JP6039326B2 - Flame-retardant finishing agent for polyester fiber, and method for producing flame-retardant polyester fiber product using the same - Google Patents

Description

  The present invention relates to a flame retardant processing agent for polyester fibers and a method for producing a flame retardant polyester fiber product using the same.

  Conventionally, as a durable flame retardant processing of a polyester fiber, a processing method using an alicyclic halogen compound represented by hexabromocyclododecane (hereinafter abbreviated as HBCD) as a flame retardant component has been mainstream. However, HBCD has been designated as a first-class monitoring chemical because it has been found to be highly degradable and highly accumulative, and in response to this, the desirability of dehalogenated flame retardants has increased in the automotive and textile industries. Has a policy to abolish the use of HBCD.

  As the flame retardant component replacing HBCD, for example, various phosphorus compounds as described in JP-A-2006-299486 (Patent Document 1) have been studied. It is described that a flame retardant having excellent durability is imparted to a polyester fiber by a compound. However, since these phosphorus compounds tend to be inferior in flame retardant effect compared to HBCD, studies on halogen compounds have been continued. Examples of such halogen compounds include tris (2,3-dibromo). Propyl) isocyanurate has attracted attention.

  However, when a halogen compound such as tris (2,3-dibromopropyl) isocyanurate is applied to the polyester fiber, there is a problem that the texture of the obtained flame-retardant polyester fiber product tends to be cured. Therefore, in Japanese Patent Application Laid-Open No. 2009-174109 (Patent Document 2), for the purpose of making the texture of the flame-retardant polyester fiber product flexible, for example, tris (2,3-dibromopropyl) isocyanurate is used. And use of a liquid phosphorus compound such as tris (dichloropropyl) phosphate. However, in the flame-retardant polyester fiber product obtained by using these liquid phosphorus compounds in combination, although there is a tendency that the texture becomes flexible to some extent, there is a problem that the friction fastness and the durability flame resistance are lowered. It was.

  In JP 2009-203595 A (Patent Document 3), for the purpose of improving the texture of the flame-retardant polyester fiber product, a halogen compound such as tris (2,3-dibromopropyl) isocyanurate is used. For example, it is described that phosphorus compounds such as triphenyl phosphate, 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are used in combination. However, the flame-retardant polyester fiber product obtained by using these phosphorus compounds in combination has a problem that the texture is not yet sufficient.

  Furthermore, JP2011-12352A (Patent Document 4) describes tris (2) by treating polyester fibers with tris (2,3-dibromopropyl) isocyanurate in the presence of a specific polyester resin. , 3-Dibromopropyl) isocyanurate is disclosed to suppress the curing of the texture. However, the flame-retardant polyester fiber product obtained by the method of Patent Document 4 also has a problem that the texture is not yet sufficient.

JP 2006-299486 A JP 2009-174109 A JP 2009-203595 A JP 2011-12352 A

  In the flame retardant processing agent in which the halogen compound such as tris (2,3-dibromopropyl) isocyanurate is combined with, for example, a surfactant described in Patent Document 3, the present inventors have demonstrated product stability. It has been found that there are problems that separation and precipitation occur when stored for a long period of time, and that the resulting flame-retardant polyester fiber product has insufficient friction fastness.

  The present invention has been made in view of the above-described problems of the prior art, has excellent stability, can impart sufficient flame retardancy with excellent durability to a polyester fiber, and is obtained. To provide a flame retardant processing agent for polyester fibers capable of sufficiently suppressing deterioration in fastness and texture hardening of a flame retardant polyester fiber product, and a method for producing a flame retardant polyester fiber product using the same. Objective.

  As a result of intensive studies to achieve the above object, the present inventors have used a specific halogen compound as a flame retardant component in a flame retardant processing agent, and by combining the specific compound, In addition, it can provide sufficient flame resistance with excellent durability, and in the obtained flame-retardant polyester fiber product, various fastnesses such as fastness to friction and fastness to light, and to flame-retardant components It has been found that it is possible to sufficiently suppress the resulting texture hardening. Furthermore, the present inventors have found that the above-mentioned effects can be achieved by the combined use of the halogen compound and the specific compound, and that the exhaust rate of the halogen compound to the polyester fiber is improved, thereby completing the present invention. It came to do.

That is, the flame retardant for polyester fiber of the present invention is
It contains at least one compound (A) selected from the group consisting of the following compounds (a ¹ ) to (a ³ ) and the following halogen compound (B).
<Compound (a ¹ )>
The following general formula (1):

[In Formula (1), R ¹ and R ³ are either R ¹ and R ³ each representing a hydrogen atom , or ^one of R ¹ and R ³ is a hydrogen atom and the other is represented by the following general formula ( 1a ):
-SO ₃ M ··· (1a)

Wherein (1a), M represents a water atom or a monovalent cation group. ]
In denotes an anion group represented, R ² is each independently an alkylene group having 2 to 4 carbon atoms, a is an average addition mole number of alkylene group represented by (R 2 ^-O) An integer of 3 to 1000 is shown. However, the content of the ethyleneoxy group with respect to the total amount of the oxyalkylene chain represented by (R ² —O) _a is 90% by mass or more. ]
A compound represented by
<Compound (a ² )>
The following general formula (2):

[In the formula (2), R ⁴ represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms and a c valence, or a fatty acid in which a part of carbon atoms of the aliphatic hydrocarbon group is substituted with an oxygen atom. shows a family group, ^{R 5} is each independently an alkylene group having 2 to 4 carbon atoms, ^{R 6} are each independently a hydrogen atom, lower following general formula (1a) ~ (1g):
[In formulas (1a) to (1g), M independently represents a hydrogen atom or a monovalent cation group. ]
Selected from the group consisting of an anionic group represented by any one of the above, an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, and an alkynylcarbonyl group having 2 to 22 carbon atoms. indicates either, b is an average addition mole number of alkylene group represented by ^(R 5 -O), independently represents an integer of 0 to 1000, c is an integer of 2 to 10 . However, the sum total of all b is 3-1000, and content of the ethyleneoxy group with respect to the total amount of the oxyalkylene chain represented by (R < ⁵ > -O) _b is 90 mass% or more. ]
A compound represented by
<Compound (a ³ )>
The following general formula (3):

[In Formula (3), R ⁷ represents an aliphatic hydrocarbon group having 1 to 21 carbon atoms and an e valence, R ⁸ independently represents an alkylene group having 2 to 4 carbon atoms, and R ⁹ Are each independently a hydrogen atom, an anionic group represented by any one of the general formulas (1a) to (1g), an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, Any one selected from the group consisting of an alkynyl group having 2 to 22 carbon atoms, an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, and an alkynylcarbonyl group having 2 to 22 carbon atoms , D is the average number of added moles of the alkyleneoxy group represented by (R ⁸ —O), and each independently represents an integer of 0 to 1000, and e represents an integer of 2 to 10. However, the total of all d is 3 to 1000, and the content of ethyleneoxy groups with respect to the total amount of oxyalkylene chains represented by (R ⁸ —O) _d is 90% by mass or more. ]
A compound represented by
<Halogen compound (B)>
The following general formula (4):

[In Formula (4), Y ^{1 to} Y ³ are each independently selected from the group consisting of 2,3-dibromopropyl group, 2,3-dibromoisobutyl group and 1,2-dibromoethyl group. The group of is shown. ]
A halogen compound represented by

  Moreover, as a flame retardant processing agent for polyester fibers of this invention, mass ratio (A: B) of content of the said compound (A) and content of the said halogen compound (B) is 1: 100-50: 100 is preferable.

  The method for producing a flame-retardant polyester fiber product of the present invention is characterized in that the polyester fiber is treated using the flame-retardant processing agent for polyester fiber of the present invention.

  According to the present invention, it is excellent in stability, can impart sufficient flame retardancy excellent in durability to the polyester fiber, and the exhaust rate of the flame retardant component in the polyester fiber is sufficiently high. Nevertheless, the flame retardant polyester fiber product that can sufficiently suppress the decrease in fastness and texture hardening of the obtained flame retardant polyester fiber product, and the production of the flame retardant polyester fiber product using the same It becomes possible to provide a method.

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

The flame retardant processing agent for polyester fibers of the present invention contains at least one compound (A) selected from the group consisting of the compounds (a ¹ ) to (a ³ ), and the halogen compound (B). It is characterized by.

(Compound (A))
The compound (A) according to the present invention is at least one selected from the group consisting of the following compounds (a ¹ ) to (a ³ ).

<Compound (a ¹ )>
The compound (a ¹ ) according to the present invention is a compound represented by the following general formula (1).

In the formula (1), R ¹ is a hydrogen atom, the following general formulas (1a) to (1g):

[In formulas (1a) to (1g), M independently represents a hydrogen atom or a monovalent cation group. ]
An anionic group represented by any of the above, an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an alkylcarbonyl group having 1 to 22 carbon atoms, Any one selected from the group consisting of an alkenylcarbonyl group having 2 to 22 carbon atoms and an alkynylcarbonyl group having 2 to 22 carbon atoms, wherein R ³ is a hydrogen atom, of the above general formulas (1a) to (1g); Any selected from the group consisting of an anionic group represented by any of these, an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, and an alkynylcarbonyl group having 2 to 22 carbon atoms Indicate.

When R ¹ or R ³ is an anionic group represented by any one of the above general formulas (1a) to (1g), M is a viewpoint that the action of inhibiting flame retardancy tends to be weak. Therefore, sodium, potassium, and ammonium are preferable. In the present invention, the anionic group may be an acidic group excluding the cationic group, and the degree of neutralization thereof is not particularly limited and can be appropriately adjusted.

R ¹ or R ³ is an alkylcarbonyl group having 1 to 22 carbon atoms (the alkyl group has 1 to 22 carbon atoms, the same applies hereinafter), an alkenylcarbonyl group having 2 to 22 carbon atoms (the alkenyl group has 2 to 22 carbon atoms, The same shall apply hereinafter) or an alkynylcarbonyl group having 2 to 22 carbon atoms (wherein the alkynyl group has 2 to 22 carbon atoms, the same shall apply hereinafter) and the friction fastness of the flame-retardant polyester fiber product obtained when the carbon number exceeds the upper limit. The degree decreases. Moreover, as these carbon number, it is preferable that it is 8 or less from a viewpoint that it exists in the tendency which can suppress the fall of friction fastness more.

In addition, when R ¹ is an alkyl group having 1 to 9 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an alkynyl group having 2 to 22 carbon atoms, a flame retardant for polyester fibers when the carbon number exceeds the upper limit. Product stability and friction fastness of the resulting flame retardant polyester fiber product are reduced. Moreover, as these carbon number, it is preferable that it is 8 or less from a viewpoint that it exists in the tendency which can suppress the fall of friction fastness more.

Among these, as R ¹ and R ³ , it is possible to impart more excellent flame retardancy to the polyester fiber, and the viewpoint that the texture hardening of the obtained flame-retardant polyester fiber product tends to be further suppressed. From the above, R ¹ and R ³ are both hydrogen atoms, or R ¹ and R ³ are hydrogen atoms, and the other is an anionic group represented by the general formula (1a). Is preferred.

In the formula (1), ^{R 2} represents an alkylene group having 2 to 4 carbon atoms independently. Examples of such an alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Further, the formula ^(1), a is an integer of 3 to 1000 and an average addition mole number of alkylene group represented by ^(R 2 -O). When a is less than the lower limit, the flame retardancy and friction fastness of the resulting flame-retardant polyester fiber product are lowered, and the texture and haze are deteriorated. On the other hand, when the above upper limit is exceeded, not only the flame retardancy and friction fastness of the resulting flame-retardant polyester fiber product are lowered, but also the handling of the compound represented by the formula (1) becomes difficult or for polyester fibers. The product stability of the flame retardant is reduced. Further, as such a, it is possible to impart more excellent durability flame resistance to the polyester fiber, and lower the haze value in the obtained flame retardant polyester fiber product (the haze value is better). From the viewpoint that the decrease in friction fastness and the hardening of the texture can be further suppressed, the integer is preferably 5 to 100, and more preferably 5 to 50.

However, in the compound (a ¹ ) represented by the formula (1), the content of the ethyleneoxy group with respect to the total amount of oxyalkylene chains represented by (R ² —O) _a is 90% by mass or more. When the content of the ethyleneoxy group is less than the lower limit, the flame retardancy and friction fastness of the obtained flame retardant polyester fiber product are lowered. In addition, the water solubility of the compound (a ¹ ) is improved, the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber is further improved, and the durable flame retardant is superior to the polyester fiber. From the viewpoint that the flame retardant polyester fiber product obtained tends to be able to further suppress the texture hardening and the reduction in friction fastness, the ethyleneoxy group of the total amount of the oxyalkylene chain. As content, it is preferable that it is 95 mass% or more, and it is more preferable that it is 100 mass%.

Such a compound (a ¹ ) can be obtained, for example, according to a conventional method: (I) a method of polymerizing alkylene oxide; (II) a compound obtained by (I) (ie, polyalkylene glycol) and C 2-22 A method of reacting a fatty acid or a lower alcohol ester thereof; (III) a method of adding an alkylene oxide to an alcohol; (IV) a method of anionizing a compound obtained in (I), (II) or (III) Can be obtained. In such a method, the order of reaction, the order of addition of raw materials, and the like can be changed as appropriate.

<Compound (a ² )>
The compound (a ² ) according to the present invention is a compound represented by the following general formula (2).

In the formula (2), R ⁴ is an aliphatic hydrocarbon group having 1 to 22 carbon atoms and a c valence, or a part of carbon atoms of the aliphatic hydrocarbon group is substituted with an oxygen atom. An aliphatic group is shown. The aliphatic hydrocarbon group and the aliphatic group may be linear, branched or cyclic, and may be saturated or unsaturated. In R ^4, when the number of carbon atoms exceeds the upper limit, the flame retardancy, rubbing fastness of the flame retardant polyester fiber products obtained decreases, texture is deteriorated. Further, the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber can be further improved, and more excellent flame retardancy can be imparted to the polyester fiber. From the standpoint that it is possible to further suppress the texture hardening and friction fastness of the flame-retardant polyester fiber product, R ⁴ preferably has 1 to 18 carbon atoms, specifically, , Pentaerythritol residues (residues excluding at least one hydroxy group), dipentaerythritol residues, tripentaerythritol residues, trimethylolpropane residues, ditrimethylolpropane residues, tritrimethylolpropane More preferably a residue of polyglyceryl ether, a residue of sorbitan, and in particular, a branched chain More preferably.

Further, in the above formula (2), c is a valency of ^{R 4,} represents an integer of 2 to 10. When c exceeds the upper limit, the flame retardancy and friction fastness of the resulting flame retardant polyester fiber product are lowered. As such c, the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber can be further improved, and more excellent flame resistance can be imparted to the polyester fiber. From the viewpoint that it is possible to further suppress the decrease in texture hardening and friction fastness of the obtained flame-retardant polyester fiber product, an integer of 2 to 8 is preferable.

Furthermore, in said formula (2), R < ⁵ > shows a C2-C4 alkylene group each independently. Examples of such an alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Further, in the above formula (2), b indicates the 0 to 1000 each independently an average number of added moles of alkylene group represented by ^(R 5 -O). However, the sum of all b is 3 to 1000. When the sum of b is less than the lower limit, the flame retardancy and friction fastness of the resulting flame-retardant polyester fiber product are lowered, and the texture and haze are deteriorated. On the other hand, when the above upper limit is exceeded, not only the flame retardancy and friction fastness of the resulting flame-retardant polyester fiber product are lowered, but also the handling of the compound represented by the formula (2) becomes difficult or for polyester fibers. The product stability of the flame retardant is reduced. Further, as such b, it is possible to impart more excellent durability flame resistance to the polyester fiber, and lower the haze value in the obtained flame retardant polyester fiber product (the haze value is better). From the viewpoint that the decrease in friction fastness and the hardening of the texture can be further suppressed, the total of all b is preferably 10 to 100, and more preferably 10 to 50.

Moreover, as the formula (2) compounds represented by (a ^2), is (R 5 ^-O) content of ethyleneoxy groups to the total amount of the oxyalkylene chain represented by _b is 90 mass% or more. When the content of the ethyleneoxy group is less than the lower limit, the flame retardancy and friction fastness of the obtained flame retardant polyester fiber product are lowered. In addition, the water solubility of the compound (a ² ) is improved, the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber is further improved, and the durable flame retardant is superior to the polyester fiber. From the viewpoint that the flame retardant polyester fiber product obtained tends to be able to further suppress the texture hardening and the reduction in friction fastness, the ethyleneoxy group of the total amount of the oxyalkylene chain. As content, it is preferable that it is 95 mass% or more, and it is more preferable that it is 100 mass%.

In the formula (2), R ⁶ is a hydrogen atom, an anionic group represented by any one of the general formulas (1a) to (1g), an alkylcarbonyl group having 1 to 22 carbon atoms, and 2 carbon atoms. Any one selected from the group consisting of ˜22 alkenylcarbonyl groups and alkynylcarbonyl groups of 2-22 carbon atoms is shown.

When R ⁶ is the anionic group, M is preferably sodium, potassium, or ammonium from the viewpoint that the effect of inhibiting flame retardancy tends to be weak. In the present invention, the anionic group may be an acidic group excluding the cationic group, and the neutralization degree is not particularly limited and can be appropriately adjusted.

When R ⁶ is an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, or an alkynylcarbonyl group having 2 to 22 carbon atoms, the flame retardant polyester obtained when the carbon number exceeds the upper limit The texture of the textile product is hardened and the fastness to friction is reduced. In addition, R ⁶ is preferably an alkenylcarbonyl group having 2 to 22 carbon atoms from the viewpoint of being able to further suppress texture hardening and lowering of friction fastness, and specifically, the residual oleic acid. A group (residue obtained by removing OH from a carboxyl group) is preferred.

Among these, as R ⁶ , the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber is further improved, and the resulting flame retardant polyester fiber product has a texture hardening and friction fastness. From the viewpoint that the lowering tends to be further suppressed, it is preferably a hydrogen atom, an alkenylcarbonyl group having 2 to 22 carbon atoms, or the anionic group, and a hydrogen atom or an alkenylcarbonyl group having 2 to 22 carbon atoms. The anionic group represented by the general formula (1a) is more preferable.

Such a compound (a ² ) is obtained by, for example, reacting a c-valent aliphatic hydroxy compound represented by (V) R ⁴ (OH) _c with an alkylene oxide according to a conventional method; (VI) (V ), A method of further reacting in combination with a fatty acid having 2 to 22 carbon atoms or a lower alcohol ester thereof; (VII) a method obtained by anionizing the compound obtained in (V) or (VI) . In such a method, the order of reaction, the order of addition of raw materials, and the like can be changed as appropriate.

<Compound (a ³ )>
The compound (a ³ ) according to the present invention is a compound represented by the following general formula (3).

In the formula (3), R ⁷ represents an aliphatic hydrocarbon group having 1 to 21 carbon atoms and having an e value. The aliphatic hydrocarbon group may be linear, branched or cyclic, saturated or unsaturated. In R ^7, when the number of carbon atoms exceeds the upper limit, the flame retardancy, rubbing fastness of the flame retardant polyester fiber products obtained decreases and also, texture is deteriorated. As such R ⁷ , the exhaustion rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber is further improved, and it is possible to impart superior durability flame resistance to the polyester fiber. In addition, from the viewpoint that the resulting flame-retardant polyester fiber product tends to be able to further suppress texture hardening and friction fastness, the number of carbon atoms is preferably 1-18, and is chain-like. More preferably, it is more preferably branched.

Further, in the above formula (3), e is a valence of ^{R 7,} represents an integer from 2 to 10. When e exceeds the above upper limit, the flame retardancy and friction fastness of the flame retardant polyester fiber product obtained are lowered. As such e, the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber can be further improved, and more excellent flame resistance can be imparted to the polyester fiber. From the viewpoint that it is possible to further suppress the decrease in texture hardening and friction fastness of the obtained flame-retardant polyester fiber product, an integer of 2 to 8 is preferable.

Furthermore, in said formula (3), R < ⁸ > shows a C2-C4 alkylene group each independently. Examples of such an alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Further, in the above formula (3), d represents an integer of 0 to 1000 each independently an average number of added moles of alkylene group represented by ^(R 8 -O). However, the sum of all d is 3 to 1000. If the sum of d is less than the lower limit, the flame retardancy and friction fastness of the resulting flame-retardant polyester fiber product are lowered, and the texture and haze are deteriorated. On the other hand, when the above upper limit is exceeded, not only the flame retardancy and friction fastness of the resulting flame-retardant polyester fiber product are lowered, but also the handling of the compound represented by the formula (3) becomes difficult or for polyester fibers. The product stability of the flame retardant is reduced. As such d, it is possible to impart more excellent durability flame retardancy to the polyester fiber, and lower the haze value in the obtained flame-retardant polyester fiber product (the haze value becomes better). From the viewpoint that the decrease in friction fastness and the hardening of the texture can be further suppressed, the total of all d is preferably 10 to 100, more preferably 10 to 50.

Further, the formula compounds represented by (3) as (a ³⁾ is (R 8 ^-O) content of ethyleneoxy groups to the total amount of the oxyalkylene chain represented by _d 90 mass% or more. When the content of the ethyleneoxy group is less than the lower limit, the flame retardancy and friction fastness of the obtained flame retardant polyester fiber product are lowered. Further, the water solubility of the compound (a ³ ) is improved, the exhaust rate of the flame retardant component (A) to the polyester fiber is further improved, and the durability and flame retardancy is imparted to the polyester fiber. From the viewpoint of being able to further suppress the decrease in texture hardening and friction fastness of the obtained flame-retardant polyester fiber product, the content of ethyleneoxy groups relative to the total amount of the oxyalkylene chains is as follows: It is preferably 95% by mass or more, and more preferably 100% by mass.

In the formula (3), each R ⁹ is independently a hydrogen atom, an anionic group represented by any one of the general formulas (1a) to (1g), an alkyl group having 1 to 22 carbon atoms, It consists of an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, and an alkynylcarbonyl group having 2 to 22 carbon atoms. Any one selected from the group is indicated.

When R ⁹ is an anionic group represented by the above general formulas (1a) to (1g), M is sodium, potassium, or ammonium from the viewpoint that the effect of inhibiting flame retardancy tends to be weak. Preferably there is. In the present invention, the anionic group may be an acidic group excluding the cationic group, and the neutralization degree is not particularly limited and can be appropriately adjusted.

R ⁹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkynyl group having 2 to 22 carbon atoms, an alkylcarbonyl group having 1 to 22 carbon atoms, and an alkenylcarbonyl having 2 to 22 carbon atoms. When the group is an alkynylcarbonyl group having 2 to 22 carbon atoms, the texture of the flame-retardant polyester fiber product obtained when the carbon number exceeds the upper limit is cured or the friction fastness is lowered.

Among these, as R ⁹ , the exhaust rate of the flame retardant component such as the following halogen compound (B) to the polyester fiber is further improved, and the resulting flame retardant polyester fiber product has a texture hardening and friction fastness. From the viewpoint that the lowering tends to be further suppressed, a hydrogen atom or the anionic group is preferable.

Such a compound (a ³ ) is obtained by, for example, reacting an e-valent aliphatic carboxy compound represented by (VIII) R ⁷ (COOH) _e with an alkylene oxide or polyalkylene glycol according to a conventional method; IX) A method in which a fatty acid having 2 to 22 carbon atoms or a lower alcohol ester thereof is further used in the reaction during or after the reaction of (VIII); (X) Anionization of the compound obtained in (VIII) or (IX) Can be obtained by the following method. In such a method, the order of reaction, the order of addition of raw materials, and the like can be changed as appropriate.

As the compound (A) according to the present invention, any one selected from the group consisting of the above compounds (a ¹ ) to (a ³ ) may be used alone, or two or more may be used in combination. Good. Among such compounds (A), the product stability is superior, the durability and flame retardancy can be imparted to the polyester fiber, and the resulting cured flame retardant polyester fiber product has a reduced texture. From the viewpoint of being able to suppress more, it is preferably at least one selected from the group consisting of the compounds (a ¹ ) to (a ² ), polyethylene glycol (molecular weight 400 to 2000), penta A reaction product of erythritol (1 mol) and ethylene oxide (10 to 25 mol), pentaerythritol (1 mol), ethylene oxide (10 to 25 mol), and fatty acid (1 to 2 mol) having 16 to 20 carbon atoms More preferably, it is at least one selected from the group consisting of:

(Flame retardant component)
(Halogen compound (B))
The halogen compound (B) which concerns on this invention is a flame retardant component in the flame retardant processing agent for polyester fibers of this invention, and is a compound represented by following General formula (4).

In Formula (4), Y ^{1 to} Y ³ are each independently selected from the group consisting of a 2,3-dibromopropyl group, a 2,3-dibromoisobutyl group, and a 1,2-dibromoethyl group. The group of is shown. Examples of such a halogen compound (B) include tris (1,2-dibromoethyl) isocyanurate, tris (2,3-dibromopropyl) isocyanurate, and tris (2,3-dibromoisobutyl) isocyanurate. One of these may be used alone, or two or more may be used in combination. Among these, as the halogen compound (B) according to the present invention, tris (2,3-dibromopropyl) isocyanurate is preferable from the viewpoint of excellent flame retardancy.

(Phosphorus compound)
In the flame retardant processing agent for polyester fibers of the present invention, from the viewpoint that superior flame retardancy tends to be exhibited, as a flame retardant component, in addition to the halogen compound (B), the following phosphorus compound (b preferably contains at least one phosphorus compound selected from the group consisting of ¹⁾ ~ (b ^5).

<Phosphorus compound (b ¹ )>
The phosphorus compound (b ¹ ) is a compound represented by the following general formula (5).

In the formula (5), R ¹⁰ and R ¹¹ are each independently a phenyl group optionally having an alkyl group having 1 to 4 carbon atoms as a substituent, and an alkyl having 1 to 4 carbon atoms as a substituent. Any group selected from the group consisting of naphthyl groups which may have a group, X ¹ and X ² are each independently selected from the group consisting of a direct bond, —O— and —NH—; F represents 1 or 2, and g represents 0 or 1.

Examples of such phosphorus compound (b ¹ ) include triphenyl phosphate, 1-naphthyl diphenyl phosphate, 2-naphthyl diphenyl phosphate, di (1-naphthyl) phenyl phosphate, di (2-naphthyl) phenyl phosphate, 1- Naphthyl-2-naphthylphenyl phosphate, trinaphthyl phosphate, triparacresyl phosphate, tri-2,6-xylenyl phosphate, phenoxyethyl diphenyl phosphate, di (phenoxyethyl) phenyl phosphate, phenoxyethyl dinaphthyl phosphate, di (phenoxyethyl) ) Naphthyl phosphate, naphthoxyethyl diphenyl phosphate, di (naphthoxyethyl) phenyl phosphate, naphthoxyethyl dinaphthyl phosphate, di (naphth Xylethyl) naphthyl phosphate, anilinodiphenyl phosphate, dianilinophenyl phosphate, trianilinophosphate, triphenylphosphine oxide, one of these may be used alone, or two or more may be used in combination. . Among these, as the phosphorus compound (b ¹ ), phenoxyethyl diphenyl phosphate is preferable from the viewpoint of excellent flame retardancy.

<Phosphorus compound (b ² )>
The phosphorus compound (b ² ) is a compound represented by the following general formula (6).

In the formula (6), R ¹² represents benzyl group, methylbenzyl group, phenethyl group, naphthylmethyl group, and the following general formula (6a):

[In the formula (6a), R ¹³ represents any group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a phenyl group, and a benzyl group. ]
Any group selected from the group consisting of groups represented by:

Examples of such phosphorus compounds (b ² ) include 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (4-methylbenzyl) -9,10. -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1-naphthylmethyl)- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2-naphthylmethyl) -9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide, butyl [3- (9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10- Xido-10-yl) methyl] succinimide, phenyl [3- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl) methyl] succinimide, benzyl [3- (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl) methyl] succinimide, and one of these may be used alone or two or more may be used in combination. Good. Among these, as the phosphorus compound (b ² ), 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferable from the viewpoint of excellent flame retardancy. preferable.

<Phosphorus compound (b ³ )>
The phosphorus compound (b ³ ) is a compound represented by the following general formula (7).

In the formula (7), R ^{14 to} R ¹⁷ each independently represents a phenyl group having an alkyl group having 1 to 4 carbon atoms as a substituent, and R ¹⁸ is an arylene group optionally having a substituent. H represents an integer of 1 to 5, and when h is 2 or more, R ¹⁸ may be the same or different.

Examples of such phosphorus compounds (b ³ ) include resorcinol di-2,6-xylenyl phosphate, hydroquinone di2,6-xylenyl phosphate, 4,4′-biphenoldi-2,6-xylenyl. A phosphate is mentioned, One of these may be used independently or may be used in combination of 2 or more type. Among these, as the phosphorus compound (b ³ ), resorcinol di-2,6-xylenyl phosphate is preferable from the viewpoint of excellent flame retardancy.

<Phosphorus compound (b ⁴ )>
The phosphorus compound (b ⁴ ) is a compound represented by the following general formula (8).

In the formula ^{(8), R 19} and ^{R 20} each independently represents an alkyl group having 1 to 4 carbon ^{atoms, R 21} represents a biphenyl group or a naphthyl group.

Examples of such phosphorus compound (b ⁴ ) include 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorin-2-oxide, 5,5- Dimethyl-2- (4′-phenylphenoxy) -1,3,2-dioxaphosphorin-2-oxide, 5-butyl-5-ethyl-2- (4′-phenylphenoxy) -1,3 2-dioxaphosphorinan-2-oxide, 5,5-dimethyl-2- (2′-naphthyloxy) -1,3,2-dioxaphosphorinan-2-oxide, of which One kind may be used alone, or two or more kinds may be used in combination. Among these, the phosphorus compound (b ⁴ ) is 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxa, from the viewpoint of excellent flame retardancy. Phosphorinan-2-oxide is preferred.

<Phosphorus compound (b ⁵ )>
The phosphorus compound (b ⁵ ) is a compound represented by the following general formula (9).

In said formula (9), R <^22> and R < ²³ > shows the phenyl group which may have a C1-C4 alkyl group as a substituent each independently, and i shows the integer of 3-10. .

Examples of such phosphorus compounds (b ⁵ ) include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, dodecaffenoxycyclohexaphosphazene, and hexaparamethylphenoxycyclotriphosphazene. It may be used alone or in combination of two or more. Among these, as the phosphorus compound (b ⁵ ) according to the present invention, it is preferable to use phenoxycyclophosphazene from the viewpoint that it tends to be excellent in flame retardancy.

As examples of the phosphorus compound, the phosphorus compound (b ¹⁾ may be used either one kind alone selected ^~ from the group consisting of (b ^5), may be used in combination of two or more. Among such phosphorus compounds, from the viewpoint that excellent flame retardancy tends to be exhibited when used in combination with the halogen compound (B), the following general formula (10):

[In Formula (10), R ²⁴ and R ²⁵ each independently represent a phenyl group or a naphthyl group, and j represents 1 or 2. ]
It is preferable that it is a compound represented by these, and it is more preferable that it is a phenoxyethyl diphenyl phosphate.

  In this invention, when using the said halogen compound (B) and the said phosphorus compound together, mass ratio (B of content of the said halogen compound (B) and content of the said phosphorus compound in the flame retardant processing agent for polyester fibers) : Phosphorus compound) is preferably 99: 1 to 50:50, more preferably 90:10 to 65:35, and still more preferably 90:10 to 80:20.

  In the present invention, these halogen compounds (B) and phosphorus compounds (hereinafter sometimes referred to as flame retardant components) are hydrophobic in view of the tendency to exhibit better flame retardancy. Preferably there is. That the flame retardant component is hydrophobic means that the flame retardant component does not dissolve or self-emulsify in water. The state of being dissolved or self-emulsified in water means that 200 ml of a 40% by mass aqueous dispersion of a flame retardant component is added to T.W. K. After stirring for 10 minutes at 2000 rpm under room temperature (about 25 ° C.) using HOMODISPER (manufactured by Primix Co., Ltd.), the resulting solution or water emulsion dispersion was allowed to stand at 20 ° C. for 12 hours. It means a state where there is no sedimentation and is uniformly dissolved or emulsified and dispersed.

  Furthermore, the flame retardant component is preferably solid at 20 ° C. When it is liquid at 20 ° C., the durability and flame fastness of the obtained flame-retardant polyester fiber product tend to be lowered. When a flame retardant component that is liquid at 20 ° C. is blended as necessary, the liquid flame retardant component is 5 relative to the total amount of the flame retardant component contained in the flame retardant processing agent for polyester fibers of the present invention. It is preferable that it is below mass%.

(Surfactant (C))
In the present invention, the compound (A) also functions as a surfactant component. However, as the flame retardant processing agent for polyester fibers of the present invention, the product stability and processing solution stability of the flame retardant processing agent for polyester fibers are described. From the viewpoint of improving the viscosity, it is preferable to further contain another surfactant (C). Examples of such a surfactant (C) include at least one selected from the group consisting of nonionic surfactants and anionic surfactants, and even when one type is used alone, two or more types are combined. It may be used.

  Examples of the nonionic surfactant include polyoxyalkylene alkylaryl ether, and the following general formula (11):

[In the formula (11), Ar represents a residue obtained by removing p hydroxy groups from an aromatic hydroxy compound having p hydroxy groups, and R ²⁶ and R ²⁷ each independently represents a hydrogen atom or a methyl group. R ²⁸ represents an alkylene group having 2 to 4 carbon atoms, R ²⁹ represents a hydrogen atom or an anionic group represented by any one of the general formulas (1a) to (1g), k Represents an integer of 1 to 10, m represents an integer of 1 to 3, and n represents an average added mole number of an alkyleneoxy group represented by (R ²⁸ —O), and represents an integer of 1 to 200. , P represents an integer of 1 to 10, and when n and / or p is 2 or more, a plurality of R ²⁸ may be the same or different, and when p is 2 or more, a plurality of R ²⁹ are the same But it can be different. However, k + m represents an integer of 2 to 10. ]
A polyoxyalkylene styrenated aryl ether represented by the following general formula (12):

[In Formula (12), Ar represents a residue obtained by removing s hydroxy groups from an aromatic hydroxy compound having s hydroxy groups, R ³⁰ represents an alkylene group having 2 to 4 carbon atoms, and R ³¹ Represents an anionic group represented by a hydrogen atom or any one of the general formulas (1a) to (1g), q represents an integer of 1 to 3, and r represents (R ³⁰ —O). The number of added moles of the alkyleneoxy group is an integer of 1 to 200, s represents an integer of 1 to 10, and when r and / or s is 2 or more, a plurality of R ³⁰ are the same However, they may be different, and when s is 2 or more, a plurality of R ³¹ may be the same or different. ]
And polyoxyalkylene benzylated aryl ethers, alkylamine alkylene oxide adducts, and aliphatic amidoalkylene oxide adducts.

  Examples of the anionic surfactant include a sulfate ester salt of the nonionic surfactant, a phosphate ester salt of the nonionic surfactant, a carboxylate salt of the nonionic surfactant, and the nonionic interface. Sulfosuccinic acid type anionic surfactant as activator, sulfate ester salt of higher alcohol, phosphate ester salt of higher alcohol, alkylbenzene sulfonate, alkyl naphthalene sulfonate, the following general formula (13):

[In the formula (13), R ³² and R ³³ each independently represent the following formulas (13a) to (13b):

Each of R ³⁴ and R ³⁵ independently represents a hydrogen atom or a methyl group, Z represents —SO ₃ H, —CH ₂ SO ₃ H, and these The substituent of either of the groups represented by a salt is shown, and t and u show an integer greater than or equal to 0 each independently. ]
And a phenol formaldehyde condensate having an average polymerization degree t + u + 2 of 2 to 30, a naphthalene sulfonate condensate such as a formalin condensate of naphthalene sulfonate, a creosote oil sulfonate condensate Products, lignin sulfonates, melamine sulfonate condensates, and bisphenol sulfonate condensates.

  Among these, as the surfactant (C), polyoxyalkylene styrenation represented by the above general formula (11) from the viewpoint that the product stability of the flame retardant for polyester fiber tends to be further improved. Aryl ether, polyoxyalkylene benzylated aryl ether represented by the general formula (12), phenol formaldehyde condensate, naphthalene sulfonate condensate represented by the general formula (13), creosote oil sulfonic acid It is preferably at least one selected from the group consisting of a salt-based condensate, a lignin sulfonate, a melamine sulfonate-based condensate, and a bisphenol sulfonate-based condensate.

  In the polyoxyalkylene styrenated aryl ether represented by the general formula (11) and the polyoxyalkylene benzylated aryl ether represented by the general formula (12), Ar has p and s hydroxy groups. A residue obtained by removing p and s hydroxy groups from an aromatic hydroxy compound, respectively. Examples of such residues include phenol, 2-cumylphenol, 3-cumylphenol, 4-cumylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 1-naphthol, 2 -Residues obtained by removing one hydroxy group from monovalent aromatic hydroxy compounds such as naphthol, cresol, butylphenol, octylphenol, nonylphenol, dodecylphenol; catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, etc. Residues obtained by removing two hydroxy groups from a divalent aromatic hydroxy compound; pyrogallol (1,2,3-trihydroxybenzene), 1,2,4-trihydroxybenzene, phloroglucinol (1,3,3) 5-trihydroxybe Trivalent residues excluding the three hydroxy groups from an aromatic hydroxy compound of Zen) and the like; residue obtained by removing the four hydroxy groups from tetravalent aromatic hydroxy compounds such as tetrahydroxy benzene. Among these, from the viewpoint of ease of production of the flame retardant processing agent for polyester fibers, product stability, treatment liquid stability, it is preferably a residue of a monovalent aromatic hydroxy compound, a phenol residue, More preferred are 4-cumylphenol residues, 4-phenylphenol residues, and 2-naphthol residues.

In formula (11), R ²⁶ and R ²⁷ each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferable from the viewpoint of easy availability of the compound. In formulas (11) and (12), R ²⁸ and R ³⁰ each represent an alkylene group having 2 to 4 carbon atoms. Examples of such an alkylene group having 2 to 4 carbon atoms include an ethylene group and propylene. Group, butylene group, and the like. Among them, from the viewpoint of product stability and treatment liquid stability of the flame retardant for polyester fiber, ethylene group and propylene group are preferable, and ethylene group is more preferable.

Further, in the formulas (11) and (12), p and s each represent an integer of 1 to 10, and among them, the ease of production of the flame retardant for polyester fibers, the product stability, and the treatment liquid stability From the viewpoint, it is preferably 1 to 3. When n and / or p or r and / or s is 2 or more, a plurality of R ²⁸ or R ³⁰ may be the same or different. When p or s is 2 or more, a plurality of R ²⁸ or R ³⁰ exist. R ²⁹ or R ³¹ may be the same or different. However, in the formula (11), k + m represents an integer of 2 to 10, and is 2 to 8 from the viewpoint of ease of production of the flame retardant for polyester fibers, product stability, and processing solution stability. Preferably, it is 2-5.

In formulas (11) and (12), n and r are the average added moles of alkyleneoxy groups represented by (R ²⁸ —O) and (R ³⁰ —O), respectively. An integer of 200 is shown. Among them, from the viewpoint of ease of production of the flame retardant for polyester fiber, product stability, and processing solution stability, an integer of 3 to 100 is preferable, and an integer of 5 to 50 is preferable. More preferably.

These polyoxyalkylene styrenated aryl ethers and polyoxyalkylene benzylated aryl ethers may be used singly or in combination of two or more. The polyoxyalkylene styrenated aryl ether is added in accordance with a conventional method, for example, after adding styrenes such as styrene, α-methylstyrene, vinyltoluene to an aromatic hydroxy compound represented by Ar (OH) _p , Furthermore, it can be obtained by adding an alkylene oxide or by anionizing the alkylene oxide adduct obtained above. In addition, the polyoxyalkylene benzylated aryl ether is obtained by reacting an aromatic hydroxy compound represented by Ar (OH) _s with benzyl chloride according to a conventional method, and further adding alkylene oxide. Alternatively, it can be obtained by anionizing the alkylene oxide adduct obtained above.

  The phenol formaldehyde-based condensate represented by the general formula (13) is a compound having a phenol skeleton that does not contain the substituent Z and a phenol skeleton that contains the substituent Z. The phenol skeleton not containing the substituent Z is a terminal group represented by the formula (13a) or the following formula (13c):

[In the formula (13c), R ³⁶ represents a hydrogen atom or a methyl group. ]
Means a repeating unit represented by The terminal group represented by the formula (13a) is a phenol terminal group or a cresol terminal group, and the repeating unit represented by the formula (13c) is formed by condensing phenol or cresol and formaldehyde. It is a repeating unit.

  Moreover, the phenol skeleton containing the substituent Z is a terminal group represented by the formula (13b) or the following formula (13d):

[In the formula (13d), R ³⁷ represents a hydrogen atom or a methyl group, and Z is a substituent selected from the group represented by —SO ₃ H, —CH ₂ SO ₃ H, and salts thereof. Indicates. ]
Means a repeating unit represented by The terminal group represented by the formula (13b) is a phenol terminal group or a cresol terminal group having an anionic group of any one of a sulfonic acid group, a sulfonic acid group, a methylsulfonic acid group, and a methylsulfonic acid group. The repeating unit represented by the formula (13d) is formed by condensing formaldehyde with phenol or cresol having any anionic group of sulfonic acid group, sulfonic acid group, methylsulfonic acid group and methylsulfonic acid group. Is a repeating unit formed.

  Such a phenol formaldehyde condensate includes a phenol compound not containing at least one substituent Z of phenol and cresol, phenol sulfonic acid, cresol sulfonic acid, hydroxyphenyl methane sulfonic acid, hydroxytolyl methane sulfonic acid. And a phenol-based compound containing at least one substituent Z selected from the group consisting of these salts and formaldehyde can be obtained by a condensation reaction by a known method. The condensation reaction may be random addition condensation or block addition condensation.

  In the phenol formaldehyde-based condensate, the average value of polymerization degree (t + u + 2) of the phenol formaldehyde-based condensate (hereinafter referred to as “average polymerization degree”) is 2 to 30, but the obtained flame-retardant processing for polyester fibers. From the viewpoint of product stability of the agent, treatment solution stability, and ease of handling of the phenol formaldehyde-based condensate, it is preferably 3 to 15, and more preferably 3 to 10.

In addition, the average degree of polymerization of such a phenol formaldehyde condensate can be controlled by adjusting the mixing molar ratio of formaldehyde with respect to the whole phenolic compound in the condensation reaction. For example, a phenol formaldehyde-based condensate having a predetermined average degree of polymerization can be obtained by setting the amount of formaldehyde mixed to 0.5 to 0.97 mole times the entire phenolic compound. The average degree of polymerization of the phenol formaldehyde condensate can be determined from the raw material molar ratio of the phenolic compound and formaldehyde. That is, the number of moles of phenolic compound charged is Mp, the number of moles of formaldehyde charged is Mf, the excess component of these is denominator, v = Mp / Mf or Mf / Mp, and the reaction rate is w. The degree of polymerization (Pn) is expressed by the following formula: Pn = (1 + v) / [2v (1-w) + (1-v)]
When the reaction rate is 100% (p = 1),
Pn = (1 + v) / (1-v)
Thus, the number average degree of polymerization of the phenol formaldehyde condensate can be determined. However, in the present invention, as shown in the formula (13), since the average number of phenol skeletons is the average degree of polymerization, the average degree of polymerization of the phenol formaldehyde condensate according to the present invention is (Pn + 1) / 2. It becomes.

In addition, the average degree of polymerization is determined from the combined sulfuric acid value of the phenol formaldehyde condensate, the ratio Zn: Zp of the phenol skeleton (Zn) not containing the substituent Z and the phenol skeleton (Zp) containing the substituent Z, The molecular weight of the phenol skeleton not containing the substituent Z and the ratio Zn, the molecular weight of the phenol skeleton containing the substituent Z and the ratio Zp, the amount of CH ₂ required for bonding the phenol skeleton of the ratio, and gel permeation chromatography It is also possible to calculate based on the number average molecular weight measured by lithography.

  In the compound represented by the general formula (13) according to the present invention, the phenol skeleton not containing the substituent Z (that is, the terminal group represented by the above (13a) and the repeating unit represented by the above (13c)) ) And the phenol skeleton containing the substituent Z (that is, the molar ratio of the terminal group represented by (13b) and the repeating unit represented by (13d)) is obtained as a flame retardant processing agent for polyester fibers. [(13a) + (13c)]: [(13b) + (13d)] = 1: 0.2 to 1: 2.0, from the viewpoint of product stability and processing solution stability It is more preferable that it is 1: 1.0-1: 1.5.

  The naphthalene sulfonate-based condensate is a condensate obtained by condensing a salt of naphthalene sulfonic acid with, for example, formalin. Examples of the salt include alkali metals such as sodium and potassium; alkaline earth metals such as calcium and magnesium; primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine and allylamine; dimethylamine, diethylamine and dipropylamine Secondary amines such as dibutylamine and diallylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

  Although it does not specifically limit as a polymerization degree of the said naphthalene sulfonate, It is preferable that it is 2-20. Moreover, as a weight average molecular weight, it is preferable that it is 1000-20000. In addition, the said weight average molecular weight is the value of polystyrene conversion by GPC measurement.

  Specific examples of such a naphthalene sulfonate-based condensate include naphthalene sulfonate formalin condensate, alkyl naphthalene sulfonate formalin condensate, dialkyl naphthalene sulfonate formalin condensate and the like. Further, the alkyl group as a substituent may be linear or branched. Further, the naphthalene moiety may have a substituent such as an alkyl group. Examples of such a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. , An alkyl group having 1 to 12 carbon atoms such as an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

  As the creosote oil sulfonate-based condensate, a salt of a creosote oil sulfonic acid formalin condensate is preferably used, and examples of the salt are the same as those mentioned as the salt of naphthalene sulfonate. It is done. The creosote oil sulfonate-based condensate preferably has a weight average molecular weight of 1000 to 20000.

  The lignin sulfonate is obtained by sulfonating lignin, which is a main component of wood, and examples of the salt include the same salts as those mentioned as the salt of naphthalene sulfonic acid.

  As the melamine sulfonate-based condensate, a salt of a melamine sulfonic acid formalin condensate is preferably used, and examples of the salt include the same as those mentioned as the salt of naphthalene sulfonic acid. Such a melamine sulfonate-based condensate is not particularly limited, but preferably has a weight average molecular weight of 500 to 20000.

  As the bisphenol sulfonate-based condensate, a salt of a bisphenol sulfonic acid formalin condensate is preferably used, and examples of the salt include the same as those mentioned as the salt of naphthalene sulfonic acid. Such a bisphenol sulfonate-based condensate is not particularly limited, but preferably has a weight average molecular weight of 500 to 20000.

  In the flame retardant processing agent for polyester fibers of the present invention, as the surfactant (C), one kind may be used alone, or two or more kinds may be used in combination. Among such surfactants (C), the polyoxyalkylene styrenated aryl represented by the general formula (11) from the viewpoint of product stability, flame retardancy, and economic efficiency of the flame retardant for polyester fibers. Ether and the phenol formaldehyde condensate represented by the general formula (13) are preferable, and polyoxyalkylene styrenated phenyl ether and polyoxyalkylene styrenated cumylphenyl ether are more preferable.

(Flame retardant for polyester fiber)
In the flame retardant processing agent for polyester fibers of the present invention, the mass ratio (A: B) between the content of the compound (A) and the content of the halogen compound (B) is 1: 100 to 50: 100. It is preferably 5: 100 to 25: 100, more preferably 5: 100 to 15: 100. Further, when the phosphorus compound is used in combination as the flame retardant component, as a mass ratio (A: (B + phosphorus compound)) between the content of the compound (A) and the content of the flame retardant component, The ratio is preferably 1: 100 to 50: 100, more preferably 5: 100 to 25: 100, and still more preferably 5: 100 to 15: 100. When the content of the compound (A) is less than the lower limit, the texture of the obtained flame-retardant polyester fiber product, the durability flame resistance, and the exhaustibility of the flame-retardant component to the polyester fiber tend to decrease. On the other hand, when the above upper limit is exceeded, the texture, durability flame retardance and exhaustion improvement effect commensurate with the amount of the compound (A) are reduced, and the fastness of the resulting flame retardant polyester fiber product is low. It tends to decrease.

  Furthermore, in the flame retardant processing agent for polyester fibers of the present invention, the halogen compound (B) and the phosphorus compound are contained in the halogen compound (B), and when the phosphorus compound is contained, the content is not particularly limited. As a total content, it is preferable that it is 0.1-60 mass% in the flame-retardant processing agent for polyester fibers. When the content of the halogen compound (B) or the total content is less than the lower limit, the flame retardancy of the obtained flame retardant polyester fiber product tends to be insufficient, and on the other hand, exceeds the upper limit. There is a tendency that the product stability of the flame retardant processing agent for polyester fibers of the present invention is lowered.

  Furthermore, in the flame retardant processing agent for polyester fibers of the present invention, when the surfactant (C) is further contained, the content is not particularly limited, but the content of the halogen compound (B), or When the phosphorus compound is contained, the content is preferably 0.5 to 15% by mass and more preferably 1 to 10% by mass with respect to the total content of the halogen compound (B) and the phosphorus compound. preferable. When the content of the surfactant (C) is less than the lower limit, the effect of improving the product stability of the flame retardant processing agent for polyester fibers tends to be small, and when the content exceeds the upper limit, it is obtained. The fastness and durability of the flame retardant polyester fiber products tend to decrease.

  The flame retardant processing agent for polyester fibers of the present invention is, for example, by emulsifying and dispersing the flame retardant component in an aqueous medium using the compound (A), or the compound (A), the flame retardant component, and It can be obtained by continuously emulsifying and dispersing an aqueous medium. When the halogen compound (B) and the phosphorus compound are used in combination as the flame retardant component, the halogen compound (B) and the phosphorus compound may be simultaneously emulsified and dispersed, or the halogen compound (B) and the phosphorus compound may be dispersed. You may obtain the flame retardant processing agent for polyester fibers of this invention by mixing what was separately emulsified and disperse | distributed.

  When the surfactant (C) is used, for example, the flame retardant component is emulsified and dispersed in an aqueous medium using the surfactant (C), or the flame retardant component or the surface activity is used. The flame retardant processing agent for polyester fibers of the present invention can be obtained by continuously emulsifying and dispersing the agent (C) and the aqueous medium. Further, as described above, when the halogen compound (B) and the phosphorus compound are used in combination as the flame retardant component, the halogen compound (B) and the phosphorus compound may be emulsified and dispersed simultaneously, or the halogen compound ( B) and a phosphorus compound separately emulsified and dispersed may be mixed. In addition, when using the said surfactant (C), the said compound (A) may be added in any step before emulsification dispersion | distribution of the said flame-retardant component, during emulsification dispersion | distribution, and after emulsification dispersion | distribution. As A), it may be added as it is, or it may be diluted in an aqueous medium. Among these methods, the flame retardant component is used as the surfactant (C) from the viewpoint of easy production of the flame retardant for polyester fibers and easy change of the compounding amount of the compound (A). A method of mixing the compound (A) after emulsifying and dispersing is preferred.

  The aqueous medium is preferably a mixed solvent of water, water and a hydrophilic solvent miscible with water. Examples of the hydrophilic solvent include methanol, ethanol, isopropyl alcohol, ethylene glycol, hexylene glycol, glycerin, butyl glycol, and sol-fit.

  The method for emulsifying and dispersing the flame retardant component in an aqueous medium is not particularly limited, and examples thereof include a method using a conventionally known emulsifier / disperser. Examples of the emulsifier / disperser include milders, homogenizers, and ultrasonic homogenizers. , Homomixer, bead mill, pearl mill, dyno mill, aspec mill, basket mill, ball mill, nanomizer, optimizer, and starburst. As these emulsifying dispersers, one type may be used alone, or two or more types may be used in combination.

  The flame retardant processing agent for polyester fibers of the present invention thus obtained is in the form of an emulsified dispersion. In the emulsified dispersion, the 50% cumulative particle size is preferably 0.05 to 10 μm, and 0 0.1-3 μm is more preferable, and 0.1-2 μm is even more preferable. When the 50% cumulative particle size is less than the lower limit, the effect of improving the product stability of the flame retardant for polyester fibers is small, and it tends to be economically disadvantageous because it takes time to make fine particles. When the upper limit is exceeded, the product stability of the flame retardant processing agent for polyester fibers tends to decrease. Furthermore, the flame retardant for polyester fiber of the present invention has a 90% cumulative particle size of 2.0 μm or less from the viewpoint that the product stability of the flame retardant for polyester fiber tends to be further improved. Is particularly preferred.

  In the present invention, the 50% cumulative particle size and the 90% cumulative particle size are determined by using a laser diffraction type / scattering type particle size distribution measuring device LA-920 (manufactured by Horiba, Ltd.), and the particle size of the flame retardant for polyester fiber. The percentage integrated value of 50% from the small particle diameter side can be measured as 50% integrated particle diameter, and the percentage integrated value of 90% from the small particle diameter side can be measured as 90% integrated particle diameter. it can.

  In addition to the surfactant (C), the flame retardant processing agent for polyester fibers of the present invention further contains a cationic surfactant and an amphoteric surfactant within the range not inhibiting the effects of the present invention. May be. The cationic surfactant is not particularly limited, and for example, a monoalkyltrimethylammonium salt having 8 to 24 carbon atoms, a dialkyldimethylammonium salt having 8 to 24 carbon atoms, a monoalkylamine acetate salt having 8 to 24 carbon atoms, Examples thereof include C8-24 dialkylamine acetates and C8-24 alkyl imidazoline quaternary salts. One of these may be used alone, or two or more may be used in combination.

  The amphoteric surfactant is not particularly limited. For example, alkylbetaine, fatty acid amidopropylbetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiethylenetriaminoacetic acid, dialkyldiethylenetriaminoacetic acid. And alkylamine oxides, and one of these may be used alone or two or more of them may be used in combination.

  In addition, as the flame retardant processing agent for polyester fiber of the present invention, a conventionally known flame retardant other than the halogen compound (B) and the phosphorus compound, and a fire extinguisher, as necessary, within a range not impairing the effects of the present invention. Odorant, antibacterial agent, softener, water absorbent, water and oil repellent, smoothing agent, penetrating agent, dispersion leveling agent, antistatic agent, chelating agent, antioxidant, antifoaming agent, solvent, synthetic resin (acrylic resin , Silicone resin, urethane resin, polyester resin, glyoxal resin, melamine resin, etc.), crosslinking agent, freezing stabilizer, matting agent, pigment, dye, carrier agent, fixing agent, wetting agent, light stabilizer, UV absorber, Thickeners (polyacrylamide, xanthan gum, xanthan gum, sodium polyacrylate, CMC, sodium alginate, PVA, etc.), film-forming aids, rust preventives, antiseptics, antifungal agents, anti-yellowing agents, etc. Additives may contain. Further, these additives may be used simultaneously with and / or before and after the treatment of the polyester fiber using the flame retardant for polyester fiber of the present invention.

(Method for producing flame-retardant polyester fiber product)
The method for producing a flame-retardant polyester fiber product of the present invention is to treat polyester fiber using the flame-retardant processing agent for polyester fiber of the present invention. According to the production method of the present invention, by providing the polyester fiber product with the flame retardant for polyester fiber of the present invention, the polyester fiber product has sufficient flame retardancy excellent in durability and maintains fastness. Thus, it is possible to obtain a flame-retardant polyester fiber product in which the texture hardening is sufficiently suppressed.

  As a flame retardant processing agent for polyester fibers of the present invention, it may be used as it is or as a treatment liquid appropriately diluted. In the treatment liquid, the mass ratio (A: B) of the content of the compound (A) and the content of the halogen compound (B), the content of the compound (A) in the case of using the phosphorus compound together, As the mass ratio (A: (B + phosphorus compound)) to the content of the flame retardant component, the content in the case of further containing the surfactant (C), the 50% cumulative particle size and the 90% cumulative particle size , Respectively, as described above.

  The method for applying the flame retardant for polyester fiber of the present invention to a polyester fiber product is not particularly limited, and a known method such as a dipping method, a padding method, a coating method, or a spray method can be appropriately used.

  When the immersion method is used, the flame retardant component for the polyester fiber is appropriately diluted as necessary, so that the concentration of the flame retardant in the treatment liquid is 0.01 to 15% o.d. w. f. It is preferable to be within the range. Moreover, when using the said padding method, it is preferable to make it the density | concentration of the flame-retardant part in a process liquid in the range of 0.01-15 mass%. Furthermore, in these methods, the flame retardant content supported on the polyester fiber is 0.01 to 15% o.d. w. f. It is preferable to give so that it may become. When the amount of the flame retardant is less than the lower limit, the flame retardancy of the obtained flame retardant polyester fiber product tends to be insufficient. On the other hand, when the amount exceeds the upper limit, the effect of improving the flame retardancy is obtained. In some cases, the flame retardancy may be lowered, the resulting flame retardant polyester fiber product may be whitened to deteriorate the appearance, or the fastness may be lowered or the texture may be cured.

  When using the dipping method, polyester fibers are processed at a predetermined temperature for a predetermined time using a dyeing machine that is generally used, for example, a winch, a liquid dyeing machine, a zicker, a cheese dyeing machine, or a skein dyeing machine. Then, a flame-retardant polyester fiber product can be obtained by dehydrating and drying. When using the padding method, the polyester fiber is immersed in a treatment solution, adjusted to a predetermined pick-up amount using a mangle, a roll, etc., and then dried to obtain a flame-retardant polyester fiber product. it can.

  When using the coating method, it is possible to use a treatment liquid in which the flame retardant for polyester fiber is mixed with a binder as necessary. In this case, the content of the flame retardant in the treatment liquid Is preferably in the range of 0.1 to 15% by mass. When using the said spray method, it is preferable to spray-process using the process liquid diluted suitably so that content of a flame-retardant part may exist in the range of 10-90 mass%.

In the coating method and the spray method, it is preferable that the polyester fiber is applied so that the amount of the flame retardant supported is 0.1 to 40 g / m ² . When the amount of the flame retardant is less than the lower limit, the flame retardancy of the obtained flame retardant polyester fiber product tends to be insufficient. On the other hand, when the amount exceeds the upper limit, the effect of improving the flame retardancy is obtained. It tends to be economically disadvantageous. When the coating method is used, a flame retardant polyester fiber product can be obtained by coating the polyester fiber with a treatment liquid by brush coating, roller coating, flow coater coating, electrodeposition coating, or the like and drying it.

  Drying conditions in these methods are not particularly limited, and for example, drying can be performed at 0 to 300 ° C. for about 5 seconds to several days. Moreover, you may heat-process (curing) for about 10 second-10 minutes at the temperature of 100 degreeC or more after drying as needed.

  Examples of the polyester fiber include, but are not limited to, regular polyester fiber; cationic dyeable polyester fiber; regenerated polyester fiber; and polyester fiber composed of two or more of these. Further, the polyester fiber and cotton, hemp Natural fibers such as silk and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, acrylic, polyamide, polyurethane, polyethylene, polypropylene, polytrimethylene terephthalate fibers; carbon, glass, ceramics, asbestos, metal, etc. Examples thereof include fiber products made of composite fibers, blended fibers, etc. with inorganic fibers.

  The form of the polyester fiber is not particularly limited, and examples thereof include short fiber, long fiber, yarn, woven fabric, knitted fabric, cotton, sliver, top, and nonwoven fabric. Furthermore, such a polyester fiber may be subjected to a dyeing process or a soaping process.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(1) Particle size measurement About the flame retardant processing agent for polyester fibers obtained in each Example and Comparative Example, the particle size was measured using a laser diffraction type / scattering type particle size distribution measuring device LA-920 (manufactured by Horiba, Ltd.). Was measured, and the 50% cumulative particle size was defined as a particle size having a percentage integrated value of 50% from the small particle size side.

(2) Product Stability Evaluation of Flame Retardant for Polyester Fibers Immediately after the production of the flame retardant for polyester fibers (immediately after dispersion) and after standing at 20 ° C. for 30 days, the following criteria are observed:
A: There is no separation, sedimentation and thickening B: There is separation, sedimentation and thickening, but it can be used with simple stirring C: Separation, sedimentation and thickening occur, and judgment is made according to the inability to use with simple stirring did.

(3) Texture The texture of the polyester raw fabric (flame retardant untreated fabric) used in each example and comparative example is 10 (soft), no compound (A) is used, only FRBr1 is used as a flame retardant component, and the surface activity. The texture of the flame retardant polyester fiber product obtained by using only TSP20S as the agent (C) component is 1 (coarse), and the texture of the obtained flame retardant polyester fiber product is tactile. Evaluation was made on a 10-point scale. When the performance was slightly good, “+” was assigned to the grade, and when the performance was slightly inferior, “−” was assigned to the grade.

(4) Friction fastness About the flame-retardant polyester fiber product obtained in each Example and Comparative Example, the friction fastness is the same as the dyeing fastness test method for friction described in JIS L 0849 (2004). A test was performed to determine the series. In this example, the friction tester type II (Gakuken type) described in JIS L 0849 (2004) 5.1b) was used, and the wet test described in JIS L 0849 (2004) 7.2b). Only went.

(5) Light fastness The flame retardant polyester fiber product obtained in each of the examples and comparative examples was treated at 63 ° C. for 40 hours by the dyeing fastness test method for ultraviolet carbon arc lamp described in JIS L0842 (2004). And was determined according to the determination method described in JIS L0804 (2004) using "Grayscale for color fading".

(6) Exhaustion rate (Amount of flame retardant component adhering to fabric)
The weight of the polyester untreated cloth (flame retardant untreated cloth) used in each example and comparative example was W1, the weight of the flame retardant treated cloth (flame retardant treated, no soaping) was W2, and the flame retardant treated cloth was soaped. The mass of the fabric (finished) is W3, the ratio of the flame retardant component in the solid content of the flame retardant finish is R, and the exhaustion rate is the following formula:
Exhaust rate (%) = [(W3-W1) × 100] / [(W2-W1) × R / 100]
Determined by The mass of the flame retardant untreated cloth, the flame retardant treated cloth (flame retardant treated, no soaping), and the cloth treated with the flame retardant treated cloth (finished) is 24 hours under an environment of 20 ° C. and 65% RH. Mass measured after standing.

(7) Flame retardancy For the flame retardant polyester fiber products obtained in each of the examples and comparative examples, the processed finish (before washing with water) and the processed finish after washing with water and dry cleaning, 45 ° micro burner method The flame retardancy was evaluated by a flame contact test (coil method). Washing with water and dry cleaning were performed as follows.

(7-1) 45 ° Micro Burner Method JIS L 1091 (1999) 8.1.1 A-1 method was used to measure afterflame time and combustion area. The case where the after flame time was within 3 seconds and the combustion area was 30 cm ² or less was determined as “A”, and other cases were determined as “B”.

(7-2) Flame contact test (coil method)
The number of flame contact was measured using the D method of JIS L 1091 (1999) 8.4. The number of times of flame contact was the average of 5 measurements. It is judged that the more the number of flame contacts, the better the flame retardancy.

(7-3) Washing-washing method About the flame-retardant polyester fiber product obtained by each Example and the comparative example, the ratio of 1 g / L of the weak alkaline 1st type washing detergents described in JIS K 3371 (1994) The bath ratio was 1:40, washed with water at 60 ± 2 ° C for 15 minutes, rinsed 3 times for 5 minutes at 40 ° C ± 2 ° C, and subjected to centrifugal dehydration for 2 minutes. After performing 5 cycles, washing with water was performed by the method described in JIS L 1091 (1999) except that it was dried with hot air at 60 ° C. ± 5 ° C.

(7-4) Dry cleaning method For 1 g of the flame-retardant polyester fiber product obtained in each Example and Comparative Example, cleaning is performed at 30 ° C. ± 2 ° C. for 15 minutes using 12.6 mL of tetrachloroethylene and 0.265 g of charge soap. The treatment to be performed was one cycle, and after performing this for 5 cycles, dry cleaning was carried out by the method described in JIS L 1091: 1999 except that it was suspended and dried.

(Synthesis Example 1)
<Compound (A): Reaction product of pentaerythritol, 2 mol of oleic acid and 15 mol of ethylene oxide (compound represented by the general formula (2))>
First, 136 parts by mass of pentaerythritol (1.0 mol), 280 parts by mass of oleic acid (1.0 mol), and 1 part by mass of paratoluene sulfonic acid were charged into a reaction vessel, and heated and heated in a nitrogen gas stream. The dehydration reaction was carried out at 205 to 215 ° C. for about 6 hours and then cooled to obtain pentaerythritol oleate.

  Next, 398 parts by mass (1.0 mol) of oleic acid ester of pentaerythritol and 2 parts by mass of caustic soda were charged into an autoclave, heated to about 130 ° C., and then 660 parts by mass (15 mol of ethylene oxide). ) At a temperature of 150 to 160 ° C. and a pressure of 0.39 MPa or less. After completion of the ethylene oxide addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain a 15 mol ethylene oxide adduct of pentaerythritol oleate.

  Next, 1058 parts by mass (1.0 mol) of an ethylene oxide 15 mol adduct of pentaerythritol oleate ester, 280 parts by mass (1.0 mol) of oleic acid, and 5 parts by mass of concentrated sulfuric acid were charged into a reaction vessel. The mixture was heated and heated in a nitrogen gas stream and dehydrated at 180 to 200 ° C. for about 3 hours, and then cooled to obtain a reaction product of pentaerythritol, 2 mol of oleic acid and 15 mol of ethylene oxide.

(Synthesis Example 2)
<Compound (A): Reaction product of pentaerythritol, 2 mol of oleic acid and 25 mol of ethylene oxide (compound represented by the general formula (2))>
First, 136 parts by mass of pentaerythritol (1.0 mol), 280 parts by mass of oleic acid (1.0 mol), and 1 part by mass of paratoluene sulfonic acid were charged into a reaction vessel, and heated and heated in a nitrogen gas stream. The dehydration reaction was carried out at 205 to 215 ° C. for about 6 hours and then cooled to obtain pentaerythritol oleate.

  398 parts by mass (1.0 mol) of oleic acid ester of pentaerythritol and 2 parts by mass of caustic soda were charged into an autoclave, heated to about 130 ° C., and then 1100 parts by mass (25 mol) of ethylene oxide. The addition was performed at a temperature of 150 to 160 ° C. and a pressure of 0.39 MPa or less. After completion of the ethylene oxide addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain a 25 mol ethylene oxide adduct of pentaerythritol oleate.

  Subsequently, 1498 parts by mass (1.0 mol) of an ethylene oxide 25 mol adduct of oleic acid ester of pentaerythritol obtained, 280 parts by mass (1.0 mol) of oleic acid, and 5 parts by mass of concentrated sulfuric acid were charged into a reaction vessel. The mixture was heated and heated in a nitrogen gas stream and dehydrated at 180 to 200 ° C. for about 3 hours, and then cooled to obtain a reaction product of pentaerythritol, 2 mol of oleic acid, and 25 mol of ethylene oxide.

(Synthesis Example 3)
<Compound (A): Reaction product of trimethylolpropane, 20 mol of ethylene oxide and 1 mol of oleic acid (compound represented by the general formula (2))>
First, 134 parts by mass (1.0 mol) of trimethylolpropane and 2 parts by mass of caustic soda were charged into an autoclave and heated to about 130 ° C., and then 880 parts by mass (20 mol) of ethylene oxide was added at a temperature of 150 to 160. The addition was performed at 0 ° C. and a pressure of 0.39 MPa or less. After completion of the ethylene oxide addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain an ethylene oxide 20 mol adduct of trimethylolpropane.

  Subsequently, 1014 parts by mass (1.0 mol) of an ethylene oxide 20 mol adduct of trimethylolpropane obtained, 280 parts by mass (1.0 mol) of oleic acid, and 5 parts by mass of concentrated sulfuric acid were charged into a reaction vessel, and nitrogen gas was added. The mixture was heated and heated in an air stream to cause a dehydration reaction at 180 to 200 ° C. for about 3 hours and then cooled to obtain a reaction product of trimethylolpropane, 20 mol of ethylene oxide and 1 mol of oleic acid.

(Synthesis Example 4)
<Compound (A): Reaction product of POE (13) polyglyceryl ether and 1 mol of oleic acid (compound represented by formula (2))>
POE (13) polyglyceryl ether (SC-E750, average molecular weight 750, Sakamoto Yakuhin Kogyo Co., Ltd.) 750 parts by mass (1.0 mol), oleic acid 280 parts by mass (1.0 mol) and concentrated sulfuric acid 5 parts by mass Charged into a reaction vessel, heated and heated under a nitrogen gas stream, dehydrated at 180-200 ° C. for about 3 hours, and then cooled to obtain a reaction product of POE (13) polyglyceryl ether and 1 mol of oleic acid. It was.

(Synthesis Example 5)
<Compound (A): Sulfur oxide of polyethylene glycol (molecular weight 600) (compound represented by the general formula (1))>
First, 600 parts by mass (1.0 mol) of polyethylene glycol (average molecular weight 600) was charged into a reaction kettle, and stirred with a homomixer, under a nitrogen stream, at 106.7 parts by mass (1. 1 mol) was added in two portions at 20 minute intervals. Then, it was made to react at 105-115 degreeC for about 4 hours, water, isopropyl alcohol, and aqueous ammonia were added, and the yellow liquid composition which contains 50 mass% of sulfates of polyethyleneglycol (molecular weight 600) of pH8 was obtained.

(Synthesis Example 6)
<Compound (A): Sulfur oxide of a reaction product of pentaerythritol, 2 mol of oleic acid and 15 mol of ethylene oxide = sulfur oxide of the compound of Synthesis Example 1 (compound represented by the general formula (2))>
1320 parts by mass (1.0 mol) of the compound obtained in Synthesis Example 1 was charged into a reaction kettle, and stirred with a homomixer while flowing in a nitrogen stream at 125.1 parts by mass (1.33) of sulfamic acid at 105 to 115 ° C. Mol) was added in 4 portions at 20 minute intervals. Then, it was made to react at 105-115 degreeC for about 4 hours, water, isopropyl alcohol, and aqueous ammonia were added, and the yellow liquid composition which contains 50 mass% of sulfates of the compound of the synthesis example 1 of pH8 was obtained.

(Synthesis Example 7)
<Compound (A): Reaction product of polyethylene glycol (average molecular weight 600), 1.7 mol of propylene oxide and 6.8 mol of ethylene oxide (compound represented by the general formula (1))>
First, 600 parts by mass (average molecular weight 600) of polyethylene glycol (1.0 mol) and 2 parts by mass of caustic soda were charged into an autoclave, heated to about 130 ° C., and then 100 parts by mass of propylene oxide (1.7 mols). ) And 300 parts by mass (6.8 mol) of ethylene oxide were added at a temperature of 150 to 160 ° C. and a pressure of 0.39 MPa or less. After completion of the addition reaction, the mixture was cooled and neutralized to pH 7 with glacial acetic acid to obtain a reaction product of polyethylene glycol (average molecular weight 600), 1.7 mol of propylene oxide and 6.8 mol of ethylene oxide.

(Synthesis Example 8)
<Surfactant (C): (Compound represented by formula (13))>
In a reaction vessel, 86 parts by mass of cresol (0.8 mol), 269 parts by mass of sodium hydroxytolylmethanesulfonate (1.2 mol), 130 parts by mass of 37% by weight formalin solution (1.6 mol of formaldehyde), sodium hydroxide 8 parts by mass and 625 parts by mass of water are charged and reacted at about 100 ° C. for 5 hours. The molar ratio of cresol to sodium hydroxytolylmethanesulfonate is 1: 1.5. An aqueous dispersion of the compound was obtained. Since the residual formaldehyde concentration was less than 0.1%, the average polymerization degree of this compound was 5 when the reaction rate was set to 100%, and the average degree of polymerization of this compound was determined from the raw material molar ratio of the phenol-based processed product and formaldehyde.

(Synthesis Example 9)
<Surfactant (C): (Compound represented by formula (13))>
In a reaction vessel, cresol 130 parts by mass (1.2 mol), sodium hydroxytolylmethanesulfonate 179 parts by mass (0.8 mol), 37% by mass formalin solution 130 parts by mass (formaldehyde 1.6 mol), sodium hydroxide 8 parts by mass and 602 parts by mass of water are charged and reacted at about 100 ° C. for 5 hours. The molar ratio of cresol to sodium hydroxytolylmethanesulfonate is 1: 0.67. An aqueous dispersion of the compound was obtained. It was 5 when the average degree of polymerization of this compound was calculated | required by the method similar to the synthesis example 8.
(Comparative Synthesis Example 1)
<Polyester resin>
In a reaction vessel, 77.6 parts by mass (0.4 mol) of dimethyl terephthalate, 19.4 parts by mass of dimethyl isophthalate (0.1 mol), 387.5 parts by mass of polyethylene glycol (average molecular weight: 3100) (0.125 Mol), 68.2 parts by mass (1.1 mol) of monoethylene glycol, 0.1 part by mass of antimony trioxide and 0.1 part by mass of zinc acetate, and nitrogen gas was introduced. This mixture was heated at 130 ° C., and then slowly heated from 130 ° C. to 180 ° C. over 2 hours to conduct a transesterification reaction. Further, after slowly raising the temperature from 180 ° C. to 250 ° C. over 2 hours, the introduction of nitrogen gas was stopped. Thereafter, the pressure was reduced and the reaction was carried out at 260 ° C. for 30 minutes under a pressure of 0.7 kPa to perform a transesterification reaction, thereby obtaining 500 parts by mass of a polyester resin. The weight average molecular weight of this polyester resin was 36,000. Next, 100 parts by mass of this polyester resin was dissolved in 50 g of N, N-dimethylformamide, and then 850 parts by mass of hot water was added and emulsified to obtain a polyester resin solution.

(Comparative Synthesis Example 2)
<Pentaerythritol oleic acid 2 mol ester>
A reaction vessel was charged with 136 parts by mass (1.0 mol) of pentaerythritol, 560 parts by mass of oleic acid (2.0 mol), and 1 part by mass of paratoluene sulfonic acid, and heated to a temperature of 205-205 in a nitrogen gas stream. The dehydration reaction was performed at 215 ° C. for about 6 hours, and then cooled to obtain a 2 mol oleate of pentaerythritol.

Example 1
First, disperse dye (Kayalon Polyester Black ECX300) 3% o.d. w. f. Dispersing leveling agent (Nikka Sun Salt RM-3406, manufactured by Nikka Chemical Co., Ltd.) 0.5 g / L, 80% by weight Acetic acid 0.3 cc / L, and a regular polyester satin undyed cloth It was immersed at 1:20, and dyeing processing was performed at 130 ° C. for 30 minutes. Then, soaping was performed at 80 ° C. for 20 minutes using a soaping bath containing 2 g / L of a soaping agent (Sunmol RC-700E, manufactured by Nikka Chemical Co., Ltd.), 2 g / L of sodium hydroxide and 2 g / L of hydrosulfite. After the treatment, washing with water × 5 minutes was performed twice and drying was performed at 80 ° C. for 1 hour in a hot air dryer to obtain a polyester dyed cloth (polyester unprocessed cloth).

  Subsequently, 3 parts by mass of the compound obtained in Synthesis Example 1 as the compound (A) and 3 parts by mass of the compound obtained in Synthesis Example 6, and FRBr1 (tris (2,3-dibromopropyl) isocyanurate as the halogen compound (B) ) After mixing 40 parts by mass and 44 parts by mass of ion-exchanged water (ion-exchanged water 1), pre-dispersed with a milder, a bead mill (DYNO-MILL KDL type, Willy E) filled with 0.5 mm glass beads・ Baccofen Co., Ltd.) was used to make a fine particle and emulsified and dispersed. Next, a solution prepared by dissolving 0.2 parts by mass of Rhodopol 23 (xanthan gum, Rhodia Co., Ltd.) in 9.8 parts by mass of ion-exchanged water (ion-exchanged water 2) was added and stirred uniformly to obtain a flame-retardant processing agent for polyester fibers. Obtained. The 50% cumulative particle diameter of the obtained flame retardant for polyester fiber was 0.58 μm.

  The polyester dyed cloth obtained above is dipped in a 20% soln aqueous solution of the obtained flame retardant for polyester fiber, squeezed with a roll so that the pickup becomes 50%, 3 minutes at 120 ° C, and 3 minutes at 180 ° C. It dried for minutes and obtained the flame retardant treatment cloth (a flame retardant treatment, no soaping). Next, a soaping bath containing 2 g / L of a soaping agent (Lipotol TC-350, manufactured by Nikka Chemical Co., Ltd.), 1 g / L of a soaping agent (Escudo FRN, manufactured by Nikka Chemical Co., Ltd.), and 2 g / L of soda ash is prepared. Using, after soaping treatment at 80 ° C for 20 minutes, washing with water x 5 minutes twice, drying at 120 ° C for 3 minutes and further at 180 ° C for 3 minutes to obtain a flame-retardant polyester fiber product (finished) Obtained.

(Examples 2-3 and 51-52)
A flame retardant processing agent for polyester fibers and a flame retardant polyester fiber product were obtained in the same manner as in Example 1 except that the composition of the flame retardant processing agent for polyester fibers was changed to the compositions shown in Tables 1 to 5.

Example 4
40 parts by mass of FRBr1 as the halogen compound (B), 1 part by mass of TSP20S (sulfuric ester sodium salt of an ethylene oxide 20 mol adduct of tristyrenated phenol) as the surfactant (C), and ion-exchanged water (ion-exchanged water 1) ) After mixing 24 parts by mass and pre-dispersing with a milder, a bead mill (DYNO-MILL KDL type, manufactured by Willy et Bacofen) filled with 0.5 mm glass beads was used to perform micronization treatment. Emulsified and dispersed. Subsequently, a solution prepared by dissolving 0.2 parts by mass of Rhodopol 23 (xanthan gum, manufactured by Rhodia) in 9.8 parts by mass of ion-exchanged water (ion-exchanged water 2) was added and stirred uniformly, and then PEG600 ( A solution prepared by dissolving 0.2 parts by mass of polyethylene glycol (average molecular weight 600) in 24.8 parts by mass of ion-exchanged water (ion-exchanged water 3) was added and stirred uniformly to obtain a flame retardant processing agent for polyester fibers. Except for this, the same operation as in Example 1 was performed to obtain a flame-retardant polyester fiber product. The 50% cumulative particle diameter of the obtained flame retardant for polyester fiber was 0.53 μm.

(Examples 5-33, 35-50, 53-59)
(Comparative Examples 1 to 7, 10 to 13, 17 to 18, 20, 22 to 23, 27 to 28, 30 to 31)
Except having made the composition of the flame-retardant processing agent for polyester fibers into the composition shown in Tables 1 to 9, a flame-retardant processing agent for polyester fibers and a flame-retardant polyester fiber product were obtained in the same manner as in Example 4.

(Example 34)
5 parts by mass of PEG 600 as the compound (A), 4 parts by mass of FRP1 and 36 parts by mass of FRBr1 as the flame retardant component, 1 part by mass of TSP20S as the surfactant (C), and ion-exchanged water (ion-exchanged water 1) 44 After mixing parts by mass and pre-dispersing with a milder, the mixture is emulsified and dispersed by using a bead mill (DYNO-MILL KDL type, manufactured by Willy et Bacofen) filled with 0.5 mm glass beads. I was damned. Next, a solution prepared by dissolving 0.2 parts by mass of Rhodopol 23 (xanthan gum, Rhodia Co., Ltd.) in 9.8 parts by mass of ion-exchanged water (ion-exchanged water 2) was added and stirred uniformly to obtain a flame-retardant processing agent for polyester fibers. A flame retardant polyester fiber product was obtained in the same manner as in Example 4 except that it was obtained. The 50% cumulative particle size of the obtained flame retardant processing agent for polyester fibers was 0.55 μm.

(Comparative Example 8)
40 parts by mass of FRP6 as a flame retardant component, 3 parts by mass of TSP20S as a surfactant (C), and 47 parts by mass of ion-exchanged water (ion-exchanged water 1) were mixed and emulsified and dispersed using a homogenizer. Next, a solution prepared by dissolving 0.2 parts by mass of Rhodopol 23 (xanthan gum, Rhodia Co., Ltd.) in 9.8 parts by mass of ion-exchanged water (ion-exchanged water 2) was added and stirred uniformly to obtain a flame-retardant processing agent for polyester fibers. A flame retardant polyester fiber product was obtained in the same manner as in Example 1 except that it was obtained. The 50% cumulative particle diameter of the obtained flame retardant processing agent for polyester fibers was 0.29 μm.

(Comparative Example 9)
Except having used FRP7 (cresyl diphenyl phosphate) as a flame retardant component, operation was performed in the same manner as in Comparative Example 8 to obtain a flame retardant for polyester fiber and a flame retardant polyester fiber product.

(Comparative Examples 14-16, 19, 24-26, 29)
A flame retardant processing agent for polyester fiber and a flame retardant polyester fiber product were obtained in the same manner as in Example 19 except that the composition of the flame retardant processing agent for polyester fiber was changed to the compositions shown in Tables 7-9.

(Comparative Example 21)
The polyester dyed fabric (polyester raw fabric) was used as it was as a polyester fiber product.

  About the flame retardant processing agent for polyester fibers obtained in each Example and Comparative Example, the results of particle size measurement and product stability evaluation are shown in Tables 1 to 9 together with the composition of the flame retardant processing agent for polyester fibers. Moreover, about the obtained flame-retardant polyester fiber product (finished processing), texture, friction fastness, light fastness, exhaustion rate, and flame retardance evaluation results are shown in Tables 1 to 9. The compounds in the table are as follows.

FRP1: phenoxyethyl diphenyl phosphate FRP2: 10-benzyl-9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide FRP3: resorcinol di-2,6-xylenyl phosphate FRP4: 5,5-dimethyl -2- (2′phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide FRBr1: Tris (2,3-dibromopropyl) isocyanurate HBCD: Hexabromocyclododecane FRP5: Tris (dichloropropyl) ) Phosphate FRP6: Resorcinol diphenyl phosphate FRP7: Cresyl diphenyl phosphate.

PEG400: Polyethylene glycol (average molecular weight 400)
PEG600: Polyethylene glycol (average molecular weight 600)
PEG1000: Polyethylene glycol (average molecular weight 1000)
PEG2000: Polyethylene glycol (average molecular weight 2000)
PEG 4000: Polyethylene glycol (average molecular weight 4000)
TW-O120V: Polyoxyethylene sorbitan monooleate (20EO) (Raodol TW-O120V, manufactured by Kao Corporation).

Comparative Synthesis Example 2: A solution obtained by emulsifying the compound (20 parts by mass) obtained in Comparative Synthesis Example 2 with a 30 mol adduct of tristyrenated phenol (5 parts by mass) was obtained in Comparative Synthesis Example 2. Epan 450: Polyoxyethylene polyoxypropylene block polymer (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
D-400: Polypropylene glycol (Daiichi Kogyo Seiyaku Co., Ltd., Highflex D-400)
T-30: Mono beef tallow alkyltrimethylammonium chloride 30% aqueous solution (Lion Co., Ltd., ARCARD T-30), 5% by mass in terms of nonvolatile content TR: Sodium ditridecyl sulfosuccinate 70% aqueous solution (Kao Co., Ltd., PELEX) TR), 5% by mass in terms of nonvolatile content SP-O: sorbitan monooleate (Kao Co., Ltd., Rhedol SP-O10V) (20 parts by mass) tristyrenated phenol ethylene oxide 30 mol adduct (5 parts by mass) ) Is used so that sorbitan monooleate is 5% by mass in terms of non-volatile content. IDA15E: 15 mol of ethylene oxide adduct of isodecanol.

TSP20S: Sulfuric ester sodium salt of tristyrenated phenol ethylene oxide 20 mol adduct TSP20: Ethylene oxide 20 mol adduct of tristyrenated phenol TSCP20: Ethylene oxide 20 mol adduct of tristyrenated phenol

  As described above, according to the present invention, it is excellent in stability, can impart sufficient flame retardancy excellent in durability to the polyester fiber, and exhausts the flame retardant component to the polyester fiber. Although the rate is sufficiently high, the flame-retardant processing agent for polyester fibers capable of sufficiently suppressing the decrease in fastness and texture hardening of the obtained flame-retardant polyester fiber product, and flame retardant using the same It is possible to provide a method for producing a conductive polyester fiber product.

  In addition, since the flame-retardant polyester fiber product obtained by the present invention has both a good texture and flame retardancy, for example, seat sheets, seat covers, curtains, wallpaper, carpets, ceiling cloths, tents, canvases, clothing It can use suitably for etc.

Claims (3)

A flame retardant processing agent for polyester fibers, comprising at least one compound (A) selected from the group consisting of the following compounds (a ¹ ) to (a ³ ) and the following halogen compound (B).
<Compound (a ¹ )>
The following general formula (1):
[In Formula (1), R ¹ and R ³ are either R ¹ and R ³ each representing a hydrogen atom , or ^one of R ¹ and R ³ is a hydrogen atom and the other is represented by the following general formula ( 1a ):
-SO ₃ M ··· (1a)
Wherein (1a), M represents a water atom or a monovalent cation group. ]
In denotes an anion group represented, R ² is each independently an alkylene group having 2 to 4 carbon atoms, a is an average addition mole number of alkylene group represented by (R 2 ^-O) An integer of 3 to 1000 is shown. However, the content of the ethyleneoxy group with respect to the total amount of the oxyalkylene chain represented by (R ² —O) _a is 90% by mass or more. ]
A compound represented by
<Compound (a ² )>
The following general formula (2):
[In the formula (2), R ⁴ represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms and a c valence, or a fatty acid in which a part of carbon atoms of the aliphatic hydrocarbon group is substituted with an oxygen atom. shows a family group, ^{R 5} is each independently an alkylene group having 2 to 4 carbon atoms, ^{R 6} are each independently a hydrogen atom, lower following general formula (1a) ~ (1g):
[In formulas (1a) to (1g), M independently represents a hydrogen atom or a monovalent cation group. ]
Selected from the group consisting of an anionic group represented by any one of the above, an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, and an alkynylcarbonyl group having 2 to 22 carbon atoms. indicates either, b is an average addition mole number of alkylene group represented by ^(R 5 -O), independently represents an integer of 0 to 1000, c is an integer of 2 to 10 . However, the sum total of all b is 3-1000, and content of the ethyleneoxy group with respect to the total amount of the oxyalkylene chain represented by (R < ⁵ > -O) _b is 90 mass% or more. ]
A compound represented by
<Compound (a ³ )>
The following general formula (3):
[In Formula (3), R ⁷ represents an aliphatic hydrocarbon group having 1 to 21 carbon atoms and an e valence, R ⁸ independently represents an alkylene group having 2 to 4 carbon atoms, and R ⁹ Are each independently a hydrogen atom, an anionic group represented by any one of the general formulas (1a) to (1g), an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, Any one selected from the group consisting of an alkynyl group having 2 to 22 carbon atoms, an alkylcarbonyl group having 1 to 22 carbon atoms, an alkenylcarbonyl group having 2 to 22 carbon atoms, and an alkynylcarbonyl group having 2 to 22 carbon atoms , D is the average number of added moles of the alkyleneoxy group represented by (R ⁸ —O), and each independently represents an integer of 0 to 1000, and e represents an integer of 2 to 10. However, the total of all d is 3 to 1000, and the content of ethyleneoxy groups with respect to the total amount of oxyalkylene chains represented by (R ⁸ —O) _d is 90% by mass or more. ]
A compound represented by
<Halogen compound (B)>
The following general formula (4):
[In Formula (4), Y ^{1 to} Y ³ are each independently selected from the group consisting of 2,3-dibromopropyl group, 2,3-dibromoisobutyl group and 1,2-dibromoethyl group. The group of is shown. ]
A halogen compound represented by   2. The polyester according to claim 1, wherein a mass ratio (A: B) of the content of the compound (A) and the content of the halogen compound (B) is 1: 100 to 50: 100. Flame retardant for textiles.   A method for producing a flame-retardant polyester fiber product, wherein the polyester fiber is treated with the flame-retardant processing agent for polyester fiber according to claim 1 or 2.