KR20170131798A - Flame Retardant Procesing Agents for synthetic fabrics and processing method for flame retardant using the same - Google Patents

Abstract

The present invention relates to a flame resistant processing of synthetic fibrous products such as polyester-based fibers and nylon fibers. More specifically, provided is a flame resistant processing agent which does not involve uses of halogen-based flame resistant agents which cause environmental problems previously, and is obtained by dispersing, in water and a solvent, an organic phosphorus-based flame resistant agent containing phosphorus and nitrogen having a hydrazine structure capable of making the synthetic fibers excellently flame resistant, as at least one type of a dispersant of a non-ionic surfactant or an anionic surfactant.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame retardant for synthetic fibers, and a flame retardant processing method using the flame retardant.

The present invention relates to a flame retardant processing agent for synthetic fiber products such as polyester fibers and nylon fibers, and a flame retardant processing method using the same, and it is an object of the present invention to provide flame- To a flame-retardant processing agent for organic phosphorus-based synthetic fibers containing both nitrogen and phosphorus of a hydrazine structure capable of imparting flame retardancy to the flame-retardant resin composition.

Compounds containing phosphorus (P) are known to exhibit various functions. Among them, the performance as a flame retardant has attracted attention. In general, a flame retardant which has been mainly applied to a polymer resin has been mainly used as a halogen-based flame retardant including bromine (Br). Although their flame retardancy was satisfactory, there were environmental problems such as toxic gas generation and generation of harmful substances such as dioxin and benzofuran, and the necessity of a non-halogen flame retardant agent was required due to poor compatibility with resin Research in this area has been actively developed in many fields. Examples of the non-halogen flame retardant include inorganic hydrates, nitrogen compounds, organophosphorus flame retardants, and composite flame retardants by mixing them. In the case of inorganic hydrates, too much inorganic hydrates must be used to obtain a desirable flame retardant effect, The disadvantage of poor quality is pointed out. When nitrogen oxides are used as a flame retardant, flame retardant effect is somewhat insufficient, compatibility with resins and water resistance become a problem, and flame retardants such as phosphorus tend to degrade basic physical properties of resins. It is susceptible to heat or friction shock itself, which is dangerous to handle, store, mix, and has a disadvantage in that the working environment is not good. Although other organophosphorus flame retardants still need improvement, they have been recognized as the most desirable alternative to halogen flame retardants, and the most active research has been conducted.

In the present invention, as a method for imparting flame retardancy to a synthetic fiber such as polyester fiber or nylon fiber, a method of using an organic phosphorus flame retardant that simultaneously contains nitrogen and phosphorus of a hydrazine structure without using a conventional halogen- The present invention provides a flame retardant processing agent applicable to ester and nylon fibers.

Various methods of imparting flame retardancy to a conventional polyester-based synthetic fiber product through post-processing have been known. As disclosed in Japanese Patent Publication No. 53-8840, there are known methods such as 1,2,5,6 , And 9,10-hexabromo cyclododecane are dispersed in water together with a dispersant to attach the flame retardant composition to the fiber product.

As described above, when a bromine-containing substance is used as a flame retardant, a harmful halogenated gas such as hydrogen bromide (HBr) is generated when the fiber product is burned, thereby adversely affecting the environment.

In the early stage of replacing the halogen flame retardant, a phosphoric acid ester material was used as a phosphorus-containing substance to impart flame retardancy to synthetic fiber products. An example of a phosphoric acid ester-based flame retardant substance is an aromatic diphosphate such as resorcinol bis (diphenylphosphate) usually called RDP.

These phosphoric acid ester flame retardants exhibit good thermal stability and excellent flame retardancy, but are not only problematic in that they have good compatibility with solvents used in dry cleaning, and also have a problem of lowering fastness. In addition, Phosphoric ester materials tend to migrate toward the fiber surface from the point where they attract dye molecules that are dyed to the fiber and cause a phenomenon called a "bleed" that usually stains the fiber surface .

In the present invention, in the flame-retarding process of conventional polyester and nylon fiber products, the above-described problems, that is, problems in which a harmful halogenated gas such as HBr is generated when the fiber product is burned, As a result of efforts to solve the problems of phosphoric acid ester flame retardants such as a decrease in fastness due to compatibility with a solvent during dry cleaning and a bleeding phenomenon over time or a halogen flame retardant such as bromine, It has been found that excellent flame retardancy can be imparted to polyester fibers and nylon fibers by using a phosphorus-containing flame retardant having a special structure simultaneously containing nitrogen and phosphorus of a hydrazine structure capable of exhibiting the synergistic action of nitrogen and phosphorus Thereby completing the present invention.

In the present invention, a nitrogen-containing organic phosphorus compound as a hydrazine structure represented by the following formula (I) is dispersed in a solvent together with a surfactant of at least one of a nonionic surfactant and an anionic surfactant, Based fiber and a nylon fiber product.

Wherein Ar < ₁ > And Ar ₂ Ar ₃ and Ar ₄ are each independently an aryl group or an alkyl group having 1 to 6 carbon atoms, or Ar ₃ and Ar ₄ may be connected to each other to form a ring.

Ar ₁ of the above formula (I) And Ar ₂ each independently represent an aryl group, preferably an aryl group having 6 to 18 carbon atoms. Examples of such aryl groups include biphenyl, naphthyl and phenyl groups.

Ar ₃ and Ar ₄ in the above formula (I) are each independently an aryl group or an alkyl group having 1 to 6 carbon atoms, or Ar ₃ and Ar ₄ may be connected to each other to form a ring. Examples of such aryl groups include biphenyl, Butyl and phenyl groups, and the alkyl groups include methyl, ethyl, isopropyl and the like, and the compounds which are linked together to form a ring include compounds constituting a ring formed from neopentyl glycol groups.

The compound of formula (I) is obtained by reacting a hydrazine hydrate of formula (II) with a diarylphosphorochloride derivative of formula (III) to obtain an intermediate of formula (IV) Is reacted with a phosphorochloride derivative of formula (V).

In the above formula, Ar ₁ and Ar _{2 ,} Ar _{3 and} Ar ₄ are as described above.

The above synthesis is preferably carried out by adding the hydrazine derivative of the formula (II) in the presence of an organic base such as triethylamine in a solvent and then adding the diarylphosphorochloride of the formula (III) dropwise to obtain an intermediate of the formula (IV) , And then the phosphorochloride derivative of the formula (V) is added dropwise again to obtain the target compound of the formula (I).

As the solvent which can be used in the synthesis, water and organic solvents such as water, methyl alcohol, ethyl alcohol, isopropyl alcohol, THF and toluene can be used. It is also possible to use an organic solvent and water mixed with water as a reaction solvent.

The flame retardant of the synthetic fiber product according to the present invention is obtained by dispersing a flame retardant of the formula (I) as described above in a solvent in the presence of a surfactant, wherein the solvent mainly used is water, It can also be used together.

The surfactant used as the dispersing agent may be a nonionic surfactant or an anionic surfactant, or a mixture of a nonionic surfactant and an anionic surfactant.

 In the present invention, the flame retardant is obtained by mixing the flame retarder of the above formula (I) together with the surfactant in a solvent and pulverizing the mixture using a wet pulverizer. Generally, when the fiber product is subjected to flame-retardant processing, the particle diameter of the flame retardant is important in terms of the mechanism of sticking to the fiber. In order to sufficiently diffuse into the fiber product, the particle diameter of the flame retardant is in the range of 0.3 to 15 micrometers, 3.0 micrometer range.

 The flame retardant according to the present invention is usually used by diluting it with water when the polyester fiber or the nylon fiber product is subjected to flame-retardant processing. The content of the flame retardant in the flame retardant is preferably in the range of 1 to 50 wt% The fiber adhered amount of the processing agent ranges from 0.1 to 30% by weight, preferably 0.5 to 20% by weight, of the flame retardant relative to the synthetic fibers. When the amount of fiber adhering to the flame retardant is less than 0.1%, sufficient flame retardancy can not be imparted to the fiber, and when 30% or more is adhered, the soft feeling may not be smooth.

 The method for flame-retarding a synthetic fiber product according to the present invention is not particularly limited, and it may be a method in which a flame-retarding effect is imparted to a dyeing bath when the fiber is dyed with a disperse dye, Coating or the like to temporarily adhere to the surface of the fiber, and thereafter, the fiber is heat-treated at 110 deg.

It is presumed that the reason why the material structure of the chemical formula (I) used in the present invention is comparatively simple but exhibits excellent flame retardancy is probably that hydrazine type nitrogen and phosphorus are appropriately distributed in the molecule to induce synergism.

By applying the flame retardant composition provided by the present invention to polyester fibers and nylon fibers, it is possible to solve the environmental problem in which harmful gas was generated in the combustion of fiber products by using the conventional halogen-based flame retardant, It is possible to solve the problems of the lowering of the dry crinking fastness and the problems of the bleeding phenomenon over time.

In the present invention, it is preferable that an organic phosphorus compound containing a hydrazine structure represented by the following formula (I) is dispersed in water or a solvent by using a nonionic surfactant or an anionic surfactant as at least one kind of dispersant Fiber and nylon fiber products.

Wherein Ar < ₁ > And Ar ₂ Ar ₃ and Ar ₄ are each independently an aryl group or an alkyl group having 1 to 6 carbon atoms, or Ar ₃ and Ar ₄ may be connected to each other to form a ring.

The compound of formula (I) is obtained by reacting a hydrazine hydrate of formula (II) with a diarylphosphorochloride derivative of formula (III) to obtain an intermediate of formula (IV) Is reacted with a phosphorochloride derivative of formula (V).

In the above formula, Ar ₁ and Ar _{2 ,} Ar _{3 and} Ar ₄ are as described above.

Examples of chemical structures of useful flame retardant materials that can be synthesized in this manner are the following structures. However, the present invention is not limited to compositions containing the following materials.

( Synthesis Example 1 : Synthesis of Compound 1)

To a 3-liter three-necked flask, add 1.5 liters of water, 0.5 liter of isopropyl alcohol, 206.42 g (2.04 mole) of triethylamine, and 62.5 g (1.00 mole) of 80% hydrazine hydrate and dissolve with stirring. An ice water bath is placed outside the flask and cooled by stirring so that the internal temperature is below 15 ° C.

Diphenylphosphorochloride (537.3 g, 2.00 mole) is added dropwise using a dropping funnel. The dropwise funnel is added dropwise to the dropwise funnel so that the internal temperature does not exceed 15 ° C during dropwise addition. After completion of the dropwise addition of diphenylphosphorochloride, the ice water tank disposed outside the flask was removed, and the reaction was completed by stirring the mixture at about 25 ° C for 2 hours.

After confirming the completion of the reaction by thin film chromatography (TLC), the mixture is heated for aging and further stirred for one hour at an internal temperature of 40 to 45 ° C to agitate the synthesized flame retardant particles.

After cooling, the reaction mixture was filtered at 20 to 25 ° C and washed with water to remove the triethylamine hydrochloride salt, and then dried at 110 ° C using a hot air drier to obtain 410.7 g of the target compound (yield: 82.7%) .

( Synthesis Example 2 : Synthesis of Compound 3)

To a 3-liter three-necked flask, add 1.5 liters of water, 0.5 liter of isopropyl alcohol, 206.42 g (2.04 mole) of triethylamine, and 62.5 g (1.00 mole) of 80% hydrazine hydrate and dissolve with stirring. An ice water bath is placed outside the flask and cooled by stirring so that the internal temperature is below 5 degrees Celsius.

26.8.6 g (1.00 mole) of diphenylphosphorochloride is added dropwise using a dropping funnel. The dropping funnel is added to adjust the dropping rate so that the internal temperature does not exceed 7 during the dropwise addition. After completion of the dropwise addition of diphenylphosphorochloride, the reaction mixture was stirred for 1 hour at a temperature of 5 ° C or lower to complete the synthesis of the intermediate. 144.49 g (1.00 mole) of dimethylphosphorochloride was further added dropwise at an internal temperature of 15 ° C, It does. After completion of the dropwise addition of dimethylphosphorochloride, the ice water tank placed outside the flask was removed, and the reaction was completed by stirring the mixture at about 25 ° C for 2 hours.

After confirming the completion of the reaction by thin film chromatography (TLC), the internal temperature was adjusted to 40 to 45 ° C. After vacuuming, the reaction mixture was mixed with water to remove most of the isopropyl alcohol, and the flame retardant Aging the particles.

After cooling, the reaction mixture was filtered at an internal temperature of 20 to 25 deg. C, washed with water to remove triethylamine hydrochloride salt, and dried at 110 deg. C using a hot air drier to obtain 359.7 g (yield: 96.6% .

When the reaction is carried out by changing the structure of the reaction product, the flame retardant materials represented by the formula (I), such as the compounds 2 and 3 described above, can be obtained in a yield of 90% or more.

The flame retardant materials of the flame retardant composition provided in the present invention exhibit excellent flame retardancy not only alone but also synergistic effects when mixed with common flame retardant materials having the following structure.

Hereinafter, the process for producing a polyester-based fiber and a flame retardant composition for nylon fiber according to the present invention will be described with reference to the following examples, but the present invention is not limited thereto.

Example 1

 42 parts by weight of the flame retardant (Compound 1) synthesized in the above Synthesis Example, 3.75 parts by weight of sodium naphthalenesulfonate condensate, 2.0 parts by weight of an anionic dispersant with ethylene oxide and 0.25 part by weight of xanthan gum were mixed in 50 parts by weight of water, , And the mixture was pulverized until the average particle size of the flame retardant became 0.9 micrometer.

When the flame retardant composition was measured for 1 hour at 105 deg. C using an infrared moisture meter, the concentration of the nonvolatile matter was adjusted to 40% to obtain the flame retardant according to the present invention.

    Example 2

 42 parts by weight of a flame retardant (Compound 2) synthesized by a similar method, 3,75 parts by weight of sodium dodecyldiphenyl ether sulfonate, 2.0 parts by weight of ethylene oxide-added anionic dispersant and 0.25 part by weight of xanthan gum were dissolved in water , And the mixture was put into a basket mill filled with glass beads and pulverized until the average particle size of the flame retardant became 0.9 micrometer.

When the flame retardant composition was measured for 1 hour at 105 deg. C using an infrared moisture meter, the concentration of the nonvolatile matter was adjusted to 40% to obtain the flame retardant according to the present invention.

   Example 3

42 parts by weight of a flame retardant (Compound 3) synthesized by a similar method, 3,75 parts by weight of sodium dodecyldiphenyl ether sulfonate, 2.0 parts by weight of ethylene oxide-added anionic dispersant and 0.25 part by weight of xanthan gum were dissolved in water And the mixture was put into a basket mill filled with glass beads and pulverized until the average particle size of the flame retardant became 0.9 micrometer. When the flame retardant composition was measured for 1 hour at 105 deg. C using an infrared moisture meter, the concentration of the nonvolatile matter was adjusted to 40% to obtain the flame retardant according to the present invention.

  Example 4

42 parts by weight of the flame retardant (Compound 4) synthesized in the same manner as in the above Synthesis Example was replaced by 3.75 parts by weight of sodium naphthalenesulfonate condensate, 2.0 parts by weight of ethylene oxide-added anionic dispersant and 0.25 part by weight of xanthan gum, And the mixture was put into a basket mill filled with glass beads and pulverized until the average particle size of the flame retardant became 0.9 micrometer.

When the flame retardant composition was measured for 1 hour at 105 deg. C using an infrared moisture meter, the concentration of the nonvolatile matter was adjusted to 40% to obtain the flame retardant according to the present invention.

  Comparative Example

 42 parts by weight of flame retardant 1,2,5,6,9,10-hexabromocyclododecane (HBCD), 3.75 parts by weight of sodium naphthalene sulfonate condensate, 2.0 parts by weight of ethylene oxide-added anionic dispersant and 0.25 part by weight of xanthan gum Were mixed in 50 parts by weight of water and placed in a basket mill filled with glass beads and pulverized until the average particle size of the flame retardant became 0.9 micrometer.

When the flame retardant composition was measured for 1 hour at 105 ° C using an infrared moisture meter, the non-volatile matter concentration was adjusted to 40% to obtain a comparative flame retardant.

(Test Methods)

 The bath was washed with 2% owf of a disperse dye (trade name: RED KKL, a product of M.Dohmen Korea and DISPERSE-BK CCR of Dae Young), 0.5 g / L of a dye dispersant (anionic dispersant), a flame retardant according to the present invention, And 15% owf respectively, and the bath ratio was 1:15.

 The polyester specimen was put into a salt bath, heated to 130 ° C at a heating rate of 2 ° C / min, held at that temperature for 50 minutes, sucked in a bath, washed with water, dried, and heat treated at 180 ° C for 2 minutes Respectively.

 Performance evaluation items

(1) texture (feeling)

The flame-retarded polyester fiber fabric was evaluated by feeling immediately after processing. The results are shown in Table 1 below. ≪ tb > < TABLE >

(2) Dyeability

The flame-retarded polyester fiber fabric was visually inspected immediately after processing. It was judged to be good, slightly good and bad according to dyeability. The results obtained are shown in Table 1 below.

(3) Flammability test (oxygen limit index, LOI)

Immediately after the processing of the flame-retarded polyester fiber fabric, the fabric was washed five times in accordance with the ASTM D 2863 standard, and then flame retardant performance test was carried out.

The oxygen limit index tester was a tester (Model: On-1, JP) manufactured by Suga Test Instrument and the results are shown in Table 1 below.

(4) Flammability

The presence or absence of fuming from the flame retardant when heat-treated at 150 ° C. immediately after the processing of the polyester fiber fabric subjected to the flame retardation process was confirmed, and the obtained results are shown in Table 1 below.

(5) Light fastness

Dyeing by Xenon lamp specified in KS K ISO 105-B02 immediately after processing of flame-retarded polyester fiber fabric with 2% owf of disperse dye RED KKL and 2% owf of DISPERSE-BK CCR with 15% owf of flame retardant The exposure time was evaluated as 20 hours in accordance with the fastness test, and the results obtained are shown in Table 1 below.

(6) Friction fastness

The dry friction test was carried out in accordance with the dyeing fastness test according to the friction specified in KS K ISO 105-X12 for the immediately after processing of the flame-retarded polyester fiber fabric. The fastness to rubbing is highest in the fifth grade and lowest in the first grade, and the obtained results are shown in Table 1 below.

Disperse dye  Texture Dyeability Flammability (LOI) Ductility Light Fastness Dry friction resistance Example 1
(Compound 1) Red KKL Good Good 30.0 none 5 4-5 Disperse BK CCR Good Good 30.5 none 6 4 Example 2
(Compound 2) Red KKL Good Good 30.0 none 5 4-5 Disperse BK CCR Good Good 30.5 none 6 4 Comparative Example
(Halogen type) Red KKL Good Good 29.5 none 5 4 Disperse BK CCR Good Slightly good 29.0 none 6 3

As a result, it was found that the flame retardant of the formula (I) had better flame retardancy and various fastnesses than the conventional halogen-based flame retardants of the comparative examples.

It is considered that the flame retardant composition of the present invention is applicable to nylon fiber and acetate fiber as well as polyester fiber.

Claims (2)

A process for producing a flame-retardant synthetic fiber comprising the steps of: dispersing a nitrogen-containing organic phosphorus compound having a hydrazine structure represented by the following formula (I) in a solvent together with at least one surfactant selected from a nonionic surfactant and an anionic surfactant; My.

Wherein Ar < ₁ > And Ar ₂ Ar ₃ and Ar ₄ are each independently an aryl group or an alkyl group having 1 to 6 carbon atoms, or Ar ₃ and Ar ₄ may be connected to each other to form a ring.
A flame-retardant processing method for a polyester-based fiber product, which comprises the step of flame-retarding a polyester-based fiber product with the flame retardant of claim 1.