JPH10121378A - Treating agent for fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-halogen-based flame resistant treating agent capable of imparting a flame resistance excellent in durability to a fiber by using a polyurethane compound obtained by reacting an organic diisocyanate and a specific phosphinic acid derivative and a component containing active hydrogen. SOLUTION: An organic diisocyanate such as toluene diisocyanate is reacted with a phosphinic acid derivative having two hydroxyl groups of the formula [R<1> is ethylene or 1,2-propylene; R<2> is a 1-4C alkyl, phenyl or an alkyl- substituted phenyl; OA is oxyethylene or oxypropylene; (m)+(n) is an integer of 0-20] and polyoxypropylene glycol in N,N-dimethylformamide solvent to provide a polyurethane compound having 1,000-20,000 weight average molecular weight. The objective treating agent for a fiber is obtained by emulsifying and dispersing the resultant polyurethane compound in water in the presence of a surfactant.

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.) can be added to synthetic fibers. The present inventors have found an excellent fiber treatment agent that can be applied by processing, and have reached the present invention. That is, it is 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 group-containing component (C). A fiber treating agent containing a polyurethane compound (D). [Wherein, R ¹ ethylene group or 1,2-propylene group,
R ² is an alkyl group having 1 to 4 carbon atoms or a phenyl group or an alkyl-substituted phenyl group; OA is an oxyethylene group or an oxypropylene group, which may be used alone or in combination; m + n represents an integer of 0 to 20; ]

The organic diisocyanate used in the present invention includes toluene diisocyanate (TDI),
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.

In the general formula (1) showing the phosphinic acid derivative (B) having two hydroxyl groups, R ¹ is an ethylene group or a 1,2-propylene group, preferably an ethylene group. R ² is an alkyl group having 1 to 4 carbon atoms or a phenyl group or an alkyl group substituted (usually having 1 to 4 carbon atoms).
Phenyl group, preferably a methyl group and a phenyl group.

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

Specific examples of other active hydrogen group-containing components (C) used in the present invention include high molecular diols, low molecular diols, low molecular diamines, and high molecular diamines. Examples of the polymer diols include alkylene glycol, polyoxyalkylene glycol, alkylene oxide adducts of alkylene glycol, and alkylene oxide adducts of divalent aromatic hydroxy compounds represented by bisphenol A. Of these, preferred are polyoxyalkylene glycols, and more preferred are polyoxyethylene glycol, polyoxypropylene glycol, and combinations thereof.
The molecular weight is not particularly limited, but is preferably 1,000 or less. If it exceeds 1,000, the phosphorus content is reduced, and the flame retardancy is reduced. Low molecular diols include ethylene glycol, di-, tri- and tetraethylene glycol, propylene glycol, dipropylene glycol,
Low molecular weight diols such as 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol; dimethylolpropionic acid, glyceric acid, and low molar addition products of alkylene oxides of bisphenols. Examples of low molecular diamines include alkanolamines such as ethanolamine, propanolamine, diethanolamine and dipropanolamine; aliphatic diamines such as ethylenediamine and hexamethylenediamine; alicyclic diamines such as cyclohexanediamine and isophoronediamine; xylylenediamine And aromatic diamines such as diaminodiphenylmethane; hydrazine, piperazine and the like.

In the preparation of (D), the ratio of the total number of moles of the diol component (B) and the compound (C) to the number of moles of the organic diisocyanate (A) is usually 0.5 to 2, preferably 0 to 2. 0.8 to 1.2, more preferably 0.9 to 1.
It is one. When the molar ratio exceeds 2 or is less than 0.5, the molecular weight of the obtained polyurethane compound (D) becomes low, and the durability becomes insufficient.

The above reaction can be carried out in the presence of a solvent inert to isocyanate groups. 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 and methyl ethyl ketone And ketone solvents such as methyl isobutyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; and a mixed solvent of two or more thereof, preferably N, N'-dimethylformamide,
N, N'-dimethylacetamide and methyl ethyl ketone.

As a method for polymerizing urethane, known methods can be used. For example, an organic diisocyanate (A), a diol component (C), a phosphinic acid derivative (B), and, if necessary, a solvent are charged into a reaction vessel at once. A method of reacting (one-shot method), a method in which an organic diisocyanate (A), a diol component (C) and the compound (B) are divided and subjected to a multi-stage reaction in a solvent, if necessary, and a diol component (C) and the compound A method in which an excess of organic diisocyanate is reacted with (B) to produce a prepolymer, and an elongation reaction is further carried out using a chain extender (prepolymer method). The reaction temperature is usually 30 to 180 ° C, preferably 60 to 120 ° C. In the reaction, a catalyst used in a usual urethane reaction may be used to promote the reaction. Examples of the catalyst include tin-based catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin dilaurate, stannas octoate, etc.), and lead-based catalysts (red oleate, red 2-ethylhexoate, etc.). And the like.

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; low molecular weight alkylene oxide adducts of dimethylpropionic acid, glyceric acid and bisphenols (molecular weight of 500 or less); alkanols such as ethanolamine, propanolamine, diethanolamine and dipropanolamine Amines; aliphatic diamines such as ethylenediamine and hexamethylenediamine; alicyclic diamines such as cyclohexanediamine and isophoronediamine; aromatics such as xylylenediamine and diaminodiphenylmethane Amines; hydrazine, piperazine, compounds having two or more in its molecule an active hydrogen atom reactive with isocyanate groups and water.

The weight average molecular weight of the polyurethane compound is
Usually 1,000 to 20,000, preferably 2,000
１５15,000. If the average molecular weight is less than 1,000, the durability is insufficient, and if it exceeds 20,000, the water dispersibility of the polyurethane compound decreases, and the adsorptivity to synthetic fibers also becomes 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 rub fastness of the treated synthetic fiber dyed product is reduced.

The polyurethane 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, polyvalent alcohols) 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 surfactant include sulfates (higher alcohol sulfates, higher alkyl ether sulfates, sulfated fatty acid esters, etc.),
Sulfonates (eg, alkylbenzenesulfonate, alkylnaphthalenesulfonate), and phosphate salts (eg, higher alcohol phosphate esters, higher alcohol alkylene oxide adduct phosphate ester salts, etc.).

Examples of the organic solvent include amide solvents (N, N'-dimethylformamide, N, N'-dimethylacetamide, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), and ethers used in the urethanization reaction. Solvents such as dioxane and tetrahydrofuran, ketone solvents (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), halogen solvents and two or more of these solvents A mixed solvent and the like can be mentioned.

The synthetic fiber used in the present invention is not particularly limited, and examples thereof include cotton, thread, tow, top, sash, knitted fabric, and nonwoven fabric made of synthetic fiber such as polyester and nylon. Further, there may be mentioned a blend of 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.

As a method of applying the treating agent of the present invention to synthetic fibers, high temperature and pressure (110 to 130 ° C., 98 to 29
Ordinary methods such as an exhaustion method, a padding method, and a spray method in which exhaustion is performed at 4 kPa) can be used. 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 80 to 13
0 ° C., 30 seconds to 30 minutes, heat treatment is usually 150 to 2
00 ° C., 10 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 treating agent of the present invention can be used in combination with another fiber treating agent. 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 durable flame retardancy without containing halogen compared to conventional ones, particularly by treating synthetic fibers.

[0025]

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 A four-port colben equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 51 parts of TDI, 29 parts of polyoxypropylene glycol (number average molecular weight 400), and the following formula (2) 70 parts of a phosphinic acid derivative and 100 parts of N, N′-dimethylformamide were charged and reacted at about 80 ° C.
A polyurethane compound solution having a weight average molecular weight of 7,000, a phosphorus content of 4.8% and a solid content of 60% was obtained. Nonylphenol in this solution 50 parts of a 15 mol adduct of ethylene oxide were added, and
At 80 ° C., gradually add 700 parts of hot water (80 ° C.) to form particles, cool to room temperature, and pulverize continuously for 30 minutes with a Viscomil (IMEX horizontal wet fine powder disperser) to obtain the powder of the present invention. 1,000 parts of treating agent "1" were obtained. "1"
Is a milky white dispersion having a viscosity of 0.33 Pa · s (25
° C), the average particle size was 0.3 µm, and the pH was 7.1.

Example 2 63 parts of TDI, 14 parts of polyoxypropylene glycol (number-average molecular weight 400), and 4 parts of the following formula (3) were added to a four-necked corben equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet pipe. 74 parts of a phosphinic acid derivative and 100 parts of N, N'-dimethylformamide were charged and reacted at about 80 ° C. Thereafter, n-butylamine was charged at 50 ° C. in order to block unreacted isocyanate groups and reacted for 30 minutes. Excessive n-butylamine was distilled off at 40 ° C. under reduced pressure to obtain a weight average molecular weight of 8,500 and phosphorus. A polyurethane compound solution having a content of 6.4% and a solid content of 60% was obtained. In this solution,
Nonylph Add 50 parts of an adduct of 15 mol of ethylene oxide, uniformly dissolve at 80 ° C., gradually add 700 parts of hot water (80 ° C.) to form particles, cool to room temperature, and cool with biscomil (IMEX horizontal wet fine powder). (Dispersing machine) for 30 minutes to give 1,000 parts of the treating agent "2" of the present invention.
"2" is a milky white dispersion having a viscosity of 0.45 Pa · s
(25 ° C.), average particle size 0.3 μm, pH 6.8.

Example 3 In the same manner as in Example 1, 70 parts of MDI and 22 polyoxypropylene glycol (number average molecular weight 400) were prepared.
Parts, phosphinic acid derivative (2) 57 parts, and N, N'-dimethylformamide 100 parts were charged and reacted at 60 ° C. to obtain a polyurethane compound having a weight average molecular weight of 7,500, a phosphorus content of 4.9%, and a solid content of 60%. A solution was obtained. Nonylphenol ethylene oxide 15 mol adduct 5
Add 0 parts and dissolve uniformly at 80 ° C.
0 parts were gradually added to form particles, cooled to room temperature, and continuously pulverized for 30 minutes with a Viscomil (IMEX horizontal wet fine powder disperser) to obtain 1,000 parts of the treating agent "3" of the present invention. . "3" is a milky white dispersion having a viscosity of 0.53P
a · s (25 ° C.), average particle size 0.3 μm, and pH 7.

Comparative Example Each component having the following formulation was continuously mixed and pulverized for 1 hour with a Viscomil (IMEX horizontal wet fine powder dispersing machine) 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 555 parts of water

<Flame Retardancy Test> Tables 1 and 2 show the results of a high temperature treatment and a normal temperature treatment using the treating 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 an aqueous dispersion containing
(Tsujii Dyeing Machine), treatment at 130 ° C for 30 minutes, washing with water and drying (100 ° C for 3 minutes) followed by heat treatment (17
(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.

[0032]

[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 (active ingredient of flame retardant 40%) 100g / l

[0034]

[Table 2]

[0035]

The treating agent of the present invention shows excellent durability and excellent flame retardancy by treating synthetic fibers, and contains no halogen atoms. It does not generate chemical gas and is also effective in 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 (2)

[Claims] 1. Derived from an organic diisocyanate (A) and a phosphinic acid derivative (B) or (B) having two hydroxyl groups represented by the following general formula (1) and another component (C) containing an active hydrogen group: A fiber treating agent comprising the polyurethane compound (D). [Wherein, R ¹ ethylene group or 1,2-propylene group,
R ² is an alkyl group having 1 to 4 carbon atoms or a phenyl group or an alkyl-substituted phenyl group; OA is an oxyethylene group or an oxypropylene group, which may be used alone or in combination; m + n represents an integer of 0 to 20; ] 2. The fiber treating agent according to claim 1, wherein the polyurethane compound (D) has a weight average molecular weight of 1,000 to 20,000.