JP2002339248A - Flame retardant and method for polyester fiber products - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] A flame-retardant agent and a flame-retardant method capable of imparting excellent flame retardancy to polyester fiber products. A flame retardant comprising (A) a halogen-free phosphate ester, and (B) a general formula (I) (R1 and R2 are each independently a hydrogen atom, C1-22
Alkyl, C2-22 alkenyl, C5 or 6 cycloalkyl group, C6-14 aryl group or C7-1
8 arylalkyl groups. However, R1 and R2 may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n is an integer of 0-2. A) a flame-retardant agent comprising, as a binder resin, a polyester comprising a phosphinic acid derivative as a dicarboxylic acid component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to flame retardant processing of polyester fiber products. That is, the present invention relates to a flame retardant for a polyester fiber product, a method for flame retarding a polyester fiber product, and a flame retarded polyester fiber product. A flame-retardant agent for polyester fiber products that can impart excellent flame resistance to washing resistance and dry-cleaning resistance without lowering the feeling, in particular, without roughening the fiber cloth. , A flame-retardant processing method of a polyester fiber product using such a processing agent, and a flame-retardant processed polyester fiber product obtained by such a flame-retardant process,
In particular, it relates to a flame retarded polyester fiber fabric.

[0002]

2. Description of the Related Art Conventionally, various methods have been known for imparting flame retardancy to polyester fibers, particularly fabrics, by post-processing. For example, using a dispersant, 1, 2, 5, 6,
A method is known in which a brominated cycloalkane such as 9,10-hexabromocyclododecane is dispersed as a flame retardant in water and a flame-retardant processing agent is attached to a polyester fiber cloth (Japanese Patent Publication No. 53-8840). No.). However, according to the method of imparting flame retardancy by attaching a halogen compound to the polyester fiber cloth as described above,
When such a polyester fiber fabric is burned, there is a problem that a harmful halogenated gas is generated, which has a harmful effect on the environment. Therefore, in recent years, the use of such a halogen compound as a flame retardant has been regulated.

[0003] In view of the above, flame retardancy has been imparted to polyester fiber products by using a phosphoric acid ester containing no halogen as a flame retardant instead of such a halogen compound. As such a phosphoric acid ester, for example, an aromatic monophosphate such as tricresyl phosphate, an aromatic diphosphate such as resorcinol bis (diphenyl phosphate), and the like are known. However, such a phosphate ester, which is conventionally known as a flame retardant, can impart flame retardancy excellent in washing resistance to a polyester fiber product,
Insufficient dry cleaning resistance.

For example, textiles such as curtains, dark curtains, curtains, carpets, and fabric blinds used in high-rise buildings, department stores, theaters, hospitals, and other facilities must be fireproof articles (the Fire Service Law). ) Therefore, such a fiber product is subjected to flame-retardant processing in advance for the purpose of fire prevention and used for use.

[0005] However, such a fiber product adheres dust and grease and the like after a long-term use, and must be washed with water or dry-cleaned in order to remove such soil. It is necessary that the desired flame retardancy is maintained even after such water washing and dry cleaning. As described above, a conventionally known flame retardant comprising a phosphate ester can impart flame resistance excellent in washing resistance, but has a problem of poor dry cleaning resistance.

[0006] Further, a polyester containing a dicarboxylic acid composed of a certain phosphinic acid derivative as a dicarboxylic acid component unit described in JP-A-2000-154465 is already known as a halogen-free flame retardant. . However, since this polyester has a low phosphorus content in the molecule, in order to impart sufficient flame retardancy to the polyester fiber product, a large amount of the polyester fiber product must be adhered to the fiber product. In particular, the fabric has a problem that it becomes coarse and hard, the hand is remarkably reduced, and discoloration is caused.

The present inventors have conducted intensive studies to solve the above-mentioned problems in the conventional flame retardant processing of polyester fiber products. As a result, in the flame retardant processing of polyester fiber products, the dicarboxylic acid comprising the phosphinic acid derivative was converted to Paying attention to the effect of polyester containing as a dicarboxylic acid component unit as a binder resin, by fixing a flame retardant comprising a phosphoric acid ester containing no halogen to the polyester fiber product using the polyester as a binder resin, the polyester fiber product The present invention has been found to be capable of performing flame-retardant processing which is not only excellent in washing resistance but also excellent in dry cleaning resistance, without lowering the desired feeling of the material. It is.

[0008]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a polyester fiber product without lowering the feeling, in particular, without imparting a coarse or hard feeling to the fiber cloth, and not only for washing resistance, An object of the present invention is to provide a flame-retardant agent and a flame-retardant processing method capable of imparting flame retardancy excellent in dry-cleaning resistance. Combustion-treated polyester fiber products,
In particular, it is an object to provide a flame-retardant processed polyester fiber cloth.

[0009]

According to the present invention, (A)
A flame retardant comprising a halogen-free phosphate ester and (B) a general formula (I)

[0010]

Embedded image

(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms,
2 represents an alkenyl group, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms having an aryl group having 6 to 14 carbon atoms as a substituent. However, R ¹ and R ² may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n is an integer of 0 to 2. A) a dicarboxylic acid composed of a phosphinic acid derivative represented by formula (I) as a dicarboxylic acid component unit, and having a weight average molecular weight of 1000 to 5
And a binder resin comprising a polyester having a phosphorus content in the range of 2 to 10% by weight in the range of 0000 and a flame retardant for polyester fiber products.

Further, according to the present invention, (A) a flame retardant comprising a phosphoric acid ester containing no halogen is added to (B) a general formula (I)

[0013]

Embedded image

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 22 carbon atoms,
2 represents an alkenyl group, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms having an aryl group having 6 to 14 carbon atoms as a substituent. However, R ¹ and R ² may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n is an integer of 0 to 2. A) a dicarboxylic acid composed of a phosphinic acid derivative represented by formula (I) as a dicarboxylic acid component unit, and having a weight average molecular weight of 1000 to 5
A flame-retardant processing method for a polyester fiber product characterized by being fixed to a polyester fiber product using a binder resin made of polyester having a phosphorus content in a range of 0000 to 2 to 10% by weight. .

Further, according to the present invention, the flame-retardant agent is fixed to a polyester fiber product, or the flame-retardant polyester fiber product obtained by the flame-retardant processing method, in particular,
A flame retarded polyester fiber fabric is provided.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a polyester fiber product is a fiber containing at least polyester fiber,
Yarns containing such fibers, cotton, fabrics such as knitted and nonwoven fabrics, and preferably polyester fibers, yarns made therefrom, cotton, and fabrics such as knitted and nonwoven fabrics.

The flame retardant for polyester fiber products according to the present invention comprises (A) a flame retardant comprising a halogen-free phosphoric acid ester and (B) a general formula (I)

[0018]

Embedded image

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 22 carbon atoms,
2 represents an alkenyl group, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms having an aryl group having 6 to 14 carbon atoms as a substituent. However, R ¹ and R ² may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n is an integer of 0 to 2. A) a dicarboxylic acid composed of a phosphinic acid derivative represented by formula (I) as a dicarboxylic acid component unit, and having a weight average molecular weight of 1000 to 5
And a binder resin composed of a polyester having a phosphorus content in the range of 2 to 10% by weight.

In the present invention, the flame retardant comprising a halogen-free phosphoric acid ester preferably has the general formula (IV)

[0021]

Embedded image

(Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms as a substituent Represents an arylalkyl group having 7 to 18 carbon atoms, Z represents a divalent organic group, and m represents an integer of 0 to 5.) Here, in the general formula (IV), m is preferably 0 or 1.

In the above general formula (IV), the substituent R ⁷ ,
When R ⁸ , R ⁹ or R ¹⁰ is an alkyl group, specific examples of such an alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s -Butyl group, t-butyl group, n-
Pentyl group, 3-methylbutyl group, n-hexyl group, 2
-Ethylbutyl group, n-heptyl group, isoheptyl group,
2-ethylhexyl group, isononyl group, n-decyl group,
Isodecyl group, n-dodecyl group, n-hexadecyl group,
Examples thereof include an n-octadecyl group, an n-icosyl group, and an n-docosyl group. Among them, an alkyl group having 1 to 8 carbon atoms is preferable from the viewpoint of flame retardancy.

When the substituent R ⁷ , R ⁸ , R ⁹ or R ¹⁰ is an aryl group, specific examples of such an aryl group include, for example, phenyl, tolyl, xylyl, mesityl, cumenyl, Examples thereof include an octylphenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Of these, a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

When the substituent R ⁷ , R ⁸ , R ⁹ or R ¹⁰ is an arylalkyl group, specific examples of such an arylalkyl group include a benzyl group and a phenethyl group.

In the above general formula (IV), the group Z is a divalent organic group, preferably a divalent group containing an aromatic nucleus.

[0027]

Embedded image

And the like.

Therefore, according to the present invention, as a preferred specific example of the above-mentioned halogen-free phosphate ester, when m is 0, that is, as a monophosphate, for example, triphenyl phosphate, tricresyl phosphate, diphenyl Examples thereof include cresyl phosphate, cresyl diphenyl phosphate, diphenyloctyl phosphate, trixylenyl phosphate, xylenyl diphenyl phosphate, and t-butylphenyl phosphate.

When m is 1, that is, as specific examples of diphosphate, for example, resorcinol bis (diphenyl phosphate), resorcinol bis (dicylyl phosphate), resorcinol bis (dicresyl phosphate), bisphenol A bis ( Diphenyl phosphate), bisphenol S bis (diphenyl phosphate) and the like.

Further, the binder resin has a general formula (I)

[0032]

Embedded image

(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms,
2 represents an alkenyl group, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms having an aryl group having 6 to 14 carbon atoms as a substituent. However, R ¹ and R ² may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n is an integer of 0 to 2. A) a dicarboxylic acid composed of a phosphinic acid derivative represented by formula (I) as a dicarboxylic acid component unit, and having a weight average molecular weight of 1000 to 5
Consist of polyesters having a phosphorus content in the range of 2 to 10% by weight. When the phosphorus content in the polyester is less than 2% by weight, sufficient flame retardancy cannot be imparted even if the polyester fiber product is treated with a flame retardant using this as a binder resin. When the phosphorus content in the polyester exceeds 10% by weight, the resulting flame-retardant processed polyester fiber article has insufficient friction fastness.

In the above formula (I), the substituent R ¹
Or when R ² is an alkyl group, specific examples of such an alkyl group include, for example, a methyl group, an ethyl group, an n-
Propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl,
3-methylbutyl group, n-hexyl group, 2-ethylbutyl group, n-heptyl group, isoheptyl group, 2-ethylhexyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, n-hexadecyl group, n Examples thereof include -octadecyl group, n-icosyl group, and n-docosyl group. Among them, from the viewpoint of phosphorus content, an alkyl group having 1 to 6 carbon atoms is particularly preferable.

When the substituent R ¹ or R ² is an alkenyl group, specific examples of such an alkenyl group include, for example, vinyl group, 1-propenyl group, 2-propenyl group,
Isopenyl group, 2-butenyl group, 2-pentenyl group,
Examples thereof include a decenyl group, a dodecenyl group, a tridecenyl group, a hexadecenyl group, an octadecenyl group, an icosenyl group, and a docosenyl group. Among them, from the viewpoint of phosphorus content, an alkenyl group having 2 to 6 carbon atoms is particularly preferable.

When the substituent R ¹ or R ² is a cycloalkyl group, specific examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Further, when the substituent R ¹ or R ² is an aryl group, specific examples of such an aryl group include, for example, a phenyl group, a tolyl group, a xylyl group, a mesityl group,
Examples thereof include a cumenyl group, an octylphenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among them, a phenyl group or a biphenylyl group is particularly preferable.

When the substituent R ¹ or R ² is an arylalkyl group, specific examples of such an arylalkyl group include a benzyl group and a phenethyl group.

The dicarboxylic acid composed of such a phosphinic acid derivative is already known.
No. 0-154465.

According to the present invention, among the dicarboxylic acids composed of such phosphinic acid derivatives, the substituents R ¹ and R ² are both (alkyl-substituted) phenyl groups, or the substituents R ¹ and R 2 Those in which ² are bonded to each other to form an (alkyl-substituted) 2,2′-biphenylylene group are preferred.

Accordingly, in the present invention, the dicarboxylic acid component unit composed of such a phosphinic acid derivative is preferably represented by the formula (II):

[0042]

Embedded image

(Wherein R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A and b are each an integer of 0 to 4; A dicarboxylic acid component unit represented by the general formula (III):

[0044]

Embedded image

(Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. C and d are each an integer of 0 to 4; A dicarboxylic acid component unit represented by the following formula: These dicarboxylic acid component units may be used alone or in combination in a dicarboxylic acid component unit composed of a phosphinic acid derivative.

Preferred specific examples of such a dicarboxylic acid component unit comprising a phosphinic acid derivative include, for example,
Examples represented by the following formulas (1) to (4) can be given.

[0047]

Embedded image

In the present invention, the binder resin is a linear polyester having a dicarboxylic acid component unit composed of a phosphinic acid derivative unit and an aromatic dicarboxylic acid component unit and a diol component unit as structural units. Such a polyester is produced by a conventionally known polyester production method, that is, by polycondensing a dicarboxylic acid component corresponding to the dicarboxylic acid component and a diol component corresponding to the diol component unit. Obtainable.

That is, the above polyester is represented by the general formula (V) corresponding to the dicarboxylic acid component unit composed of the phosphinic acid derivative represented by the general formula (I).

[0050]

Embedded image

(Wherein R ¹ , R ² and n are the same as above, and Y is a group represented by the general formula (VI)

[0052]

Embedded image

(Wherein R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a compound of the general formula (VII)

[0054]

Embedded image

(Wherein, R ¹² represents an ethylene group, a propylene group or a butylene group, and r is an integer of 1 to 10). ) Or the following formula (VIII)

[0056]

Embedded image

The group represented by A) a dicarboxylic acid comprising a phosphinic acid derivative, a dialkyl ester thereof, an alkylene oxide adduct thereof or an anhydride thereof and an aromatic dicarboxylic acid, an anhydride thereof or a dialkyl ester thereof, as a dicarboxylic acid component, And polycondensation.

Accordingly, as a preferred specific example of the dicarboxylic acid component comprising the phosphinic acid derivative, corresponding to the dicarboxylic acid component unit comprising the phosphinic acid derivative represented by the general formula (II) or (III), General formula (I
X)

[0059]

Embedded image

(Wherein R ³ , R ⁴ , Y, a, b and n are the same as those described above), and the general formula (X)

[0061]

Embedded image

(Wherein, R ⁵ , R ⁶ , Y, c, d and n are the same as those described above).

According to the present invention, among the dicarboxylic acid components comprising such phosphinic acid derivatives, for example,
Expressed by the following equations (5) and (6)

[0064]

Embedded image

A dimethyl ester of dicarboxylic acid comprising a phosphinic acid derivative as described above is preferably used.

Examples of the aromatic dicarboxylic acid component include, for example, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Examples of the dialkyl ester include dimethyl ester. Can be mentioned.

Examples of the diol component include alkylene glycol, polyoxyalkylene glycol, alkylene oxide adducts of alkylene glycol, and alkylene oxide adducts of divalent aromatic hydroxy compounds represented by bisphenol A. it can. Of these, alkylene glycols are preferred, and linear or branched alkylene glycols having 2 to 10 carbon atoms are particularly preferred, and ethylene glycol is most preferred. The molecular weight of such a diol component is not particularly limited, but is usually 1,000 or less.

Thus, preferably, the phosphine is obtained by polycondensing dimethyl ester of dicarboxylic acid comprising the phosphinic acid derivative and dimethyl ester of aromatic dicarboxylic acid as a dicarboxylic acid component and alkylene glycol as a diol component. A polyester containing a dicarboxylic acid composed of an acid derivative as a dicarboxylic acid component unit can be obtained.

According to the present invention, in the production of the above polyester, although not particularly limited, the molar ratio of the above aromatic dicarboxylic acid dimethyl ester: alkylene glycol: dicarboxylic acid dimethyl ester composed of a phosphinic acid derivative is as follows. , Usually 1: (1-15):
(0.2 to 5), preferably 1: (1 to 1)
12): It is in the range of (0.3-3).

In the present invention, the polyester thus obtained has a weight average molecular weight of usually 10
In the range of 00 to 50,000, preferably 2000
２５25000. When the weight-average molecular weight of the polyester is less than 1,000, even if the above-mentioned flame retardant comprising a phosphate ester is applied to a polyester fiber product as a binder resin, the durability of the flame retardancy is insufficient. If it exceeds 50,000, the dispersibility is poor when used as an aqueous dispersion.

According to the present invention, the above-mentioned flame retardant comprising a phosphoric acid ester containing no halogen is used as a polyester fiber by using a polyester containing a dicarboxylic acid component unit as a binder resin. By giving the polyester fiber product, durable flame retardancy can be imparted to the polyester fiber product without lowering its feeling.

According to the present invention, as a preferred embodiment, the above-mentioned phosphoric ester flame retardant is dispersed in water to form a dispersion, and the polyester containing the dicarboxylic acid composed of the phosphinic acid derivative as a dicarboxylic acid component unit is dissolved in water. Into a dispersion, mixed with this to form an aqueous dispersion, and using this, a polyester fiber product was treated,
Perform flame retardant treatment. However, if necessary, the polyester containing the phosphoric acid ester flame retardant and the dicarboxylic acid composed of the phosphinic acid derivative as a dicarboxylic acid component unit is dispersed in water to form a dispersion, which is applied to a polyester fiber product. Thus, a flame retardant treatment can be performed.

For dispersing the phosphate ester flame retardant in water, there is no particular limitation. For example, the phosphate ester may be dispersed together with a surfactant such as a nonionic surfactant or an anionic surfactant and an organic solvent. What is necessary is just to mix, dissolve uniformly, and emulsify and disperse while gradually adding warm water.

Similarly, for dispersing a polyester containing a dicarboxylic acid composed of the above-mentioned phosphinic acid derivative as a dicarboxylic acid component unit in water, there is no particular limitation. For example, the above-mentioned polyester can be dispersed in a nonionic surfactant or A surfactant such as an anionic surfactant and an organic solvent may be mixed together, uniformly dissolved, and emulsified and dispersed while gradually adding warm water.

Examples of the nonionic surfactant include higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, Examples thereof include polyoxyalkylene-type nonionic surfactants such as fatty acid amide alkylene oxide adducts, and polyhydric alcohol-type nonionic surfactants such as alkyl glycooxides and sucrose fatty acid esters.

Further, as the above-mentioned anionic surfactant,
For example, sulfates such as higher alcohol sulfates, higher alkyl ether sulfates and sulfated fatty acid esters, sulfonates such as alkyl benzene sulfonates and alkyl naphthalene sulfonic acids, higher alcohol phosphates, higher alcohol phosphates and the like. Phosphoric acid ester salts such as alkylene oxide adducts of alcohols and the like.

Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene; ketones such as acetone and methyl ethyl ketone;
Examples thereof include ethers such as dioxane and ethyl cellosolve, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and halogenated hydrocarbons such as methylene chloride and chloroform.

The above-mentioned surfactants and organic solvents may be used alone or, if necessary, in combination of two or more.

According to the present invention, the binder resin is
It is preferably used in the range of 5 to 100 parts by weight, more preferably 8 to 80 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the phosphoric ester flame retardant. Used in the range.

When the amount of the binder resin is less than 5 parts by weight with respect to 100 parts by weight of the phosphoric ester flame retardant, the flame retardancy of the polyester fiber product which has undergone the flame retardancy is reduced, especially the durability to dry cleaning. It will be inferior. On the other hand, when the binder resin is more than 100 parts by weight based on 100 parts by weight of the phosphate ester flame retardant,
The feeling of the flame-retarded polyester fiber product is remarkably reduced, and particularly when the polyester fiber product is a fabric, it becomes extremely coarse and hard.

Further, according to the present invention, the adhesion amount of the polyester fiber product of the phosphate ester flame retardant is preferably in the range of 1 to 20% by weight, particularly 5 to 15% by weight.
A range of weight% is preferred. When the amount of the phosphate ester flame retardant attached to the polyester fiber product is less than 1% by weight, the flame retardancy may be insufficient.
If the amount exceeds 10% by weight, the fiber product may have a sticky feeling or the dyeing fastness may decrease.

According to the present invention, in order to apply a phosphate ester flame retardant to a polyester fiber product by using the above binder resin, an appropriate method conventionally known may be used according to the form of the fiber product. For example, when the fiber product is a fabric, a conventionally known appropriate method such as a padding method may be used. If necessary, a functional processing agent such as a softening agent or an antistatic agent can be added as long as the flame retardancy of the polyester fiber product is not impaired.

For example, in order to flame-retard a polyester fiber cloth by a padding method, more specifically, after a polyester fiber cloth is dyed, a phosphate ester flame retardant is added to the polyester fiber cloth using the binder resin. The fabric is subjected to a flame-retardant treatment, and then dried at a temperature of 120 to 130 ° C, and then subjected to a heat treatment at a temperature of 150 to 190 ° C.

[0084]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In Examples and Comparative Examples, "parts" is parts by weight in terms of solid content. The evaluation of the flame retardancy and its durability was performed as follows.

(1) Flame Retardancy A flame-retardant cloth and a cloth which was washed five times with water or dry-cleaned (DC) five times were subjected to JIS L
1091 A-1 method (micro burner method) and JIS
The evaluation was performed by the L 1091 D method (coil method). In the micro-burner method, the residual flame is less than 3 seconds, the residual dust is less than 5 seconds, and the carbonization area is 30c.
Those within m ² were rated as ○. In the coil method, if the number of times of flame contact is 3 or more, it can be said that the flame retardancy is excellent.

The water washing and the dry cleaning were performed as follows. (Water washing) Washing: 60 ± 2 ° C. × 15 minutes (JIS K 3371 weak alkaline type 1 detergent 1 g / L), bath ratio 1:40 Rinsing: 40 ± 2 ° C. × 5 minutes × 3 times Dehydration: Centrifugal dehydration 2 Minute drying: hot air drying 60 ± 5 ° C. The above was regarded as one cycle, and a total of five cycles were performed.

(Dry cleaning) 30 ± 2 ° C. × 15 minutes Per gram of sample, 2.6 mL of tetrachloroethylene,
Charge soap (nonionic surfactant (nonylphenol ether ethylene oxide 10 mol adduct): anionic surfactant (dioctyl sulfosuccinate sodium salt): water = 10: 10: 1) 0.265 g Five cycles were performed.

(2) Hand The flame-retardant processed polyester fiber cloth is JIS
L 1079, 5.17, and the evaluation was made by the bending resistance A method (45 ° cantilever method), and the average value was obtained.

Examples 1 to 3 and Comparative Examples 1 to 3 (Sample polyester fiber cloth) A 75 denier / 72 filament full dull yarn made of polyester fiber was used as a warp, and a 150 denier / 64 filament black soaked weft was used. A woven fabric having a warp density of 368 yarns / inch, a weft density of 71 yarns / inch, and a basis weight of 239 g / m ² was subjected to scouring, presetting, and dyeing by a usual method to obtain a sample polyester fiber cloth. .

(Production of Aqueous Dispersion of Binder Resin A) 129 parts of dimethyl terephthalate, ethylene glycol 3
14 parts and 127 parts of a dicarboxylic acid dimethyl ester composed of the phosphinic acid derivative of the above formula (5) (molar ratio of dimethyl terephthalate: ethylene glycol: dicarboxylic acid dimethyl ester composed of phosphinic acid derivative =
1: 7.6: 0.51), 0.1% by weight of manganese acetate, 0.5% by weight of lithium acetate and 0.5% by weight based on the total weight of the dimethyl ester of dicarboxylic acid composed of the dimethyl terephthalate and the phosphinic acid derivative. 0.03% by weight
Of antimony trioxide as a catalyst, and the mixture
After a transesterification reaction at 0 to 220 ° C, polymerization was performed at 240 ° C under reduced pressure to obtain a polyester having a weight average molecular weight of 5,500.

150 parts of this polyester, 100 parts of dimethylformamide and 50 parts of a nonionic surfactant nonylphenol ethylene oxide 15 mol adduct were added at 80 ° C.
And then gradually added 700 parts of 80 ° C. hot water to form particles, and then cooled to room temperature. The obtained particles were pulverized by a wet pulverizer to obtain 1,000 parts of an aqueous dispersion of particles of the polyester having a particle diameter of 0.4 μm. This is used as an aqueous dispersion of the binder resin A.

(Production of aqueous dispersion of binder resin B) 129 parts of dimethyl terephthalate, ethylene glycol 4
34 parts and 125 parts of a dimethyl ester of a dicarboxylic acid comprising a phosphinic acid derivative of the above formula (6) (molar ratio of dimethyl terephthalate: ethylene glycol: dimethyl ester of a dicarboxylic acid comprising a phosphinic acid derivative =
1: 10.5: 0.52), 0.1% by weight of manganese acetate, 0.5% by weight of lithium acetate and 0.5% by weight based on the total weight of the dimethyl terephthalate and the dimethyl ester of the dicarboxylic acid comprising a phosphinic acid derivative. 0.03% by weight of antimony trioxide was mixed as a catalyst,
After a transesterification reaction at 60 to 220 ° C, 250 ° C
Under reduced pressure to obtain a polyester having a weight average molecular weight of 14,500.

150 parts of the polyester, 100 parts of dimethylformamide, 30 parts of a nonionic surfactant nonylphenol ethylene oxide 15 mol adduct and 80 mol of lauryl alcohol ethylene oxide adduct were mixed with 80 parts.
The resulting mixture was uniformly dissolved at a temperature of 700 ° C., and 700 parts of hot water at 80 ° C. was gradually added thereto to form particles, followed by cooling to room temperature. The obtained particles are pulverized by a wet pulverizer to obtain a particle diameter of 0.4 μm.
To obtain 1000 parts of an aqueous dispersion of particles of the above polyester. This is used as an aqueous dispersion of the binder resin B.

(Production of Aqueous Dispersion of Flame Retardant C) 500 parts of t-butyldiphenyl phosphate and 60 parts of a nonionic surfactant sorbitan monostearate ethylene oxide (20 mol) were uniformly dissolved at 60 ° C.
The mixture was gradually added to 440 parts of warm water at ℃ and emulsified to obtain 1000 parts of an emulsion. This is used as an aqueous dispersion of the flame retardant C.

(Production of Flame Retardant D) 450 parts of resorcinol bis (diphenyl phosphate), 50 parts of a nonionic surfactant stearyl alcohol ethylene oxide (50 parts) and 100 parts of toluene were uniformly dissolved at 60 ° C. The mixture was gradually added to 400 parts of warm water at 60 ° C. and emulsified to obtain 1,000 parts of an emulsion. This is used as an aqueous dispersion of the flame retardant D.

As shown in Table 1, the above sample polyester fiber cloth was immersed in an aqueous dispersion of a binder resin, an aqueous dispersion of a flame retardant, or a mixture thereof at room temperature, and the drawing ratio was set to 70%. Squeeze with mangle, then 120 ° C
For 3 minutes, heat and dry at 180 ° C. for 2 minutes, heat-treat, scour at a bath ratio of 1:30, temperature of 80 ° C., heat and dry at 120 ° C. for 3 minutes, 180 1 in ° C
Heating for a minute and heat treatment were performed to evaluate the initial flame retardancy and the flame retardancy after washing. Table 1 shows the results.

Comparative Example 4 Table 1 shows the flame retardancy of the sample polyester fiber fabric itself before the flame retarding treatment.

[0098]

[Table 1]

As shown in Comparative Example 1, when the sample polyester fiber cloth was flame-retarded using only the phosphate ester as a flame retardant, the feeling of the cloth was clear as compared with Comparative Example 4. Although almost the same as before the flame-retardant processing, the flame retardancy is inferior to the dry cleaning resistance. On the other hand, as shown in Comparative Examples 2 and 3, when only a polyester containing a dicarboxylic acid component unit composed of a phosphinic acid derivative is used as a flame retardant, a large amount is fixed to improve the washing resistance and the dry cleaning resistance. Although excellent flame retardancy can be imparted, the fabric becomes extremely coarse and hard. However, if a small amount is fixed to suppress the reduction in hand, the desired flame retardancy cannot be imparted.

However, as shown in Examples 1-3, according to the present invention, a polyester containing a dicarboxylic acid component unit composed of a phosphinic acid derivative was used as a binder resin, and a flame retardant composed of a phosphate ester was used as a sample polyester fiber cloth. By adhering to the fabric, it is possible to impart not only washing resistance but also flame retardancy which is excellent not only in dry cleaning resistance, but also while maintaining the soft feeling without making the cloth coarse and hard.

[0101]

As described above, the flame retardant for polyester fiber products according to the present invention is a polyester containing a dicarboxylic acid comprising the halogen-free phosphate ester flame retardant and the phosphinic acid derivative as a dicarboxylic acid component unit. By adhering such a flame-retardant processing agent to polyester fiber products, it does not reduce the feeling of the fiber products, and is not only durable, that is, not only washing-resistant but also dry-resistant. Flame retardancy, which is also excellent in cleaning properties, can be provided.

In particular, according to the present invention, the polyester fiber cloth can be subjected to flame-retardant processing while keeping its soft feel without making it rough. Therefore, the flame-retardant agent and the flame-retardant method according to the present invention are not particularly limited, but are suitable for, for example, flame-retardant processing of polyester fiber cloth such as curtains, blackout curtains, curtains, carpets, and fabric blinds. is there.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Kazuyuki Oya, 167 Nunu, Hamacho, Negami-cho, Nomi-gun, Ishikawa Prefecture (72) Kounosuke Uozumi 167 Nunu, Hamacho, Negami-cho, Nomi-gun, Ishikawa Komatsu Seiren Co., Ltd. (72) Inventor Seiji Horie 11-11, Hitotsubashi-Honcho, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Teruhumi Iwaki 1 Nishinokyo Uchihata-cho, Nakagyo-ku, Kyoto Daikyo Chemical Co., Ltd. (72) Invention Person Katsuo Sasa 1 Nishinokyo Uchihata-cho, Nakagyo-ku, Kyoto F-term (reference) in Daikyo Chemical Co., Ltd. 4L033 AA07 AB01 AB05 AB06 AC05 BA39 CA46

Claims (11)

[Claims] 1. A flame retardant comprising (A) a halogen-free phosphate ester and (B) a general formula (I) (Wherein, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms,
It represents an arylalkyl group having 7 to 18 carbon atoms and having an aryl group of 14 or an aryl group of 6 to 14 carbon atoms as a substituent. However, R ¹ and R ² may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n
Is an integer of 0 to 2. A) a binder resin comprising a polyester having a dicarboxylic acid composed of a phosphinic acid derivative represented by formula (I) as a dicarboxylic acid component unit, having a weight average molecular weight in the range of 1,000 to 50,000, and a phosphorus content in the range of 2 to 10% by weight; A flame retardant for polyester fiber products, comprising: 2. A dicarboxylic acid comprising a phosphinic acid derivative represented by the general formula (II): (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A and b are each an integer of 0 to 4, and n is an integer of 0 to 2. Is.)
And a dicarboxylic acid represented by the general formula (III): (Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. C and d are each an integer of 0 to 4, and n is an integer of 0 to 2. Is.)
The flame retardant for polyester fiber products according to claim 1, which is at least one member selected from the group consisting of dicarboxylic acids represented by the formula: 3. The phosphoric ester of the general formula (IV) (Wherein, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a carbon atom having an aryl group having 6 to 14 carbon atoms as a substituent. The polyester according to claim 1 or 2, wherein an arylalkyl group represented by Formulas 7 to 18, Z represents a divalent organic group, and m represents an integer of 0 to 5). Flame retardant for textile products. 4. A flame retardant (A) 10 comprising a phosphate ester
The flame retardant for polyester fiber products according to any one of claims 1 to 3, comprising 5 to 100 parts by weight of the binder resin (B) with respect to 0 parts by weight. 5. A flame retardant comprising (A) a halogen-free phosphoric acid ester, (B) a compound represented by the following general formula (I): (Wherein, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms,
It represents an arylalkyl group having 7 to 18 carbon atoms and having an aryl group of 14 or an aryl group of 6 to 14 carbon atoms as a substituent. However, R ¹ and R ² may combine with each other to form a ring together with the phosphorus atom P and the oxygen atom O. n
Is an integer of 0 to 2. A) a binder resin comprising a polyester having a dicarboxylic acid composed of a phosphinic acid derivative represented by the formula (1) as a dicarboxylic acid component unit, having a weight average molecular weight in the range of 1,000 to 50,000, and a phosphorus content in the range of 2 to 10% by weight. A flame-retardant processing method for a polyester fiber product, wherein the method is used to adhere to a polyester fiber product. 6. A dicarboxylic acid comprising a phosphinic acid derivative represented by the general formula (II): (Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A and b are each an integer of 0 to 4, and n is an integer of 0 to 2. Is.)
And a dicarboxylic acid represented by the general formula (III): (Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. C and d are each an integer of 0 to 4, and n is an integer of 0 to 2. Is.)
The flame-retardant processing method for a polyester fiber article according to claim 5, which is at least one selected from dicarboxylic acids represented by the following formulae: 7. The phosphoric ester of the general formula (IV) (Wherein, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each represent an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aryl group having 6 to 14 carbon atoms as a substituent. The polyester according to claim 5 or 6, wherein an arylalkyl group represented by Formulas 7 to 18, Z represents a divalent organic group, and m represents an integer of 0 to 5.) Flame retardant processing method for textiles. 8. A flame retardant (A) 10 comprising a phosphate ester
The method for flame-retarding polyester fiber products according to any one of claims 5 to 7, comprising 5 to 100 parts by weight of the binder resin (B) based on 0 parts by weight. 9. The flame-retardant processing of a polyester fiber article according to claim 5, wherein the flame retardant (A) comprising a phosphate ester is fixed in the range of 1 to 20% by weight based on the polyester fiber article. Law. 10. A flame-retardant polyester fiber product obtained by fixing the flame-retardant agent according to claim 1 to a polyester fiber product. 11. A flame-retardant polyester fiber product obtained by flame-retarding a polyester fiber product by the method according to claim 5.