JPH10131056A - Fiber treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject halogen-free treatment agent that contains a polyamide derived from a dicarboxylic acid, a diamine and a specific phosphinic acid derivative and imparts durable flame retardancy to synthetic fibers through the posttreatment. SOLUTION: This treatment agent contains a polyamide derived from (A) a dicarboxylic acid or its acid chloride, (B) a diamine and (C) a phosphinic acid derivative of formula I [R<1> and R<2> are each H independently from each other, a 1-22C alkyl, a 2-22C alkenyl, a 5 or 6C cycloalkyl, a 6-14C aryl; a 7-13C arylalkyl; Y is a monovalent organic group of formula II (Z is hydroxyl, Cl)]. The polyamide is prepared through a melt or solution polycondensation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fiber treatment agent. More specifically, the present invention relates to a treatment agent for flame retarding synthetic fibers.

[0002]

2. Description of the Related Art Conventionally, an aqueous dispersion of hexabromocyclododecane (JP-A-57-137377) has been known as a flame retardant treatment agent for synthetic fibers such as polyester and polyamide. However, the use of halogen compounds has become a problem from the viewpoint of environmental protection, and non-halogen flame retardants have been sought.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a treating agent which imparts durable flame retardancy to synthetic fibers by post-processing using a compound containing no halogen atom.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that good flame retardancy and durability (washing resistance, dry cleaning resistance, etc.) are obtained from polyester synthetic fibers. The present inventors have found an excellent fiber treating agent which can be provided by post-processing, and have reached the present invention. That is, the present invention comprises a polyamide compound (D) derived from a dicarboxylic acid or its acid chloride (A), a diamine component (B) and a phosphinic acid derivative (C) represented by the following general formula (1). Fiber treating agent. [Wherein, R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 14 carbon atoms,
An arylalkyl group having 7 to 13 carbon atoms, which may be the same or different, and wherein R ¹ and R ² may be bonded to each other to form a ring together with P; It is a monovalent organic group represented by the formula (2), and Z represents a hydroxyl group or a chlorine atom. ]

Specific examples of the dicarboxylic acid or its acid chloride (A) used in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; phthalic acid, terephthalic acid,
Aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid; and their acid chlorides.
Preferred among these are adipic acid, terephthalic acid and their acid chlorides.

Specific examples of the diamine component (B) used in the present invention include aliphatic diamines such as ethylenediamine, hexamethylenediamine, 1,7-diaminoheptane and 1,12-diaminododecane; piperazine, isophoronediamine, and the like. Cyclohexanediamine, 4,4'-
Alicyclic diamines such as bis (p-aminocyclohexyl) methane; m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 4,4′-methylenedianiline, 4,4 '-Diaminophenyl ether, 4,4'-diaminodiphenylamine, 4,4'-diaminobiphenyl (benzidine), 2,5-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3, Aromatic diamines such as 5-diaminotoluene; benzoguanamine, acetoguanamine, 2,6-diaminopyridine,
4,5-diaminopyrimidine, 2,4-diamino-5
Phenyl-1,3-thiazole, 2,4-diamino-5
And heterocyclic diamines such as -phenyl 1,3-oxazole. Of these, aliphatic, alicyclic, and aromatic diamines having 2 to 6 carbon atoms are preferable, and aliphatic ethylene diamine, hexamethylene diamine, and alicyclic cyclohexanediamine are particularly preferable. Also,
Two or more diamine components can be used in combination.

The alkyl group of the substituents R ₁ and R ₂ of the phosphinic acid derivative (C) represented by the general formula (1) is a linear or branched alkyl group having 1 to 22 carbon atoms, such as a methyl group. , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, n-hexyl group, 2-ethylbutyl group, n-
Heptyl group, isoheptyl group, 2-ethylhexyl group,
Isononyl group, n-decyl group, isodecyl group, n-dodecyl group, n-hexadecyl group, n-octadecyl group, n
-Icosyl group and n-docosyl group, and from the viewpoint of phosphorus content, an alkyl group having 1 to 6 carbon atoms is preferable.

The alkenyl group for the substituents R ₁ and R ₂ is a linear or branched alkenyl group having 2 to 22 carbon atoms,
Examples include vinyl group, 1-propenyl group, 2-propenyl group, isopenyl group, 2-butenyl group, 2-pentenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, icosenyl group and docosenyl group. From the viewpoint of phosphorus content, an alkenyl group having 2 to 6 carbon atoms is preferable.

The cycloalkyl group for the substituents R ₁ and R ₂ is a cyclopentyl group or a cyclohexyl group.

The aryl group of the substituents R ₁ and R _{2 is} an aryl group having 6 to 14 carbon atoms, such as a phenyl group,
Tolyl group, xylyl group, mesityl group, cumenyl group, octylphenyl group, biphenylyl group, naphthyl group, anthryl group, phenanthryl group, and phenyl group,
Biphenylyl groups are preferred.

The arylalkyl group for the substituents R ₁ and R _{2 is} an arylalkyl group having 7 to 13 carbon atoms, and is preferably a benzyl group or a phenethyl group. Examples of R ₁ and R ₂ bonded to each other to form a ring together with P include a naphthylene group, a phenanthrene group, and an alkylene group having 3 to 5 carbon atoms.

[0012] In the general formula (1), n is an integer of 0 to 2, preferably 1.

Y in the general formula (1) is the same as the general formula (2)
Is a monovalent organic group represented by Substituent Z is a hydroxyl group or a chlorine atom.

In the general formula (3), p and q are each 0.
An integer of 2 to 2, preferably 0.

Further, R ³ and R ⁴ in the general formula (2)
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and s.
ec-butyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, n-hexyl group, 2-ethylbutyl group, n-heptyl group, isoheptyl group, 2-ethylhexyl group, preferably a hydrogen atom It is a methyl group, more preferably a hydrogen atom.

In the present invention, specific examples of the phosphinic acid derivative (C) represented by the general formula (1) include:
The following compounds (C1) to (C9) are exemplified, but not limited thereto.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The phosphinic acid derivative (C) used in the present invention
As the above, the compounds (C7) to (C9) in which the substituents R ₁ and R ₂ in the formula are a biphenyl group and form a ring with each other are particularly preferable.

The polyamide compound (D) can be produced by a conventionally known polyamide production method, for example, a melt polycondensation method or a solution polycondensation method.

The polyamide compound (D) in the present invention
Can be produced by subjecting a dicarboxylic acid or its acid chloride (A), diamine component (B) and phosphinic acid derivative (C) to a dehydration or dehydrochlorination reaction by a known method. In the amidation reaction, the total number of moles (m1) of (A) and (C) and the number of moles of (B) (m
The ratio (m1 / m2) of 2) is usually 0.5 to 2, preferably 0.8 to 1.2.

The phosphorus content in the polyamide compound (D) is
Usually, it is 0.5 to 10% by weight, preferably 1 to 8% by weight. If it is less than 0.5% by weight, the flame retardancy when treated into fibers is insufficient, and if it exceeds 10% by weight, the rub fastness of the treated synthetic fiber dyed product is reduced.

The weight average molecular weight of the polyamide compound is usually from 1,000 to 20,000, preferably from 2,000 to 2,000.
15,000. If the average molecular weight is less than 1,000, the durability is insufficient.
The dispersibility of the polyamide compound is poor, and the adsorptivity to the synthetic fiber is also poor.

The polyamide compound is usually used by dispersing or dissolving in water or an organic solvent as the fiber treating agent of the present invention. As a method for dispersing the compound in water, for example, the compound, a surfactant such as a nonionic surfactant and an anionic surfactant and an organic solvent are blended and uniformly dissolved, and gradually added with hot water to emulsify. There is a method of dispersing.

Examples of the nonionic surfactant 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 polyhydric alcohol-type nonionic surfactants (alkyl glycosides, sucrose fatty acid esters, etc.).

Examples of the anionic surfactants include sulfate salts (higher alcohol sulfate salts, higher alkyl ether sulfate salts, sulfated fatty acid esters, etc.),
Sulfonates (eg, alkylbenzene sulfonates, alkylnaphthalene sulfonates), and phosphate salts (eg, higher alcohol phosphates, higher alcohol alkylene oxide adduct phosphates, etc.).

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

The synthetic fibers used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, and polyethylene terephthalate / 5-sodisulfolate. Polyester fiber such as isophthalate, polyethylene terephthalate / polyoxybenzoyl, polybutylene terephthalate / isophthalate, polyhexamethylene adipamide, polycaprolactam, polyhexamethylene terephthalamide, poly-m-xylyleneazi Cotton, thread, tow, top, sash, knitted fabric, non-woven fabric, etc. made of nylon fiber such as pamide. Further, there may be mentioned a blend of the above-mentioned synthetic fibers with other natural, regenerated, semi-synthetic, synthetic fibers, and a cross-woven fabric.

The treating agent of the present invention is usually used in the form of a treating solution diluted with water. The solid concentration in the processing solution is 1
0 to 50% by weight. The amount of the treatment agent applied to the fiber varies depending on the type of the fiber product.
It is 5 to 30% by weight, preferably 0.5 to 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.

Examples of the method for applying the treating agent of the present invention to synthetic fibers include ordinary methods such as an exhaustion method, padding method and spray method. Except for the exhaustion method, the treatment temperature may be room temperature. After the treatment agent is applied, drying and heat treatment are performed in a usual manner. Drying is usually performed at 80 to 130 ° C. for 30 seconds to 30 minutes, and heat treatment is usually performed at 150 to 200 ° C. for 10 seconds.
Seconds to 10 minutes.

The treatment agent of the present invention is used before dyeing synthetic fibers.
It may be performed at the same time as the dyeing or at any time after the dyeing, and the method performed at the same time as the dyeing is preferable in terms of work efficiency.

The treatment agent of the present invention can be used in combination with other fiber processing agents. Examples of such a fiber processing agent include a softening agent, a water absorbing agent, an antistatic agent, a water / oil repellent, a hard finish,
Examples include a texture adjusting agent and an anti-slip agent.

The treating agent of the present invention can impart a more durable flame retardancy without containing a halogen as compared with the conventional one, particularly by treating a synthetic fiber.

[0041]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. Parts in Examples are parts by weight, and% means% by weight.

Example 1 49 parts of adipic acid, 223 parts of a phosphinic acid derivative of the compound (C8), 62 parts of ethylenediamine, and 3 parts of acetic acid
And reacting at 220 ° C. for 4 hours under pressure. After the reaction, the pressure was gradually reduced to a reduced pressure, and the pressure was raised to atmospheric pressure with nitrogen, and the temperature was raised to 260 ° C. Thereafter, the pressure was gradually reduced to 133 Pa or less, and the mixture was reacted at 260 ° C. for 3 hours to obtain a polyamide having a weight average molecular weight of 8,000 and a phosphorus content of 6.0%. 150 parts of the polyamide compound, 100 parts of dimethylformamide, and 50 parts of a 15 mol nonylphenol ethylene oxide adduct
The solution was uniformly dissolved at 0 ° C., gradually added to 700 parts of hot water (80 ° C.) to form particles, cooled to room temperature, and then pulverized continuously for 30 minutes with a biscomil (IMEX horizontal wet fine powder disperser). 1,000 parts of the treating agent "1" was obtained. "1"
Is a milky white dispersion having a viscosity of 0.43 Pa · s (25
° C), the average particle size was 0.4 µm, and the pH was 7.

Example 2 30 parts of terephthalic acid, 277 parts of the phosphinic acid derivative of the compound (C8), 62 parts of ethylenediamine and 3 parts of acetic acid were mixed and reacted at 240 ° C. for 4 hours under pressure. After the reaction, the pressure was gradually reduced to a reduced pressure, and then the pressure was raised to atmospheric pressure with nitrogen and the temperature was set to 270 ° C. Thereafter, the pressure was gradually reduced to 133 Pa or less, and the mixture was reacted at 260 ° C. for 3 hours to obtain a polyamide compound having a weight average molecular weight of 6,500 and a phosphorus content of 7.5%. 150 parts of the polyamide compound, 100 parts of dimethylformamide, 15 mol of nonylphenol ethylene oxide 15 mol adduct
, 20 parts of lauryl alcohol ethylene oxide adduct was uniformly dissolved at 80 ° C, and hot water (80 ° C) 7
After gradually adding 00 parts to form particles, the mixture was cooled to room temperature, and then pulverized continuously for 30 minutes with a Viscomil (IMEX horizontal wet fine powder dispersing machine) to obtain 1,000 parts of the treating agent "2" of the present invention. "2" is a milky white dispersion having a viscosity of 0.3 Pa
S (25 ° C.), average particle size 0.5 μm, and pH 7.2.

Example 3 63 parts of adipic acid, 190 parts of a phosphinic acid derivative of the compound (C8), 119 parts of hexamethylenediamine and 3 parts of acetic acid as a terminal blocker are mixed and reacted at 220 ° C. for 4 hours under pressure. After the reaction, the pressure was gradually reduced to a reduced pressure, and the pressure was raised to atmospheric pressure with nitrogen, and the temperature was raised to 260 ° C. Thereafter, the pressure was gradually reduced to 133 Pa
The reaction was carried out at 260 ° C. for 3 hours to obtain a polyamide compound having a weight average molecular weight of 7,000 and a phosphorus content of 5.1%. 150 parts of the present polyamide compound, 100 parts of dimethylformamide, 30 parts of an adduct of 15 mol of nonylphenol ethylene oxide and 20 parts of an adduct of 18 mol of lauryl alcohol ethylene oxide are uniformly dissolved at 80 ° C., and 700 parts of hot water (80 ° C.) are gradually added. After cooling to room temperature, the mixture was continuously pulverized with a Viscomil (horizontal wet fine powder disperser manufactured by IMEX) for 30 minutes to obtain 1,000 parts of a treating agent "3" of the present invention. "3" is a milky white dispersion having a viscosity of 0.55 Pa · s (25 ° C.) and an average particle size of 0.3.
μm, pH was 7.3.

Comparative Example Each component having the following formulation was continuously mixed and pulverized for 1 hour with a Viscomil (IMEX horizontal wet fine powder disperser) to obtain 1,000 parts of a comparative treating agent "4". “4” is a pale yellow milky white dispersion having a viscosity of 1 Pa · s (25 ° C.) and a pH of 6.5,
The average particle size was 0.8 μm. Formulation: 1,2,5,6,9,10-hexabromocyclododecane 400 parts Nonylphenol ethylene oxide 20 mol adduct 30 parts Lauryl alcohol sulfate sodium salt 10 parts Carboxymethyl cellulose sodium salt 5 parts Water 555 parts

<Flame Retardancy Test> Tables 1 and 2 show the results of a high temperature treatment and a normal temperature treatment using the treatment agents [1] to [4], and a performance test as a flame retardant.

Test Method 1 (High temperature treatment) A 300 g / m ² polyester undyed woven fabric was dyed [Kay
alon Polyester NavyBlue 2R-SF (Nippon Kayaku)] 2%
o. w. f. 0.5 g / l of dispersing and leveling agent [Ionette RAP-250 (manufactured by Sanyo Chemical Industries)], 15% o. w. f. 7.5% o., Comparative treatment agent (active ingredient of flame retardant 40%). w. f. In a water dispersion containing 1 at a bath ratio of 1:20, using a color master (a dyeing machine manufactured by Tsujii Dyeing Machine) at 130 ° C. for 30 minutes, washing with water and drying (100 ° C. for 3 minutes), followed by heat treatment (17 ° C.).
(0 ° C. × 1 minute). Table 1 shows the results of a test on the flame retardancy of this according to the method D of JIS L-1091. In addition,
Washing is JIS L-1042. Dry cleaning is J.
According to IS L-1018.

[0048]

[Table 1]

Test Method 2 (Normal Temperature Treatment) A 300 g / m ² polyester undyed woven fabric was padded in the following treatment bath (80% squeezing ratio) and dried (10%).
0 ° C. × 5 minutes) and heat set (190 ° C. × 50
Sec), and the same flame retardancy test as in Test Method 1 was performed. (Treatment bath) Dye [Kayalon Polyester Navy Blue 2R-SF (manufactured by Nippon Kayaku)] 10 g / l Sodium alginate 2 g / l Treatment agent of the present invention (active ingredient of flame retardant 15%) 200 g / l Comparative treatment agent ( 100% of active ingredient of flame retardant) 100g / l

[0050]

[Table 2]

[0051]

The treatment agent of the present invention shows excellent durability and excellent flame retardancy by treating synthetic fibers and, at the same time, contains no halogen atoms. It does not occur and is effective for environmental protection. Due to the above effects, the fiber treating agent of the present invention is useful as a flame retardant for synthetic fibers for post-processing.

Claims (5)

[Claims] 1. A polyamide compound (D) derived from a dicarboxylic acid or its acid chloride (A), a diamine component (B) and a phosphinic acid derivative (C) represented by the following general formula (1). Fiber treatment agent. [Wherein, R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, an aryl group having 6 to 14 carbon atoms,
An arylalkyl group having 7 to 13 carbon atoms, which may be the same or different, and wherein R ¹ and R ² may be bonded to each other to form a ring together with P; It is a monovalent organic group represented by the formula (2), and Z represents a hydroxyl group or a chlorine atom. ] 2. The fiber treating agent according to claim 1, wherein the phosphinic acid derivative (C) is represented by the following general formula (3). Embedded image [In the formula, Z represents a hydroxyl group or a chlorine atom. R ³ ,
R ⁴ represents an alkyl group having 1 to 8 carbon atoms, which may be the same or different. p and q each represent an integer of 0 to 2, and n represents an integer of 0 to 2]. 3. The fiber treating agent according to claim 1, wherein the polyamide compound (D) has a weight average molecular weight of 1,000 to 20,000. 4. The fiber treating agent according to claim 1, wherein said dicarboxylic acid or its acid chloride (A) is adipic acid or terephthalic acid or their acid chloride. 5. The fiber treating agent according to claim 1, wherein said diamine component (B) is an aliphatic or aromatic diamine having 2 to 6 carbon atoms.