JPH09170178A - Treating agent for yarn and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a treating agent for a nonhalogen-based flame-retardant processing for a polyester yarn, by reacting a diol component with a phosphinic acid derivative to give a specific polyester compound and emulsifying and dispersing the compound. SOLUTION: A diol component A of a 2-10C alkylene glycol is reacted with a phosphinic acid derivative of formula I (R<1> is a 1-12C bifunctional aliphatic or alicyclic hydrocarbon; R<2> is a 1-6C alkyl or phenyl; R<3> and R<4> are each H or a 1-6C alkyl) at 100-230 deg.C and, if necessary, successively reacted at 250-300 deg.C to give a polyester compound of formula II (R<1> and R<2> are each as shown above; R<5> is a bifunctional residue of the diol component A), formula III (R<1> , R<2> and R<5> and each as shown above; R<6> and R<7> are each H or R<5> OH; (m) is 1-300) or formula IV (R<1> , R<2> , R<5> and R<6> are each as shown above; (n) is 1-300), having 1,000-50,000 weight-average molecular weight. The polyester composition is emulsion and dispersed in the presence of a surfactant to give the objective treating agent for a yarn.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fiber treatment agent. More specifically, it relates to a non-halogen flame retardant processing agent for polyester synthetic fibers.

[0002]

2. Description of the Related Art Conventionally, as a treatment agent for flame-retardant processing of polyester synthetic fibers, an aqueous dispersion of hexabromocyclododecane (for example, JP-A-57-137377).
However, the use of halogen-containing compounds has become a problem from the viewpoint of environmental protection, and there has been a demand for non-halogen flame retardant treatment agents.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a treating agent which imparts durable flame retardancy to a polyester synthetic fiber by post-processing using a halogen-free compound.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that good flame retardancy and durability (wash resistance, dry cleaning resistance, etc.) The present invention has been completed by finding an excellent fiber treating agent to be applied by post-processing. That is, the present invention relates to a fiber treating agent containing a polyester compound obtained by reacting a diol component (A) with a phosphinic acid derivative (B) represented by the following general formula (1). [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ³ , R ⁴ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms and may be the same or different. ]

The polyester compound (C) of the present invention includes, for example, polyester compounds having structures represented by the following general formulas (2), (3) and (4). For example, the compound (2) is a polyester compound obtained by a reaction in which the molar ratio of the diol component (A) and the phosphinic acid derivative (B) is 1: 1. The compound (3) is a polyester compound obtained by a reaction in which the diol component (A) and the phosphinic acid group (B) have a molar ratio of m: m + 1 and having a phosphinic acid group or a derivative group thereof at its terminal. Compound (4)
Is a compound obtained by reacting the diol component (A) and the phosphinic acid derivative in a molar ratio of n: n + 1, like the compound (3). This is a polyester compound having a carboxyl group or its derivative group at the terminal. .

[0006] [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ⁵ represents a divalent residue of the diol component (A). ]

[0007]

Embedded image

[Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or (substituted) phenyl Group; R ⁵ is a divalent residue of the diol component (A); R ⁶ and R ⁷
Are each independently a hydrogen atom or —R ⁵ OH, and m is 1 to
Represents a number of 300. ]

[0009]

Embedded image

[Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or (substituted) phenyl Group; R ⁵ is a divalent residue of the diol component (A); R ⁶ and R ⁷
Are each independently a hydrogen atom or —R ⁵ OH, and n is 1 to
Represents a number of 300. ]

Further, the polyester compound (C) of the present invention
Includes a polyester compound obtained by further reacting the polyester compounds having the structures of the general formulas (2), (3) and (4) mentioned above.

Specific examples of the diol component (A) used in the present invention include alkylene glycol, polyoxyalkylene glycol, alkylene oxide adduct of alkyle glycol, and divalent aromatic hydroxy represented by bisphenol A. Examples thereof include alkylene oxide adducts of compounds. Of these, preferred are alkylene glycols, more preferably 2 to 2 carbon atoms.
Of the 10 linear or branched alkylene glycols, ethylene glycol, propylene glycol, tetramethylene glycol and neopentyl glycol are particularly preferred. Also, two or more diol components can be used in combination. The molecular weight is not particularly limited, but it is 10
00 or less is preferable, and if it exceeds 1000, the phosphorus content becomes low and the flame retardancy is lowered.

R ¹ of the phosphinic acid derivative (B) represented by the general formula (1) is a divalent aliphatic or aliphatic hydrocarbon group having 1 to 12 carbon atoms. Preferably an ethylene group,
Propylene group, tetramethylene group, pentamethylene group,
A hexamethylene group and a cyclohexamethylene group. R
² is a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group, and preferably,
A methyl group and a phenyl group. R ³ and R ⁴ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms and may be the same or different. Preferably R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrogen atom.

As a typical example of the phosphinic acid (B), 2-carboxyethyl (phenyl) phosphinic acid of the following formula (5) can be obtained by the method described in US Pat. No. 4,033,936.

The polyester compound of the present invention is produced, for example, by the following method. The diol component (A) and the phosphinic acid derivative (B) were mixed with (A) :( B) = 1.5: 1.
0 to 1.0: 1.0, preferably 1.1: 1 to 1.0
At a molar ratio of 5: 1, first, an esterification or transesterification reaction is carried out at 100 to 230 ° C., preferably 130 to 200 ° C., and dehydration or de-alcohol reaction is carried out to obtain the above (2) to (4). A relatively low molecular weight precondensate polyester compound having the structure of is obtained. When R ³ and R ⁴ of the compound (1) are hydrogen atoms, the esterification reaction proceeds by heating without using a catalyst. When R ³ and R ⁴ of the compound (1) are alkyl groups having 1 to 6 carbon atoms, the reaction proceeds promptly due to the presence of a conventionally known catalyst for transesterification, such as manganese acetate.
This relatively low molecular weight initial condensate also has excellent flame retardancy as the treating agent of the present invention. In order to impart higher durability as necessary, subsequently, the temperature and the degree of reduced pressure are gradually increased in the presence of, for example, antimony trioxide as a polyesterification catalyst, and finally 250 to 300 ° C., preferably 260 to 280 ° C. At a reduced pressure of 1 mmHg or less,
React for 5 to 5 hours to further increase the molecular weight.

The polyester compound (C) of the present invention is
It is obtained by reacting (A) and (B) as essential components, but if necessary, a polyfunctional diol component (A ′) which reacts with these may be partially polycondensed. For example, a part of the diol component (A) may be a hydrophilic group [sulfuric acid (salt)].
Group, carboxylic acid (salt) group, nitrate base, etc.] (eg, ethylene glycol diester of sulfophthalic acid, ethylene glycol diester of sulfonaphthalenedicarboxylic acid, sulfophenoxyphthalic acid, ethylene oxide adduct of sulfamic acid, Tartaric acid, nitrophthalic acid ethylene glycol diester, etc.) component (A ′) may be substituted for the reaction.

The weight average molecular weight of the polyester compound (C) is usually 1,000 to 50,000, preferably 2,000 to 25,000. Weight average molecular weight is 1
When it is less than 000, the durability such as washing resistance is insufficient, and when it exceeds 50,000, the emulsification dispersibility is lowered and the adhesion to the polyester-based synthetic fiber is also poor.

The phosphorus content in the polyester compound is
It is usually 3 to 20% by weight, preferably 5 to 18% by weight. If it is less than 3% by weight, the flame retardancy when treating the fiber is insufficient, and if it exceeds 20% by weight, the weight average molecular weight of the polyester compound becomes low and the durability becomes insufficient.

The polyester compound (C) itself of the present invention is usually a solid substance, which is emulsified and dispersed in water or an organic solvent and used as a treating agent for fibers. The method of emulsifying and dispersing in water may be a known method. For example, the polymer, a surfactant such as a nonionic surfactant or an anionic surfactant, and an organic solvent are blended and uniformly dissolved, and gradually warmed with warm water. A method of adding and emulsifying and dispersing is used.

The nonionic surfactants include polyoxyalkylene type nonionic surfactants (higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, Higher alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, etc.) and polyvalent alcohol type nonionic surfactants (alkyl glycosides, sucrose fatty acid esters, etc.).

As the anionic surfactant, a sulfuric acid ester salt (a higher alcohol sulfuric acid ester salt, a higher alkyl ether sulfuric acid ester salt, a sulfated fatty acid ester, etc.),
Examples thereof include sulfonates (alkylbenzene sulfonates, alkylnaphthalene sulfonates, etc.) and phosphoric acid ester salts (higher alcohol phosphoric acid ester salts, alkylene oxide adduct phosphoric acid ester salts of higher alcohols, etc.).

As the organic solvent, toluene, xylene,
Aromatic hydrocarbons such as alkylnaphthalene; ketones such as acetone and methyl ethyl ketone; dioxane;
Examples thereof include ethers such as ethyl cellosolve; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; and mixtures of two or more thereof.

The polyester-based synthetic fibers applied in the present invention include cotton, yarn, tow, top and case made of polyester fibers such as polyethylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / paraoxybenzoate, polyethylene terephthalate / butylene terephthalate. , Knitted fabrics, non-woven fabrics, and the like. Furthermore, the above polyester fibers and other natural, regenerated, semi-synthetic, synthetic fibers blended,
Examples include mixed woven fabrics.

The treatment agent of the present invention is usually diluted with water and used in the form of a treatment liquid. The solid content concentration of the treatment agent in the treatment liquid varies depending on the type of fiber product to which the treatment liquid is applied, but is usually 0.05 to 30% by weight, preferably 0.5 to
It is 20% by weight. If the amount is less than 0.05% by weight, the flame retardancy becomes poor, and if it exceeds 30% by weight, the texture of the treated fiber becomes coarse and hard.

The method for applying the present treating agent to the polyester fiber is under high temperature and pressure (110 to 130 ° C., 1 to 3).
The usual methods such as an exhaust method of exhausting at atmospheric pressure), a dipping method, a padding method and a spray method can be mentioned. Other than the exhaust method, the treatment temperature may be room temperature. After application, it is dried and heat treated in the usual way. Drying is usually 80 to 13
At 0 ° C. for 1 to 10 minutes, the heat treatment is usually 150 to 200.
C., 10 seconds to 10 minutes.

The treatment agent of the present invention can be used in combination with a fiber processing agent. As such a fiber processing agent, a softening agent,
Examples include water-absorption processing agents, antistatic agents, water / oil repellent agents, hard finishing agents, texture modifiers, and antislip agents.

The treatment agent of the present invention can impart durable flame retardancy such as washing resistance without containing harmful halogen as compared with the conventional one by treating the polyester fiber. At the same time, the same flame retardancy and durability can be imparted even if the amount used is reduced. Further, since the polyester compound of the present invention has an appropriate hygroscopicity, it can also impart antistatic properties and does not impair the texture.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

[0029]

【Example】

Production Example 1 A 1 L Kolben equipped with a stirrer, a thermometer, a nitrogen blowing tube and a distilling tube was charged with 199 g of ethylene glycol and 642 g of 2-carboxyethyl (phenyl) phosphinic acid represented by the following chemical formula (5): The reaction was carried out at 200 ° C for 4 hours while distilling and removing the produced water while blowing nitrogen into the liquid. Subsequently, a vacuum pump was attached, 250 mg of antimony trioxide was added as a catalyst, the reaction vessel was gradually heated, and the system was depressurized. Temperature 270 ℃, Decompression degree 1mmHg
And allowed to react for 1 hour to obtain a polyester compound (C-1) having a weight average molecular weight of 7,500 and a phosphorus content of 12.8%. The present compound (C-1) (300 parts), dimethylformamide (50 parts), and nonylphenolethylene oxide (20 mol) adduct (50 parts) were uniformly dissolved at 80 ° C, and hot water (80
600 ° C.) was gradually added to emulsify / dilute and then cooled to room temperature to obtain the treating agent “1” of the present invention. "1" was a pale yellowish-white emulsion.

Production Example 2 Neopentyl glycol (343 g) was added to a 1 L Kolben equipped with a stirrer, a thermometer, a nitrogen blowing tube and a distillation tube.
-Carboxyethyl (phenyl) phosphinic acid 642 g
Was charged, and the reaction was carried out at 130 ° C. for 6 hours while distilling and removing the produced water while blowing nitrogen into the liquid. Subsequently, a vacuum pump was installed, 170 mg of antimony trioxide was added as a catalyst, the reaction vessel was gradually heated, and the system was depressurized. The reaction was carried out at a temperature of 270 ° C. and a reduced pressure of 0.5 mmHg for 3 hours to obtain a polyester compound (C-2) having a weight average molecular weight of 9,500 and a phosphorus content of 10.9%.
This compound (C-2) 300 parts, dimethylformamide 5
0 parts, nonylphenol ethylene oxide 30 mol adduct 30 parts, lauryl alcohol ethylene oxide 2
20 parts of 0 mol adduct was uniformly dissolved at 80 ° C.
(0 ° C.) 600 parts were gradually added to emulsify and dilute, and then cooled to room temperature to obtain the treating agent “2” of the present invention. "2" was a pale yellowish milky emulsion.

Production Example 3 In a 1 L Kolben equipped with a stirrer, a thermometer, a nitrogen blowing tube and a distillation tube, 199 g of ethylene glycol and 2-carboxyethyl (methyl) represented by the following chemical formula (6).
Phosphinic acid (456 g) was charged, and the reaction was carried out at 200 ° C. for 2 hours while distilling and removing the produced water while blowing nitrogen into the liquid. Subsequently, a vacuum pump was installed, 140 mg of antimony trioxide was added as a catalyst, the reaction vessel was gradually heated, and the system was depressurized. Temperature 270 ℃, Decompression degree 1mmHg
And allowed to react for 1 hour to obtain a polyester compound (C-3) having a weight average molecular weight of 7,000 and a phosphorus content of 17.2%. 300 parts of the present compound (C-3), 50 parts of dimethylformamide, 30 parts of nonylphenol ethylene oxide 20 mol adduct, 20 parts of lauryl alcohol ethylene oxide 20 mol adduct are uniformly dissolved at 80 ° C, and hot water (80 ° C) is used. Emulsified / diluted by gradually adding 600 parts, and cooled to room temperature to obtain the treating agent "3" of the present invention. "3"
It was a light yellow milky white emulsion.

Comparative Example 1 Each component having the following formulation was continuously mixed and pulverized for 30 minutes with a viscomill (horizontal wet fine powder disperser manufactured by Igarashi Kikai Kogyo KK) to obtain a comparative treatment agent "4". "4" was a milky white dispersion. Formulation: 1,2,5,6,9,10-hexabromocyclododecane 300 parts Nonylphenol ethylene oxide 20 mol adduct 35 Lauryl alcohol sulfate sodium salt 10 Carboxymethylcellulose sodium salt 5 Water 650

<Performance test> The treatment agents [1] to [4] are treated with a color master on an undyed woven fabric made of polyethylene terephthalate, and the result of a performance test as a flame retardant is shown in Table 1.

[0034]

[Table 1]

<Test method> 25 g of polyester undyed woven fabric of 300 g / m ² and Kayaron polyester Navy Blue 2R-SF (manufactured by Nippon Kayaku) 2% as a dye
o. w. f. , Dispersing and Leveling Agent Ionet RAP-250
(Manufactured by Sanyo Kasei Co., Ltd.) 0.5 g / l, the above treating agent [1]
~ [4] 10% o. w. f. , 130 ° C with a color master (Tsujii Dyeing Machine dyeing machine) in an aqueous solution with a bath ratio of 1:20
Treated for × 30 minutes, washed with water and dried (100 ° C × 3 minutes), and then heat treated (170 ° C × 1 minute), JIS L-1091
A flame retardancy test was conducted according to Method D. JISL-02 for washing
17 (103 method), dry cleaning is JIS L-
Followed 1018.

[0036]

Industrial Applicability The treatment agent of the present invention shows excellent flame retardancy when added to a polyester fiber as a post-treatment agent, and is a useful treatment agent which does not contain halogen and has durability. . Because of the above effects, the textile agent of the present invention is useful as a polyester flame retardant for post-processing.

Claims (8)

[Claims] 1. A diol component (A) and the following general formula (1):
A treatment agent for fibers, which comprises a polyester compound (C) obtained by reacting the phosphinic acid derivative (B). [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ³ , R ⁴ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms and may be the same or different. ] 2. The treating agent for fibers according to claim 1, wherein the polyester compound (C) contains a structural unit represented by the following general formula (2). [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ⁵ represents a divalent residue of the diol component (A). ] 3. The treating agent for fibers according to claim 1, wherein the polyester compound (C) is represented by the following general formula (3). Embedded image [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ⁵ is a divalent residue of the diol component (A); R ⁶ and R ⁷ each independently represent a hydrogen atom or —R ⁵ OH, and m represents a number of 1 to 300. ] 4. The treating agent for fibers according to claim 1, wherein the polyester compound (C) is represented by the following general formula (4). Embedded image [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ⁵ is a divalent residue of the diol component (A); R ⁶ and R ⁷ are each independently a hydrogen atom or —R ⁵ OH, and n is a number of 1 to 300. ] 5. The polyester compound (C) has a weight average molecular weight of 1,000 to 50,000.
The treatment agent for fibers according to any one of the above. 6. The diol component (A) has 2 to 10 carbon atoms.
6. The treatment agent for fibers according to claim 1, which is the linear or branched alkylene glycol. 7. A diol component (A) and the following general formula (1):
The phosphinic acid derivative (B) represented by
A method for producing a treating agent for fibers, which comprises reacting at 0 ° C and, if necessary, subsequently at 250 to 300 ° C. [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ³ , R ⁴ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms and may be the same or different. ] 8. A diol component (A) and the following general formula (1):
The method for producing a treating agent for fibers, which further comprises reacting an initial condensate derived from the phosphinic acid derivative (B) represented by the above at 250 to 300 ° C. [Wherein R ¹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a (substituted) phenyl group; R 2 ³ , R ⁴ are hydrogen atoms or alkyl groups having 1 to 6 carbon atoms and may be the same or different. ]