceeds 1.0% by weight, a remarkable decrease in mechanical properties or thermal properties inherent to polyester is observed.

The organic phosphorus-containing compound to be added to and incorporated into the flame-retardant polyester produced by the above method in the present invention is represented by the following general formula:

Embedded image (Wherein, R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxymethyl group having 1 to 6 carbon atoms, or a C 1 to C 4
An aryloxymethyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms; an alkyl group having 1 to 4 carbon atoms; an aryl group having 6 to 18 carbon atoms; an aralkyl group having 7 to 20 carbon atoms;
A is a divalent aromatic organic residue (however, a halogen atom is not included), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l and m are 1 to 2 And may be l = m or l ≠ m).

These organic phosphorus-containing compounds have the general formula

Embedded image (Wherein X is an alkyl group having 1 to 4 carbon atoms, 6 to 1 carbon atoms)
8, an aryl group, an aralkyl group having 7 to 20 carbon atoms, a saturated alicyclic group having 6 to 14 carbon atoms, and L represents a halogen atom. ) Wherein the phosphorus atom is pentavalent, such as dichlorophenylphosphine oxide, dibromophenylphosphine oxide, dichloromethylphosphine oxide, dibromomethylphosphine oxide,
Dichloroethyl phosphine oxide, dibromoethyl phosphine oxide, dichloro-m-toluyl phosphine oxide, dibromo-m-toluyl phosphine oxide, dichloro-p-toluyl phosphine oxide, dibromo-p-toluyl phosphine oxide, dichloroxylyl phosphine oxide, dichlorooxy phosphine oxide, dibromo Organic phosphorus halides such as silylphosphine oxide, dichlorobenzylphosphine oxide, dibromobenzylphosphine oxide, dichloro-m-ethylbenzylphosphine oxide, dibromo-m-ethylbenzylphosphine oxide, dichlorodimethylphenylphosphine oxide, and dibromodimethylphenylphosphine oxide; , General formula

Embedded image (In the formula, A is a divalent aromatic organic residue (however, halogen is not included), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, = M or 1 ≠ m.) Can be obtained through a reaction with a bishydroxy compound represented by the formula: When adding and compounding these organic phosphorus-containing compounds to the polyester copolymer, one kind or a mixture of two or more kinds may be used.

These organic phosphorus-containing compounds have the general formula

Embedded image And an organic phosphorus halide represented by the general formula

Embedded image (In the formula, B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, and even if l = m,
1 ≠ m. ) And other general formulas

Embedded image (In the formula, A is a divalent aromatic organic residue (however, halogen is not included), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, = M or 1 ≠ m), or a reaction with a mixture of one or more bishydroxy compounds represented by the general formula:

Embedded image (Hereinafter, a mixture of these bishydroxy compounds will be simply referred to as a mixture of bishydroxy compounds).

These bishydroxy compounds are prepared by reacting (a) glycol or (b) an epoxy compound with a bishydroxy compound or a mixture of bishydroxy compounds having a divalent aromatic organic residue as a skeleton. Or
(C) It is obtained by reacting a halogenated alcohol in the presence of an alkaline earth metal. Of course, an alkyl group having about 1 to 4 carbon atoms may be bonded to these skeletons, but a halogen atom is not bonded.
Examples of the glycol component in the case of (a) include ethylene glycol, n-propylene glycol, i-propylene glycol, 1,4-butanediol, diethylene glycol and the like. Examples of the epoxy compound in the case of (b) include ethylene oxide and propylene oxide. Examples of the halogenated alcohol in the case of (c) include ethylene chlorohydrin, ethylene bromohydrin, and 3-bromopropanol. -1 and the like.

Either of these methods may be used, but in the case of (a), since the transesterification reaction is one of the usual polyester production steps, it can be easily extracted from that step. Further, it can be obtained by depolymerizing a polyester. Such a glycol or epoxy compound can be selected depending on the purpose and application, but when it is necessary to increase the phosphorus content of the organic phosphorus-containing compound to be formed, ethylene glycol or ethylene oxide having a small number of carbon atoms is preferred. The reaction has the general formula

Embedded image L, m of the compound represented by the formula is 1-2, preferably l + m
Is preferably adjusted to be 2 or more.

General formula

Embedded image A which forms the skeleton of the bishydroxy compound represented by

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image (However, D represents an alkylene group having 2 to 4 carbon atoms, an alkylidene group, O, S, SO ₂ , and CO.) Of course, an alkyl group having about 1 to 3 carbon atoms, a sulfonic acid group, A phosphate group and a metal salt thereof may be bonded. Examples of diol compounds having such a skeleton include hydroquinone, resorcin, 2-methylresorcin, 1,5-dihydroxybenzene-3-sulfonic acid soda, 4,4'-dihydroxydiphenyl, and 2,2'-
Dihydroxydiphenyl, 4,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (2,6-dimethylphenol), 4,4'-methylenebisphenol, 4,4'- Methylenebis (2,6-dimethylphenol), 4,4'-sulfonebis (2,6
-Dimethylphenol), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 4,5-dihydroxynaphthalene-2,7-disulfonic acid sodium, hydroxybenzophenone, 1, 5-dihydroxyanthraquinone, 1,8-
And dihydroxyanthraquinone.

General formula which is an intermediate of an organic phosphorus compound

Embedded image The organic phosphorus-containing oligomer represented by the general formula

Embedded image And an organic phosphorus halide represented by the general formula

Embedded image After performing a reaction with a bishydroxy compound represented by or a reaction with a bishydroxy compound mixture,
It is obtained by hydrolysis. For the reaction, a conventionally known technique such as a solution method, a melting method or an interfacial reaction method can be applied.
Among them, the solution method is preferred because the scale-up is easy, the reaction efficiency is high, and the amount of by-products is small. Solvents for the solution method include benzene, toluene, xylene, mesitylene, tetrahydrofuran, trichlene, dichloroethane, trichloroethylene, chloroform, chlorobenzene and the like. Among them, aromatic hydrocarbon solvents such as toluene and xylene are preferable.

It is well known that a side reaction easily proceeds in a reaction under a high temperature.

Embedded image The organophosphorus halide represented by the formula is extremely reactive and has the general formula

Embedded image Since the bishydroxy compound or bishydroxy compound mixture represented by the formula (1) is also highly reactive, the reaction easily proceeds at a relatively low temperature, and a reactant having a high degree of polymerization can be obtained. Therefore, arbitrarily, the general formula

Embedded image (N) can be adjusted. The average value of (n) is preferably adjusted to 1 to 50, and more preferably to 10 to 20, in order to uniformly introduce it into the main chain of the polyester. (N) is 50
If the ratio exceeds the above range, the softening point and the melt viscosity of the oligomer become too high, which causes problems in the isolation and purification during the synthesis of the oligomer and the addition and blending during the spinning.

Therefore, the amount charged during the reaction is represented by the general formula

Embedded image The number of moles of the bishydroxy compound or the mixture of bishydroxy compounds is in the range of 0.9 to 2.0, preferably 0.95 to 1.5 per mole of the organic phosphorus halide represented by As the number of moles approaches the equimolar ratio, the degree of polymerization (n) increases. On the other hand, when the number of moles of the bishydroxy compound or the mixture of the bishydroxy compounds exceeds 2 moles, unreacted bishydroxy compound or the mixture of the bishydroxy compounds is mixed, which causes deterioration of the mechanical properties inherent in the polyester.

According to the present invention, the general formula

Embedded image Reaction of an organophosphorus halide represented by the formula with a bishydroxy compound or a mixture of bishydroxy compounds at a reaction temperature of 10
The reaction is carried out at 0 ° C or higher, preferably at 120 to 150 ° C for 1 hour or longer. Further, if necessary, calcium chloride, magnesium chloride or the like is added to accelerate the reaction.

In addition, the general formula

Embedded image When a bishydroxy compound represented by the formula (1) is used, it is mixed with another bishydroxy compound so that its content is at most 50 mol%, preferably 40 mol% or less, more preferably 30 mol% or less. . If it exceeds 50 mol%, Bis-S (nE
O) is suspended and the reaction becomes non-uniform, and the molecular weight of the organic phosphorus-containing oligomer is reduced, and the mechanical properties inherent to the polyester added and blended are reduced.

According to the present invention, after completion of the reaction, a product obtained by hydrolyzing a PL bond (L is a halogen atom) is reacted with an epoxy compound. These epoxy compounds include, for example, ethylene oxide, propylene oxide,
1,2-epoxybutane, 1,2-epoxyhexane,
1,2-epoxyoctane, 1,2-epoxydecane,
Examples thereof include 1,2-epoxyethylbenzene, phenylglycidyl ether, methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, and butyl glycidyl ether.

That is, the reaction product after completion of the reaction is represented by the general formula

Embedded image When the molar ratio of the bishydroxy compound or the mixture of bishydroxy compounds to the organic phosphorus halide represented by

Embedded image Many oligomers having a P-OH bond as represented by As the number of these oligomers increases, the terminal acid value increases, and the mechanical or thermal properties of the polyester to which these oligomers are added are remarkably reduced and the coloring becomes remarkable.

However, the addition reaction of the epoxy compound gives a compound of the general formula

Embedded image As shown by, the terminal P-OH bond is converted into an ester bond and the acid value decreases. In addition, the number of moles of the added amount of epoxy is represented by the general formula

Embedded image The organic phosphorus-containing oligomer represented by
4.0 equivalents, preferably in the range of 1.0 to 2.0 equivalents. If less than 1.0 equivalent, the acid value does not fall sufficiently,
Even if it exceeds 4.0 equivalents, the effect will be saturated.

The terminal acid value is preferably less than 10, preferably less than 5, and more preferably less than 1. Terminal acid value is 1
When the value is 0 or more, not only remarkable deterioration of the mechanical properties or thermal properties of the polyester, but also coloring occurs.

In the present invention, the terminal acid value is reduced by reacting the reaction product with an epoxy compound. When this is added to polyester, coloring can be prevented, and the mechanical properties or thermal properties inherent to polyester can be attained. A flame-retardant polyester fiber without deteriorating physical properties can be produced.

In the present invention, the amount of the organic phosphorus-containing compound further added to the flame-retardant polyester copolymer is from 0.4 to 0.4.
The content is 2.0% by weight, preferably 0.5 to 1.0% by weight, and more preferably 0.6 to 0.9% by weight.
If the content exceeds 2.0% by weight, not only the flame retardant effect is saturated, but also the mechanical properties or thermal properties inherent to the polyester deteriorate. If the amount is less than 0.4% by weight, the flame retardancy is not sufficient.

The method of adding the organic phosphorus-containing compound in the present invention includes polymerization blend, chip blend, spinner polymer tube blend, spinner head blend, spinneret blend and the like. Among these, a polymer blend, a chip blend, and a polymer tube blend of a spinning machine are preferable for uniformly blending in a polyester copolymer, and a polymer tube blend of a spin machine is more preferable.

Further, when added to the polyester copolymer, the compound represented by the general formula

Embedded image May be used alone or as a mixture of two or more kinds.

Embedded image As in the case of using the bishydroxy compound represented by the formula, an organic phosphorus-containing compound composed of two or more bishydroxy components may be used. Alternatively, an organic phosphorus-containing compound composed of a single bishydroxy component or two or more bishydroxy components may be synthesized, and mixed and used at an arbitrary ratio.

[0050]

As described above, in the highly flame-retardant polyester fiber of the present invention, two kinds of flame retardants are added and blended by copolymerization and kneading, respectively, in an optimum amount. Excellent flame retardancy can be exhibited without significantly deteriorating physical properties or thermal physical properties. That is, as the amount of the flame retardant added gradually increases, the flame retardancy improves, but the inherent mechanical properties or thermal properties of the polyester decrease. When the amount of the flame retardant added is increased to some extent, not only the flame retardancy is saturated, but also the mechanical properties, thermal properties, and the like of the polyester are significantly reduced. We have:
The amounts of the two types of flame retardants added to the polyester were determined so that the mechanical properties or thermal properties inherent to the polyester immediately before the flame retardancy of the polyester was saturated were not reduced. In addition, by doing so, the flame retardant does not fall off as seen in the kneading method, bleed out or the melting point does not significantly decrease as seen in the sublimation or copolymerization method, and good flame retardancy can be exhibited. .

According to the method of the present invention, flame-retardant polyester fibers which are effective and non-polluting in a small amount and which do not degrade the mechanical properties or thermal properties inherent to the polyester can be obtained. It is a useful material having permanent properties such that the flame retardant does not elute or fall off during use of the product or during treatment such as washing, and the flame retardant performance does not decrease. Furthermore, it has excellent light fastness and whiteness, and has good dyeability. Furthermore, the atom which imparts flame retardancy is only a phosphorus atom, and even if the molded article comes into contact with a flame, there is no generation of gas harmful to the human body, and it is a highly safe and useful substance.

The flame-retardant polyester fiber obtained by the present invention can be spun, drawn or false-twisted by a usual method, can be post-treated by a usual method, and can be woven or knitted without any special consideration. Loom and knitting machine can be used. Further, even when mixed spinning, cross-weaving and cross-knitting with ordinary non-flame-retardant fibers, for example, polyester, cationic dyeable polyester, acrylic and the like, it can exhibit sufficient flame retardancy to be used. Furthermore, various kinds of flame-retardant fiber products can be obtained by a known technique, for example, by performing a composite spinning or using a yarn mixed with other fibers such as polyester cotton and acrylic into a woven or knitted fabric having a multilayer structure using other fibers. I can do it. Further, the present polymer can easily obtain a flame-retardant product such as a film, a foil or a bottle by extrusion, compression or injection molding in a usual manner. Examples of such fiber products and molded articles include, for example, heavy fabrics, clothing, carpets, curtains, nonwoven fabrics, pants, bottles, films, structural parts, mechanically conductive parts, and the like.

[0053]

The present invention will be described in detail with reference to the following examples. In the examples, “parts” means “parts by weight” unless otherwise specified, and “%” in the examples means “% by weight” unless otherwise specified. The intrinsic viscosity “η” is 2 in a mixed solvent of phenol / tetrachloroethane = 6/4.
It was determined at 0 ° C. by a conventional method. The melting point was determined from an endothermic peak of a differential scanning calorimeter (hereinafter, referred to as DSC) manufactured by Rigaku Corporation. The phosphorus analysis was performed by using a P-5200 type dual monochrome inductively coupled plasma emission spectrometer (hereinafter referred to as ICP) manufactured by Hitachi, Ltd.
Chromatography (hereinafter referred to as GPC)
The nuclear magnetic resonance spectrum (hereinafter, referred to as NMR) was measured using OSOH HCL-8020 and using FT-NMR R-1900 manufactured by Hitachi, Ltd.
The infrared absorption spectrum (hereinafter referred to as IR) is
The measurement was performed using a Perkin Elmer-1650 manufactured by Kin Elmer. The evaluation of flame retardancy is based on the limiting oxygen index method (JI
SK-7201). The evaluation of the color fastness was made by terasil pink 3GN 1
% Owf, ionet RAP 310 2 cc / l, acetic acid (1:30), and dyeing at 130 ° C. for 60 minutes. The light resistance test was carried out according to JIS L0842 method at a back panel temperature of 63 ° C. The ultraviolet irradiation was performed for 19 hours and 76 hours. The wear test is based on JIS
According to the L0849 method, the washing test is performed according to JIS L0844.
Dry cleaning test according to JIS L08
Performed according to the 60 method.

Reaction Example 1 2 mol of ethylene oxide was added to 1 mol of 4,4'-isopropylidenebisphenol to obtain the following diol compound.

Embedded image A reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube, and distillation tube port

Embedded image (From the analysis results, the number of moles of ethylene glycol added, l + m
= 2.02. ), 100 parts of xylene and 0.1 part of calcium chloride, and N ₂ gas was flown.
While heating to 120 ° C. to dissolve. Next, 19.5 parts of phenylphosphonic dichloride was gradually added dropwise from the dropping funnel while stirring at an internal temperature of 120 to 130 ° C. for about 30 minutes. The diol component is equimolar to 1 mole of phenylphosphonic dichloride. The temperature was raised to 140 ° C., and the reaction was performed for 1 hour. The acid value of the reaction product obtained at this time was 12.4. Thereafter, the mixture was cooled to 100 ° C., and 0.2 parts of water was added, followed by a reaction for 1 hour. After heating again, unreacted water was distilled off by azeotropic distillation with xylene, and then cooled to 80 ° C.
1.5 parts of 1,2-epoxybutane was added and reacted for 1 hour. Thereafter, the temperature was raised again to 140 ° C., and the pressure in the system was gradually reduced to remove xylene.
The temperature was adjusted to mHg and the mixture was further heated for 30 minutes. The obtained product was a colorless and transparent resin. The molecular weight was 6,000 by GPC measurement. Further, the acid value was 0.1. Further, the results of NMR and IR analyzes suggested the following structure.

Embedded image

Example 1 388 parts of dimethyl terephthalate, 248 parts of ethylene glycol and 14.8 parts of the general formula

Embedded image A mixture of 0.07% of zinc acetate, 0.02% of titanyl oxalate and 0.01% of antimony trioxide with respect to dimethyl terephthalate and 150 to 230 ° C. The mixture was heated for 120 minutes to perform a transesterification reaction. Then, the temperature in the system is required for 30 minutes and 2
Reduce the pressure in the system to 75 ° C in 45 minutes and reduce to 0.2m
The reaction was continued for 60 minutes as mHg. Next, the polymer was extruded in a cord shape and cut into pieces of 2.5 mmφ × 3.
The pellets had a size of mm. The resulting polymer had an intrinsic viscosity [η] of 0.57 and a melting point of 245 ° C. or,
As a result of ICP analysis, it was found that the P content was 0.65%, and a substantially theoretical amount of P was contained.

Next, the pellets were dried with a water content of 0.005%.
When the polymer is melt-spun with an extruder after drying until the polymer reaches the polymer tube, the polymerization degree (n) obtained in Reaction Example 1 is 1 to 50 and the melting point is 4
The organic phosphorus-containing compound at 4 to 58 ° C is injected by using a press-in device so that the blending ratio becomes 5% or 10%, and the mixture is uniformly kneaded with a static mixer of Kenix Co., Ltd., and the spinning temperature is 285 ° C. The melt spinning was performed at a winding speed of 1000 m / min.

Subsequently, a magnification of 3.6 and a stretching speed of 730 m /
The film was drawn with a roller heater at 85 ° C. for a minute and set with a plate heater at 150 ° C. to obtain a 75d / 24f drawn yarn. Yarn quality is 5.49% added and strength is 4.49
g / d, elongation of 30.2% and 10% were added and blended, and the strength was as good as 4.19 g / d and elongation was 32.7%.

Next to 3 Hongo yarn cylinder knitting the fiber, scouring, those dry, also conventional polyester (75 this fiber
d / 24f, melt spinning of semi-dal tip in the usual way,
The knitted yarn was knitted so that the ratio of the number of stretched yarns to the number of yarns was 2/1, and the flame retardancy test was performed after scouring and drying.

Reaction Example 2 4,4'-isopropylidenebisphenol was converted to 4,4 '
-Isopropylidenebis (2,6-dimethylpheno-
All the steps were carried out in the same manner as described in Reaction Example 1 except for changing to (1). The product obtained by this method was also a colorless and transparent resin. The molecular weight was 7,000 as measured by GPC. Further, the acid value was 0.1. Further, the results of NMR and IR analyzes suggested the following structure.

Embedded image

Example 2 The procedure of Example 1 was repeated except that the organic phosphorus-containing compound to be injected with a press-in machine was changed to that obtained in Reaction Example 2. The yarn quality was 4.5% added and the strength was 4.5.
8g / d, elongation of 30.4% and 10% were added and blended, and the strength was as good as 4.37g / d and the elongation was 32.9%.

Reaction Example 3 4,4'-Sulfonebis (2,6-dimethylpheno-
1) 2 moles of ethylene oxide were added to 1 mole to obtain the following diol compound.

Embedded image A reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube, and distillation tube port

Embedded image (From the analysis results, the number of moles of ethylene glycol added, l + m
= 2.02. ), 100 parts of xylene and 0.1 part of calcium chloride, and N ₂ gas was flown.
While heating to 90 ° C. to dissolve. Next, 19.5 parts of phenylphosphonic dichloride was gradually added dropwise from the dropping funnel while stirring at an internal temperature of 90 to 100 ° C. for about 30 minutes. The diol component is equimolar to 1 mole of phenylphosphonic dichloride. Thereafter, all reaction examples 1
The procedure was as described. The product obtained by this method was also a colorless and transparent resin. The molecular weight was 8,000 by GPC measurement. Further, the acid value was 0.1. Further, the results of NMR and IR analyzes suggested the following structure.

Embedded image

Example 3 The procedure of Example 1 was repeated except that the organic phosphorus-containing compound to be press-fitted by the press-in machine was changed to that obtained in Reaction Example 3. The yarn quality is 5% added and blended, and the strength is 4.4
8 g / d, elongation of 31.4% and 10% were added and blended, and the strength was as good as 4.31 g / d and elongation was 32.0%.

Comparative Example 1 In comparison with the method described in Example 1, the procedure was the same as in Example 1, except that the injection of the organic phosphorus-containing compound using a press-in device was omitted.

Comparative Example 2 Compared with the method described in Example 1, the general formula

Embedded image When the organophosphorus compound represented by the formula (1) is copolymerized, the amount of P added in the obtained polymer is increased by increasing the amount of the compound added.
Each step was carried out by the method described in Example 1 except that the content was 30% and that the injection of the organic phosphorus-containing compound using a press-in device was omitted during melt spinning. Three fibers were knitted in a twin yarn tube and evaluated for flame retardancy. Table 1 shows the above results. In the following tables, the compounding ratio is the compounding ratio of the organic phosphorus-containing compound, W _SD is a 75 d / 24 f semi-dull polyester fiber spun and stretched by an ordinary method, and P content is the P of the entire fiber. Is described.

[0065]

[Table 1]

The flame-retardant polyester fiber obtained in Comparative Example 2 and the flame-retardant polyester fiber obtained in Example 1 (the content of the organic phosphorus-containing compound was 10%, the P content was 1.29%, and Compared to the case of the present twin yarn knitting), as in the former case, even if a high content of an organic phosphorus compound is added and blended in the fiber only by polymerization, the decrease in melting point is close to 25 to 30 ° C.,
The yarn quality is 3.13 g / d in strength and 23.9% in elongation.
And the original mechanical properties of polyester cannot be maintained. On the other hand, the yarn quality of the flame-retardant polyester fiber obtained in Example 1 (having a compounding ratio of the organic phosphorus-containing compound of 10%, a P content of 1.29%, and a three-ply yarn knitting process) was , Strength is 4.1
9 g / d and elongation were as good as 32.7%. It was also found that there was almost no lowering of the melting point (the lowering of the melting point was about 2 to 4 ° C.).

Reaction Example 4 One mole of 4,4'-isopropylidenebisphenol was added with 2 moles of ethylene oxide to give the following diol compound.

Embedded image 1 mole of 4,4'-isopropylidenebis (2,6-dimethylphenol) was added with 2 moles of ethylene oxide to give the following diol compound.

Embedded image The above bishydroxy compound mixture (based on the analysis results, both ethylene glycol addition moles l + m = 2.02) was placed in a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube, and distillation tube port. Yes, and the mixing ratio is 7 for the former
0 mol%, the latter being 30 mol%. ), 33.3 parts, xylene 100 parts and calcium chloride 0.1 part,
The mixture was heated to 120 ° C. while flowing N ₂ gas to dissolve it. Next, 19.5 parts of phenylphosphonic dichloride was gradually added dropwise from the dropping funnel while stirring at an internal temperature of 120 to 130 ° C. for about 30 minutes. The diol component is equimolar to 1 mole of phenylphosphonic dichloride. The temperature was raised to 140 ° C., and the reaction was performed for 1 hour. The acid value of the reaction product obtained at this time was 12.4. Then 10
After cooling to 0 ° C., 0.2 parts of water was added and reacted for 1 hour.
After heating again, unreacted water was distilled off by azeotropy with xylene, and then cooled to 80 ° C.
Was added and reacted for 1 hour. Thereafter, the temperature was raised again to 140 ° C., and the inside of the system was gradually reduced in pressure to remove xylene, and the pressure in the system was adjusted to 5 mmHg in 30 minutes, and the system was further heated for 30 minutes. The obtained product was a colorless and transparent resin. The molecular weight was 6,000 by GPC measurement. or,
The acid value was 0.1.

Example 4 The procedure of Example 1 was repeated, except that the organic phosphorus-containing compound to be injected with a press-in machine was changed to that obtained in Reaction Example 4. The yarn quality is 5% added and blended, and the strength is 4.4
2g / d, elongation of 31.9% and 10% were added and blended, and strength was 4.33g / d and elongation was 33.7%.

Reaction Example 5 The procedure was as described in Reaction Example 4 except that 4,4'-isopropylidenebis (2,6-dimethylphenol) was changed to 4,4'-sulfonbisphenol. . In this case, the reaction system was almost uniform until the end of the reaction. Also in this case, the obtained product was a colorless and transparent resin. GPC measurement revealed a molecular weight of 4000. or,
The acid value was 0.1.

Example 5 The procedure of Example 1 was repeated, except that the organic phosphorus-containing compound to be injected with a press-in machine was changed to that obtained in Reaction Example 5. The yarn quality was 4.5% added and the strength was 4.5.
5 g / d, elongation of 31.1% and 10% were added and blended, and the strength was as good as 4.36 g / d and the elongation was 32.3%.

[0071]

[Table 2]

Reaction Example 6 The mixing ratio of the bishydroxy compound was determined by the chemical formula

Embedded image 90 mol% of a bishydroxy compound represented by the following formula:

Embedded image Was carried out by the method described in Reaction Example 4 except that the amount of the bishydroxy compound represented by was changed to 10 mol%. The product obtained by this method was also a colorless and transparent resin. In this case, the reaction system was almost uniform until the end of the reaction. The molecular weight was 6,000 by GPC measurement. Further, the acid value was 0.1.

Example 6 An organic phosphorus-containing compound to be injected by a press-in machine was changed to that obtained in Reaction Example 6, and the obtained drawn yarn was knitted into a three-ply tube and evaluated for flame retardancy. All procedures were performed in the same manner as in Example 4, except that the steps were omitted. Yarn quality was added and blended at 5%, strength was 4.45 g / d, and elongation was 34.1.
%, Strength of 4.32 g / d with addition of 10%,
The elongation was as good as 32.9%.

Reaction Example 7 The mixing ratio of the bishydroxy compound was

Embedded image 50 mol% of a bishydroxy compound represented by the following formula:

Embedded image All were carried out by the method described in Reaction Example 4, except that the amount of the bishydroxy compound represented by was changed to 50 mol%. The product obtained by this method was also a colorless and transparent resin. The molecular weight was 2,000 by GPC measurement. Further, the acid value was 0.1.

Example 7 The organic phosphorus-containing compound to be press-fitted by a press-fitting machine was changed to that obtained in Reaction Example 7, and the obtained drawn yarn was knitted into three ply tubes to evaluate the flame retardancy. All procedures were performed in the same manner as in Example 4, except that the steps were omitted. Yarn quality is 5.49 g / d and elongation is 30.0% with 5% added.
%, 10% added and strength is 4.31 g / d,
The elongation was as good as 32.0%.

Comparative Example 3 The mixing ratio of the bishydroxy compound was

Embedded image 30 mol% of a bishydroxy compound represented by the following formula:

Embedded image All were carried out by the method described in Reaction Example 4, except that the bishydroxy compound represented by was changed to 70 mol%. In this case, the suspension is very large from the start of the reaction,
According to PC measurement, the molecular weight was very small, <1000.

Subsequently, the pressure of the organic phosphorus-containing compound to be injected was changed to that obtained in Comparative Example 3, and the obtained drawn yarn was knitted into a three-ply tube and evaluated for flame retardancy. Except for omitting, all were carried out by the method described in Example 4.
The yarn quality is 5% added and blended, and the strength is 3.31 g / d,
With elongation of 24.0% and 10% added, the strength is 3.12 g / d and the elongation is 23.3%, so that the original mechanical properties of polyester cannot be maintained. Table 3 shows the above results. However, in Table 3, the amount of suspension at the time of synthesis means the amount of suspension at the time of synthesis of the organic phosphorus-containing oligomer, and the molecular weight is
The molecular weight of the organic phosphorus-containing compound is referred to as the yarn quality, and the yarn quality of the drawn yarn obtained by adding and blending the organic phosphorus-containing compound is described.Evaluation is based on the above-described quantitative results. Is good, Δ is slightly poor but practical, and X is poor and lacks practicality.

[0078]

[Table 3]

Example 8 1000 parts of dimethyl terephthalate and ethylene glycol
0.02 to 800 parts of dimethyl terephthalate
% Of manganese acetate 4H ₂ O and 0.04% of antimony trioxide were subjected to transesterification at 170 to 220 ° C. Then, at 220 ° C, the chemical formula

Embedded image Was added and esterified, the pressure in the system was gradually reduced, the temperature was raised, and finally the internal temperature 2
A polycondensation reaction was performed at 75 ° C. and an internal pressure of 0.2 mmHg to obtain a polymer having a melting point of 244 to 248 ° C. Further, as a result of ICP analysis, it was found that the P content was 0.99%, which was almost a theoretical amount of P.

Next, the pellets were treated with a water content of 0.005%.
After drying to the full, all were carried out by the method described in Example 1. The yarn quality was 5% added and blended, and the strength was 4.44.
g / d, elongation of 30.4% and 10% were added and blended, and the strength was as good as 4.31 g / d and elongation was 31.0%.

Example 9 Reaction Example 4 using an organic phosphorus-containing compound to be injected using an injection device
Except for changing to those described, all were carried out by the method described in Example 8.

Comparative Example 4 Compared to the method described in Example 8, except that the P content was changed to be 1.65% and that the press-in of the organic phosphorus-containing compound using a press-in device was omitted. All were carried out by the method described in Example 8. Table 4 shows the above results.

[0083]

[Table 4]

Comparative Example 5 Ordinary polyester fiber (75 d / 24 f in semi-dull)
When the polymer is melt-spun, the organic phosphorus-containing compound obtained in Reaction Example 1 is pressed using a press-in device just before the polymer reaches the polymer tube so that the P content of the whole fiber is 1.35%. The mixture was press-fitted using a press-fitting device, kneaded uniformly with a static mixer manufactured by Kenix, and melt-spun at a spinning temperature of 285 ° C and a winding speed of 1000 m / min.

Subsequently, a magnification of 3.6 and a stretching speed of 730 m /
The film was drawn with a roller heater at 85 ° C. for a minute and set with a plate heater at 150 ° C. to obtain a 75d / 24f drawn yarn. Next, this fiber was knitted in a tube (one piece), refined, dried, and then tested for dyeing fastness.

Embodiment 1, Embodiment 3, Embodiment 4, Embodiment 8
The drawn yarns collected at a blending ratio of the organic phosphorus-containing oligomer of 10% were also knitted in a tube (one piece) and tested for dyeing fastness. Table 5 shows the above results.

[0087]

[Table 5]

From the above results, even if a high content of P is added and blended only by kneading, the color fastness of the produced fiber, particularly the light fastness, abrasion, and various fastnesses of sublimation, are remarkably deteriorated. In addition, in Example 8, the result of dyeing fastness was very good even though P was added in a higher content than Comparative Example 5. Further, the yarn quality of the yarn obtained by the method described in Comparative Example 5 was 3.11 g / d and the elongation was 24.1%, so that the mechanical properties inherent to polyester could not be maintained.

Continuation of the front page (56) References JP-A-49-10242 (JP, A) JP-A-52-10350 (JP, A) JP-A-51-145561 (JP, A) JP-A-6-184821 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) D01F 6/92 301-309 D01F 1/07 D01F 6/84 306 C08K 5/5397

Claims (3)

(57) [Claims] 1. A organophosphorus compound in the polyester phosphorus atom content is at most 1.0% by weight so as to by copolymerizing in the polymer, organic phosphorus halides with Bisuhidoro
A reaction product with a xy compound is hydrolyzed and then reacted with an epoxy compound to reduce the terminal acid value to less than 10, and the polymerization degree (n) is 1 to 50. (Wherein, R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxymethyl group having 1 to 6 carbon atoms, or a C 1 to C 4
An aryloxymethyl group which may be substituted with an alkyl group, X is an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and 6 carbon atoms.
A is a divalent aromatic organic residue (excluding a halogen atom), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l and m are 1 to 2 And 1 or more of organic phosphorus-containing compounds represented by the following formula: wherein the phosphorus atom content of the whole fiber is 0.4 to 2. A highly flame-retardant polyester fiber, which is added and blended to be 0% by weight. 2. A general formula which is a constitutional unit of one bishydroxy compound. (In the formula, B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, and even if l = m,
1 ≠ m. ) And a general formula which is a structural unit of the other bishydroxy compound: (In the formula, A is a divalent aromatic organic residue (however, a halogen atom is not included), B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and l and m are integers of 1 to 2, even l = m, it may be a l ≠ m.) at least one or more are arranged at random, generally
Formula 4 The highly flame-retardant polyester fiber according to claim 1, wherein at least one kind of an organic phosphorus-containing compound having a content of a structural unit of the bishydroxy compound represented by the formula below of 50 mol% or less is used. 3. A compound of the general formula (In the formula, B is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, l and m are integers of 1 to 2, and even if l = m,
1 ≠ m. 2) other than the structural unit of the bishydroxy compound represented by
The highly flame-retardant polyester fiber according to claim 1, wherein at least one kind of an organic phosphorus-containing compound composed of at least one kind of a bishydroxy compound is used.