JP3479193B2 - Fiber treatment agent - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a treating agent for fibers. More specifically, it relates to a treatment agent for flame-retardant processing of synthetic fibers.

[0002]

2. Description of the Related Art Conventionally, an aqueous dispersion of hexabromocyclododecane (Japanese Patent Laid-Open No. 57-137377) is known as a treatment agent for flame-retardant processing of synthetic fibers such as polyester and polyamide. However, the use of a halogen compound has become a problem from the viewpoint of environmental protection, and a non-halogen flame retardant treatment agent is required.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to obtain 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 As a result of intensive studies to achieve the above object, the present inventors have found that good flame retardancy and durability (washing resistance, dry cleaning resistance, etc.) The present invention has been completed by finding an excellent fiber treating agent that can be applied by processing. That is, a polyurethane derived from an organic diisocyanate (A) and a phosphinic acid derivative (B) having two hydroxyl groups represented by the following general formula (1) or (B) and another active hydrogen-containing component (C). A treatment agent for fibers containing the compound (D). [Wherein R ¹ and R ² are 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, and an arylalkyl group having 7 to 13 carbon atoms, They may be the same or different, and further R ¹
And R ² may combine with each other to form a ring with P; A is an ethylene group or a propylene group, which may be used alone or in combination; m + n represents an integer of 0 to 20; Z
Is an aliphatic hydrocarbon group having 2 to 12 carbon atoms. ]

The organic diisocyanates used in the present invention include toluene diisocyanate (TDI), 4,
4'-diphenylmethane diisocyanate (MDI),
Aromatic diisocyanates such as 1,4-phenylene diisocyanate (PPDI) and naphthalene diisocyanate (NDI); 1,4 cyclohexane diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexa Examples thereof include aliphatic or alicyclic diisocyanates such as methylene diisocyanate (HDI), and TDI and MDI are preferable.

The alkyl group of the substituents R ¹ and R ² of the compound (B) is a linear or branched alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, n-propyl group and isopropyl group. , N-butyl group, isobutyl group, 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, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, n-hexadecyl group, n -Octadecyl group, n-icosyl group, and n-docosyl group are mentioned, and among them, an alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of phosphorus content.

The alkenyl group represented by the substituents R ¹ and R ² is a linear or branched alkenyl group having 2 to 22 carbon atoms,
Examples thereof 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. Among them, an alkenyl group having 2 to 6 carbon atoms is preferable from the viewpoint of phosphorus content. I

The cycloalkyl group of 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, 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 with P include a naphthylene group, a phenanthrene group, and an alkylene group having 3 to 5 carbon atoms.

OA of the compound (B) is an oxyethylene group or an oxypropylene group, which may be used alone or in combination, and is preferably an addition of an oxyethylene group alone.
m and n are each independently 0 to 20, preferably 0.
It is -10. Number of moles of alkylene oxide added (m
+ N) is usually 0 to 20 mol, preferably 2 to 10 mol. When the number of added moles (m + n) exceeds 20 moles, the phosphorus content becomes low and the flame retardancy is lowered.

P, q in the general formula (2) or (3)
Are each an integer of 0 to 2, and preferably 0.

Further, R ³ and R ⁴ in the general formula (2) or (3) are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group and 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,
It represents a 2-ethylhexyl group, preferably a hydrogen atom and a methyl group, and more preferably a hydrogen atom.

Z of the compound (B) is a linear, branched or cyclic aliphatic hydrocarbon group having 2 to 12 carbon atoms, and examples thereof include the following (b1) to (b4). However,
(P) and (OH) are residues bonded to Z

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6] In the present invention, specific examples of the phosphinic acid derivative (B) represented by the general formula (1) include the following compounds (B1) to (B9), but are not limited thereto. Absent.

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

Phosphinic acid derivative (B) used in the present invention
Are preferably the above compounds (B4) to (B9) in which the substituents R ₁ and R ₂ in the formula are biphenyl groups to form a ring, and more preferably (B4), (B6) and (B
7) and (B9).

Specific examples of the other active hydrogen group-containing component (C) used in the present invention include high molecular diols, low molecular diols, amino alcohols, low molecular diamines,
Polymeric diamines may be mentioned. Examples of the polymer diols include alkylene glycol, polyoxyalkylene glycol, alkylene oxide adduct of alkylene glycol, and alkylene oxide adduct of divalent aromatic hydroxy compound represented by bisphenol A. Of these, polyoxyalkylene glycol is preferable, and polyoxyethylene glycol, polyoxypropylene glycol, and a combination thereof are more preferable. Although the molecular weight is not particularly limited, it is preferably 1000 or less, and when it exceeds 1000, the phosphorus content becomes low and the flame retardancy is lowered. Examples of the low molecular weight diols include ethylene glycol, di-, tri- and tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like. Low molecular weight diols; dimethylolpropionic acid, glyceric acid, and low molar addition products of alkylene oxides of bisphenols. Amino alcohols include alkanolamines such as ethanolamine, propanolamine, diethanolamine and dipropanolamine; low molecular weight diamines include aliphatic diamines such as ethylenediamine and hexamethylenediamine; alicyclic diamines such as cyclohexanediamine and isophoronediamine. Aromatic diamines such as xylylenediamine and diaminodiphenylmethane; hydrazine and piperazine.

In the production of (D), the phosphinic acid derivative (B) having two hydroxyl groups with respect to the number of moles of the organic diisocyanate (A) and the other active hydrogen group-containing component (C).
The ratio of the total number of moles is usually 0.5 to 2, preferably 0.
It is 8 to 1.2, and more preferably 0.9 to 1.1.
If the molar ratio exceeds 2, or less than 0.5, the molecular weight of the polyurethane (D) obtained will be low and the durability will be insufficient.

The above reaction can be carried out in the presence of a solvent inert to the isocyanate group. Examples of the solvent include amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and tetrahydrofuran; cyclohexanone, methyl ethyl ketone and methyl. Examples thereof include ketone solvents such as isobutyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; and a mixed solvent of two or more kinds of these, preferably N, N-dimethylformamide, N, N.
-Dimethylacetamide, methyl ethyl ketone.

As a method for polymerizing urethane, a known method can be used. For example, an organic diisocyanate (A), a phosphinic acid derivative having two hydroxyl groups (B), another active hydrogen group-containing component (C), and If necessary, a method of charging a solvent all at once into a reaction vessel to carry out a reaction (one-shot method), if necessary, in a solvent, an organic diisocyanate (A), a phosphinic acid derivative (B) having two hydroxyl groups, and another active hydrogen group A method of dividing the contained component (C) into a multistage reaction to react an excess organic diisocyanate with the phosphinic acid derivative (B) having two hydroxyl groups and other active hydrogen group-containing component (C). Examples thereof include a method of producing a polymer and subjecting the polymer to an elongation reaction using a chain extender (prepolymer method). The reaction temperature is usually 30 to 180 ° C., preferably 6
It is 0 to 120 ° C. In the reaction, a catalyst used in a usual urethane reaction may be used to accelerate the reaction. Examples of the catalyst include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin dilaurate, stannas octoate, etc.), lead catalysts (red oleate, red 2-ethylhexoate, etc.). Etc.

The chain extenders used in the prepolymer method include ethylene glycol, di-, tri- and tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3- and 1,4-butanediol, 1,6. -Low molecular weight diols such as hexanediol and neopentyl glycol; alkylene oxide low molar adducts of dimethylpropionic acid, glyceric acid and bisphenols; alkanolamines such as ethanolamine, propanolamine, diethanolamine and dipropanolamine; ethylenediamine, hexa Aliphatic diamines such as methylenediamine; cyclohexanediamine,
Alicyclic diamines such as isophoronediamine; aromatic diamines such as xylylenediamine and diaminodiphenylmethane; compounds having two or more active hydrogen atoms in the molecule that are reactive with isocyanate groups such as hydrazine, piperazine and water. .

The weight average molecular weight of the polyurethane compound is
Usually 1,000 to 20,000, preferably 2,000
~ 15,000. If the average molecular weight is less than 1,000, the durability will be insufficient, and if it exceeds 20,000, the water dispersibility of the polyurethane compound will decrease, and the adsorptivity to synthetic fibers will be poor.

The phosphorus content of the polyurethane compound is usually 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 friction fastness of the treated synthetic fiber dyeing is lowered.

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

As the nonionic surfactant, a polyoxyalkylene type nonionic surfactant (higher alcohol alkylene oxide adduct, alkylphenol alkylene oxide adduct, fatty acid alkylene oxide adduct, polyhydric alcohol fatty acid ester alkylene oxide adduct, 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.).

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, the amide-based solvent (N, N-dimethylformamide, N, N-dimethylacetamide, etc.) used in the above urethane reaction, ester-based solvent (ethyl acetate, butyl acetate, etc.), ether-based solvent (Dioxane, tetrahydrofuran, etc.), ketone-based solvent (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic hydrocarbon solvent (toluene,
Xylene, etc.), halogen-based solvents and these 2
Examples include mixed solvents of at least one species.

The synthetic fiber to be used in the present invention is not particularly limited, but examples thereof include cotton, yarn, tow, top, case, knitted woven fabric and nonwoven fabric made of synthetic fiber such as polyester, cation dyeable polyester and nylon. .
Furthermore, the polyester fiber and other natural, regenerated, semi-synthetic, synthetic fiber mixed spinning, mixed woven fabric, etc. may be mentioned.

The treating agent of the present invention is usually used in the form of a treating solution diluted with water. The solid content concentration in the treatment liquid is 1
It is 0 to 50% by weight. The amount of the treatment agent applied to the fiber varies depending on the type of fiber product, but is usually 0.0
5 to 30% by weight, preferably 0.5 to 20% by weight. If the applied 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.

As a method for applying the treating agent of the present invention to synthetic fibers, high temperature pressure (110 to 130 ° C., 98 to 29) is applied.
The usual methods such as an exhaust method of exhausting at 4 kPa), a padding method and a spray method can be mentioned. With the exception of the exhaust method, the treatment temperature may be room temperature, and after applying the treatment agent, drying and heat treatment are performed by a usual method. Drying is usually 80-13
The heat treatment is usually 150 to 2 at 0 ° C. for 30 seconds to 30 minutes.
00 ° C., 10 seconds to 10 minutes.

The treatment agent of the present invention is used before dyeing synthetic fibers.
It may be carried out at the same time as the dyeing or at any time after the dyeing, and the method of carrying out at the same time with 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 absorption processing agent, an antistatic agent, a water / oil repellent agent, a hard finishing agent,
Examples include texture adjusters and anti-slip agents.

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

[0046]

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

Example 1 63 parts of MDI and the above compound (B) were added to a 4-neck Kolben equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube.
4) Phosphinic acid derivative 57 parts, polyoxypropylene glycol (number average molecular weight 400) 30 parts, N, N-
100 parts of dimethylformamide was charged and reacted at about 60 ° C. to obtain a weight average molecular weight of 7,500, phosphorus content of 3.9%,
A polyurethane compound solution having a solid content of 60% was obtained. To this solution, add 50 parts of nonylphenol ethylene oxide 15 mol adduct, dissolve evenly at 80 ° C, and add hot water (80 ° C) 7
00 parts were gradually added to form particles, and after cooling to room temperature, the product was continuously pulverized for 30 minutes with a Viscomill (horizontal wet fine powder disperser manufactured by IMEX), and the treating agent "1" of the present invention was 1,000.
I got a part. “1” is a milky white dispersion liquid and has a viscosity of 0.25.
Pa · s (25 ° C.), average particle size 0.4 μm, pH 6.
It was 8.

Example 2 55 parts of TDI and the above compound (B) were added to a 4-neck Kolben equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube.
4) 77 parts of the phosphinic acid derivative, 18 parts of polyoxypropylene glycol (number average molecular weight 400), N, N-
100 parts of dimethylformamide was charged and reacted at about 80 ° C. Then, in order to block unreacted isocyanate groups, n-butylamine was charged at 50 ° C., and after reacting for 30 minutes, excess n-butylamine was distilled off at 40 ° C. under reduced pressure to obtain a weight average molecular weight of 9,000, phosphorus. Content 5.3%,
A polyurethane compound solution having a solid content of 60% was obtained. To this solution, add 50 parts of nonylphenol ethylene oxide 15 mol adduct, dissolve evenly at 80 ° C, and add hot water (80 ° C) 7
00 parts were gradually added to form particles, and after cooling to room temperature, the product was continuously crushed for 30 minutes with a Viscomill (horizontal wet fine powder disperser manufactured by IMEX), and the treating agent "2" of the present invention was 1,000.
I got a part. "2" is a milky white dispersion liquid with a viscosity of 0.37.
Pa · s (25 ° C.), average particle size 0.3 μm, and pH 7.

Example 3 47 parts of TDI and the above compound (B) were placed in a 4-neck Kolben equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube.
96 parts of the phosphinic acid derivative of 9), 8 parts of polyoxypropylene glycol (number average molecular weight 300), and 100 parts of N, N-dimethylformamide were charged and reacted at about 80 ° C. Then, n-butylamine was charged at 50 ° C. to block unreacted isocyanate groups, and the weight average molecular weight was 8,500 and the phosphorus content was 4.7 in the same manner as in Example 2.
%, A solid content of 60% polyurethane compound solution was obtained. Nonylphenol ethylene oxide 15 mol adduct 50
Add 80 parts, dissolve evenly at 80 ℃, hot water (80 ℃) 700
Parts were gradually added to form particles, cooled to room temperature, and continuously pulverized for 30 minutes with a Viscomill (horizontal wet fine powder disperser manufactured by IMEX) to obtain 1,000 parts of the treating agent "3" of the present invention. "3" is a milky white dispersion liquid having a viscosity of 0.53 Pa.
・ S (25 ° C.), average particle size 0.3 μm, and pH 7.

Comparative Example Each component of the following formulation was continuously mixed and pulverized for 1 hour with a Viscomill (horizontal wet fine powder disperser manufactured by IMEX) to obtain 1,000 parts of a comparative treatment agent "4". “4” is a pale yellowish milky white dispersion liquid 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 performance test as a flame retardant, which was subjected to high temperature treatment and room temperature treatment using the treating agents [1] to [4].

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

[0053]

[Table 1]

Test method 2 (treatment at room temperature) A polyester undyed woven fabric of 300 g / m ² was subjected to padding treatment (squeezing ratio of 80%) in the following treatment bath and then dried (10
Heat set treatment (190 ℃ × 50)
Then, 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 (15% active ingredient of flame retardant) 200 g / l Comparative treatment agent ( Active ingredient of flame retardant 40%) 100g / l

[0055]

[Table 2]

[0056]

The treatment agent of the present invention, when treated on synthetic fibers, exhibits excellent durability and flame retardancy, and at the same time, since it does not contain halogen atoms, it does not generate halogen gas during combustion of the synthetic fibers. It does not occur and is effective for environmental protection. Since the above-described effects are exhibited, the fiber treating agent of the present invention is useful as a flame retardant for post-processing synthetic fibers.

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Claims (4)

(57) [Claims] 1. A derivative derived from an organic diisocyanate (A), a phosphinic acid derivative (B) or (B) having two hydroxyl groups represented by the following general formula (1) and another active hydrogen-containing component (C). Polyurethane compound (D)
A treatment agent for fibers containing. [Wherein R ¹ and R ² are 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, and an arylalkyl group having 7 to 13 carbon atoms, They may be the same or different, and further R ¹
And R ² may combine with each other to form a ring with P; A is an ethylene group or a propylene group, which may be used alone or in combination; m + n represents an integer of 0 to 20; Z
Is an aliphatic hydrocarbon group having 2 to 12 carbon atoms. ] 2. The fiber treatment agent according to claim 1, wherein the phosphinic acid derivative (B) is represented by the following general formula (2). [Chemical 1] [In the formula, A represents an ethylene group or a propylene group, which may be used alone or in combination; m + n is an integer of 0 to 20;
R ³ and R ⁴ represent an alkyl group having 1 to 8 carbon atoms and may be the same or different. p and q are 0 to 2 respectively
Represents the integer of 3. The fiber treating agent according to claim 1, wherein the phosphinic acid derivative (B) is represented by the following general formula (3). [Chemical 2] [In the formula, A represents an ethylene group or a propylene group, which may be used alone or in combination; m + n is an integer of 0 to 20;
R ³ and R ⁴ represent an alkyl group having 1 to 8 carbon atoms and may be the same or different. p and q are 0 to 2 respectively
Represents the integer of 4. The weight average molecular weight of the polyurethane compound (D) is 1,000 to 20,000.
Any one of the fiber treatment agents.