KR20150133581A - Method of flameproofing of polyester-based textileproduct using flameproofing agent - Google Patents

Abstract

The present invention provides a method for frame retarding a polyester-based fiber comprising a method for applying a flame retardance processed product to the polyester-based fiber, and attaching the same to the polyester-based fiber. The flame retardance processed product is produced by the following steps: (a) preparing a mixture by mixing phosphoric acid amid-based compound and a non-ionic surfactant with a solvent; (b) dispersing the phosphoric acid amid-based compound, to which the non-ionic surfactant is absorbed, to the solvent by pulverizing the mixture and atomizing the same; and (c) adding an anionic surfactant to the solvent to which the phosphoric acid amid-based compound is dispersed. The present invention also provides a polyester-based fiber product for being equipped in a vehicle, to which 0.05 to 30 wt% of the flame retardance processed product processed by the method of the present invention is attached. Accordingly, a polyester-based fiber product produced by the present invention can be widely used not only for a vehicle interior material, but also for a seat, seat cover, curtain, wall paper, ceiling cross, carpet, thick layer having patterns, sheet for curing a building, tent, and the like.

Description

METHOD OF FLAMEPROOFING OF POLYESTER-BASED TEXTILE PLUS USING FLAMEPROOFING AGENT [0001]

The present invention relates to a flame retardant / flame retardant process for polyester fibers, and more particularly to a flame retardant / flame retardant process for polyester fibers using a flame retardant additive capable of imparting flame retardancy excellent in durability without using a halogen- A flame retarding method and a polyester fiber product produced therefrom.

There is known a method of imparting flame retardancy by post-processing a polyester fiber. For example, a method is known in which a flame retardant agent produced by dispersing a halogen-based compound as a flame retardant in a solvent such as water is applied to polyester fibers.

However, when flame retarding treatment is applied to a polyester fiber by using a halogen-based compound as a flame retardant, a halogenated gas, which is a harmful substance, is generated when the polyester fiber burns, thereby causing harmful effects on the environment . Therefore, recently, a halogen-based compound is regulated as a flame retardant.

As a result, recently, a method of imparting flame retardancy to a polyester fiber by using a phosphoric acid ester containing no halogen in place of a halogen compound as a flame retardant has been performed.

When phosphoric acid ester is used as the flame retardant, it is possible to impart flame retardancy with excellent washing resistance to the polyester fiber, but the dry-cleaning property is insufficient. When the polyester fiber is subjected to the flame retarding / flame retarding treatment using such phosphoric acid ester, the disperse dye or the like used for dyeing the polyester fiber with time passes to the surface together with the phosphoric acid ester dissolved therein, There is a problem that dyeing fastness is lowered due to generation of bleeding and dye adsorption is impeded, resulting in a problem that the uniformity of color and the yield are lowered.

In order to solve such environmental problems and fastness problems, a flame retardancy excellent in durability has been proposed in a polyester fiber by using a phosphoric acid amide (aminophosphate) as a flame retardant. However, when flame-retardant polyester fiber for vehicle interior is made using such a phosphoric acid amide flame retardant, it is difficult to satisfy various fastnesses and physical properties of polyester fiber for automobile interior which requires high physical properties.

In particular, when the polyester fiber used as the automobile interior material is treated under the condition of padding or adsorbing, various kinds of test standards required for automobile interior materials can not satisfy various fastness tests such as light resistance, fogging property, friction coloring property, Or the adsorption rate of the flame retardant during processing is usually 40 to 50% or less. In addition, there is a problem that it is difficult to apply to a car product as a result of the fogging test of a polyester fiber adsorbed using a processed flame retardant agent using a general processing method.

Korean Patent No. 10-659994 relates to a flame retardant processing agent and a flame retardant processing method for a polyester fiber product, which comprises a flame retardant additive selected from the group consisting of 1,4-pyrazazine diyl bis (diaryl phosphate), diaryl aminophosphate, Aminophosphate is dispersed in a solvent in the presence of a nonionic surfactant or an anionic surfactant as a flame retardant. However, it has limitations such as deterioration of flame retardancy, deterioration of taring and dyestuff, and decrease of light fastness due to lowering of absorption rate.

Accordingly, there is a need for a flame retardant agent that satisfies durability and flame retardancy / flame retardancy, various fastnesses, and physical properties required for an automobile interior material, and a method for flame retarding / flame retarding polyester fiber using the same.

1: Korea Patent No. 10-659994

Therefore, the present inventors have found that when the nonionic surfactant and the anionic surfactant are used singly or simply in the process of mixing and dispersing the flame retardant in the water in the process of atomization and dispersion, it is difficult to have satisfactory properties such as dispersibility and suckability First, an aminophosphate flame retardant and a nonionic surfactant are added to water to produce a flame retardant mixture. The flame retarder mixture is pulverized and atomized and dispersed in water, and then an anionic surfactant is added thereto to form an atomized surfactant The dispersibility of the flame retardant is improved and the stable adsorption performance of the nonionic surfactant is maintained and the dispersibility is also maintained. The flame retardant agent is adhered to the polyester fiber, To satisfy the physical properties and fastness So that the present invention has been developed.

Accordingly, an object of the present invention is to provide a flame retardant / flame retarding method for polyester fibers using a stable form of a flame retardant additive excellent in adsorption performance and dispersibility.

Another object of the present invention is to provide a polyester fiber for automobile interior materials manufactured by the flame retarding / flame retarding method of the polyester fiber.

In order to solve the above-mentioned problems, the present invention provides a process for producing a water-soluble polymer, comprising: (a) mixing a phosphoric acid amide compound and a nonionic surfactant in a solvent to prepare a mixture; (b) pulverizing and atomizing the mixture to disperse the phosphoric acid amide compound adsorbed with the nonionic surfactant in the solvent; And (c) a step of adding an anionic surfactant to a solvent in which a phosphoric acid amide compound is dispersed, to a polyester fiber, and then adhering the fiber to the polyester fiber to adhere the polyester fiber to the polyester fiber, ≪ / RTI >

Further, the present invention provides a polyester-based fiber product for automobiles, to which a flame retardant / flame retardant treated with the above method is applied in an amount of 0.05 to 30% by weight.

By using the flame retardant transfer agent according to the present invention, polyester-based fibers are subjected to a flame-retardant / flame-retardant treatment to provide not only excellent durability but also high dispersibility and adsorptivity, and satisfactory physical properties for automobile interior materials can be satisfied.

In addition, the flame-retardant / flame-retardant polyester fiber product according to the present invention can be applied not only to automobile interior materials but also to seat covers, seat covers, curtains, wallpaper, ceiling cloths, carpets, thick films with patterns, It can be widely applied.

In general, a method of adsorbing a flame retardant to a polyester fiber to perform a flame retardant / flame retardant treatment of the polyester fiber includes first mixing a flame retardant, a dye, an anti-light agent, a dispersant, and the like in a solvent such as water at 100 to 140 ° C for about 1 hour (Hereinafter referred to as "flame retardant agent") is adsorbed on the polyester-based fiber to flame-treat the polyester-based fiber. The important point here is the dispersion stability of the flame retardant to the solvent at high temperature. When the dispersion stability is unsatisfactory, problems such as a dyed yarn and a stain may occur due to the taring phenomenon of the dye during the adsorption of the flame retardant dye on the fiber.

In order to solve such a problem, an anionic dispersant is used in the process of atomizing an ordinary flame retardant in water. The anionic dispersing agent is excellent in high temperature stability and has an excellent effect of preventing a phenomenon such as a dyed ribbon caused by taring of a dye at a high temperature. However, when such an anionic dispersant is used, the dye or the flame retardant is prevented from being adsorbed and diffused into the polyester fiber, which causes the adsorption rate to be lowered.

To solve these problems, methods using nonionic surfactants have been proposed. These nonionic surfactants are prepared by the addition reaction of ethylene oxide (EO) with organic substances such as higher alcohols and fatty acids under high pressure. When a nonionic surfactant is used, hydrophilicity to water decreases However, when the nonionic surfactant is applied to the processing of the flame retardant by using the principle of reducing the hydrophilicity at high temperature, the effect of increasing the adsorption rate of the polyester fiber is exhibited. However, such a nonionic surfactant has disadvantages of poor dispersibility and thus has a problem of dyestuff and taring.

Accordingly, when the flame retardant is processed, a nonionic surfactant or an anionic surfactant is used alone as a dispersant, or the mixture is used to disperse the flame retardant in water to make the flame retarder finely. In this case, when the nonionic surfactant is used alone as described above, the adsorption efficiency is increased but the dispersibility is lowered, causing a problem of the dyestuff or taring. On the other hand, when an anionic surfactant is used singly or an anionic surfactant and a nonionic surfactant are simply mixed at the same time, when the flame retardant is dispersed in water and atomized, there is a problem that the dispersibility is excellent but the adsorption property is lowered, The cost problem of using a large amount of the flame retardant agent occurs.

Therefore, the present invention relates to a polyester resin composition which is capable of increasing the adsorption rate of the flame retardant by varying the process of atomization by dispersing it in a solvent (water) and enhancing the stability of the flame retardant, Provides a method of flame retarding / flame retarding fiber.

Hereinafter, the present invention will be described in more detail as an embodiment.

(A) preparing a mixture by mixing a phosphoric acid amide compound and a nonionic surfactant in a solvent; (b) pulverizing and atomizing the mixture to disperse the phosphoric acid amide compound adsorbed with the nonionic surfactant in the solvent; And (c) a step of adding an anionic surfactant to a solvent in which a phosphoric acid amide compound is dispersed, to a polyester fiber, and then adhering the fiber to the polyester fiber to adhere the polyester fiber to the polyester fiber, ≪ / RTI >

Further, the flame retarding / flame retarding method of the present invention refers to a flame retarding / flame retarding method of a polyester fiber including a method of mixing the flame retardancy agent with a dye during polyester-based fiber dyeing and applying the mixture to the polyester fiber. In other words, the flame retardant additive used in the present invention is a 'dyeing flame retardant flame retardant' that can be used together in the dyeing process of fibers.

First, the flame retardancy subtractive agent according to the present invention is prepared by (a) mixing a phosphoric acid amide compound and a nonionic surfactant in a solvent to prepare a mixture.

More specifically, the phosphoric acid amide compound in the step (a) may be a compound represented by the following formula (1) as a flame retardant.

(1)

In the above formula (1), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently a C ₆ to C ₆₀ aryl group.

In the compound represented by the formula (1), i.e., 1,4-piperazinediylbis (diarylphosphate), Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ each independently represents C ₆ To C ₆₀ , preferably C ₆ To C < ₁₈ > Examples of such aryl groups include phenyl, naphthyl, biphenyl and the like, preferably phenyl. This aryl group may be substituted by C ₁ To C ₄ alkyl group, and may be substituted with at least one, preferably from 1 to 3, alkyl groups. These C ₁ Examples of the aryl group substituted with an alkyl group of C ₄ include a tolyl group, a xylyl group, and a methylnaphthyl group.

A preferred specific example of the compound represented by the formula (1) may include 1,4-piperazinediylbis (diphenylphosphate). The 1,4-piperazinediylbis (diphenylphosphate) as described in JP-A-10-175985, for example, is prepared by reacting diphenylphosphorane And then reacting it with chlorochloridate.

Further, the phosphoric acid amide compound used in the present invention may be a compound represented by the following formula (2) as a flame retardant.

(2)

In the above formula (2), Ar ₁ and Ar ₂ are each independently C ₆ To C ₆₀ , R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, C ₁ C ₆ alkyl group, C ₃ ~ C ₆₀ aryl group, a cycloalkyl group, C ₆ ~ C ₆₀ of, C ₃ To C ₆₀ allyl group or C ₇ Or an aralkyl group of C < _{60 &} gt ;, or R < ₁ > and R < ₂ > may combine with each other to form a ring together with the nitrogen atom bonded to the phosphorus atom.

In the compound represented by the formula (2), i.e., in the diarylaminophosphate, Ar ₁ and Ar ₂ are each independently C ₆ To C ₆₀ , preferably C ₆ To C < ₁₈ > Examples of such aryl groups include phenyl, naphthyl, biphenyl and the like, preferably phenyl. This aryl group may be substituted by C ₁ To C ₄ alkyl group, and may be substituted with at least one, preferably from 1 to 3, alkyl groups. These C ₁ Examples of the aryl group substituted with an alkyl group of C ₄ include a tolyl group, a xylyl group, and a methylnaphthyl group.

Specific examples of the compound represented by the formula (2) include aminodiphenyl phosphate, methylaminodiphenyl phosphate, dimethylaminodiphenyl phosphate, ethylaminodiphenyl phosphate, diethylaminodiphenyl phosphate, propylaminodiphenylphosphate, di Propyl amino diphenyl phosphate, octyl amino diphenyl phosphate, diphenyl undecyl amine phosphate, cyclohexylaminodiphenyl phosphate, dicyclohexylaminodiphenyl phosphate, allylaminodiphenyl phosphate, anilinodiphenyl phosphate, di-o -Cresylphenylaminophosphate, diphenyl (methylphenylamino) phosphate, diphenyl (ethylphenylamino) phosphate, benzylaminodiphenylphosphate, morpholinodiphenylphosphate, and the like. Such a diarylaminophosphate can be obtained by reacting diarylphosphorochloridate with an organic amine compound in the presence of an amine catalyst in an organic solvent as disclosed in Japanese Patent Laid-Open No. 2000-154277.

The phosphoric acid amide compound used in the present invention may be a compound represented by the following formula (3) as a flame retardant.

(3)

In the above formula (3), Ar ₁ represents C ₆ To C ₆₀ , R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, C ₁ - a cycloalkyl group of C ₆ alkyl group, C ₃ ~ C ₆₀ of, C ₆ - an aryl group of C _60, C ₃ ~ C ₆₀ allyl group, or a C ₇ ~ Represents the aralkyl group of C _60, or R ₁ and R ₂ may bond to one another to form a ring, and R ₃ and R ₄ may form a ring together with the nitrogen atom bonded to the phosphorus atom bonded to each other can do.

In the compound represented by the formula (3), i.e., aryldiaminophosphate, Ar ₁ is C ₆ To C ₆₀ , preferably C ₆ To C < ₁₈ > Examples of such aryl groups include phenyl, naphthyl, biphenyl and the like, preferably phenyl. This aryl group may be substituted by C ₁ To C ₄ alkyl group, and may be substituted with at least one, preferably from 1 to 3, alkyl groups. Examples of the aryl group substituted by such a C ₁ -C ₄ alkyl group include a tolyl group, a xylyl group, and a methylnaphthyl group.

Preferred examples of the compound represented by the formula (3) include diaminophenyl phosphate, aminomethylaminophenyl phosphate, bis (methylamino) phenylphosphate, aminoethylaminophenylphosphate, bis (ethylamino) phenylphosphate, aminopropylaminophenyl (Aminophenyl) phosphate, bis (propylamino) phenyl phosphate, aminooctylaminophenyl phosphate, aminoundecylaminophenyl phosphate, aminocyclohexylaminophenyl phosphate, biscyclohexylaminophenyl phosphate, bisallylaminophenyl phosphate, Anilinophenylphosphate, anilinomethylaminophenylphosphate, ethylaminophenylaminophenylphosphate, bisbenzylaminophenylphosphate, dimorpholonophenylphosphate, and the like. Such aryl diaminophosphate can be obtained by reacting arylphosphorodichloridate with an organic amine compound in an organic solvent in the presence of an amine catalyst as described in JP 2000-154277 A.

In general, when a fiber product is subjected to a flame-proofing process by post-processing, the particle size of the phosphoric acid-based compound flame retardant used has a significant influence on the flame retardant performance imparted to the fiber product by the flame retarding treatment. The smaller it is, the higher the flame retardant performance can be given to the textile product. When the particle size of the flame retardant is large in the flame retarding treatment, the adsorption performance on the surface of the polyester fiber is deteriorated and the use efficiency of the flame retardant is decreased, so that an excessive amount of flame retardant must be used. Therefore, according to the present invention, the particle diameter (average particle diameter) of the flame retardant is usually 0.3 to 20 占 퐉 so that the flame retardant is sufficiently diffused into the interior of the polyester fiber product by the post-processing so that the flame retardant performance by the flame retardant agent is durable. 0.2 to 0.8 mu m, and more preferably 0.5 mu m.

The mixture of step (a) is preferably mixed with 100 parts by weight of the phosphoric acid amide compound and 100 parts by weight of the solvent and 1 to 30 parts by weight of the nonionic surfactant. When mixing less than 1 part by weight of the nonionic surfactant, the stability of the product is significantly deteriorated. When the amount of the nonionic surfactant is more than 30 parts by weight, the flame retardant is plasticized to cause bleeding problems. .

The nonionic surfactant in the step (a) may be at least one selected from the group consisting of polyoxyalkylene type nonionic surfactants, polyhydric alcohol type nonionic surfactants, polyoxyethylene styrenated phenyl ether type nonionic surfactants, distyrylphenyl ethoxylate ethylene (Distylrylphenyl ethoxylate Ethylene oxide) adduct and Tridecyl ethoxylate Ethylene oxide adduct are preferably used.

Specifically, the nonionic surfactant is selected from the group consisting of higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol aliphatic ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, Polyoxyalkylene type nonionic surfactants such as fatty acid amide alkylene oxide adducts, polyhydric alcohol type nonionic surfactants such as alkyl glycoxides and sucrose fatty acid esters, or polyoxyethylene styrenated phenyl ethers, for example, Polyoxyethylene styrenated phenyl ether, polyoxyethylene styrenated phenyl ether, and the like. It is also possible to use a fatty acid ester such as sorbitol oleic acid ester, sorbitan lauryl ester, sorbitan cetyl fatty acid ester, sorbitan stearyl fatty acid ester, glycerol oleic fatty acid ester, diglycerol oleic fatty acid ester, polyglycerol fatty acid ester, An alkylphenol, a fatty acid, or a lower part of ethylene oxide or propylene oxide of aliphatic alcohol and a polyoxyethylene glycol polypropylene glycol block polymer. In the present invention, distilylphenylethoxylate ethylene oxide (Distylrylphenyl ethoxylate Ethylene oxide) adduct and Tridecyl ethoxylate Ethylene oxide adduct were used, but the present invention is not limited thereto.

In addition, it is preferable to use a compound having an HLB value (Hydrophile-Lipophile Balance) of 8 to 14 among the nonionic surfactants, more preferably an HLB value of 10 to 12. For storage stability, the cloud point is preferably 100 ° C or less, more preferably 50 to 80 ° C.

When the above-mentioned cloud point is 50 캜 or lower, there is a problem in the storage stability of the product. For example, a nonionic surfactant having a hydrophilic polyol (HLB) of 10 to 15 in which a nonionic polyhydric alcohol or a lower portion of ethylene oxide or propylene oxide is used as a hydrophilic group.

In the step (b), the phosphoric acid amide compound adsorbed by the nonionic surfactant is dispersed in a solvent by pulverizing the mixture prepared in the step (a) and atomizing the mixture. In the method of pulverizing and finely pulverizing the flame retardant, A grinding method commonly used in the technical field of the invention can be used. For example, a mill filled with a glass bead, a mill filled with a geo-no-bead, or a sand grinder ) Or the like may be used.

In addition, as described above, when the flame retardant that has been atomized using only the nonionic surfactant is used for the fiber flame retardant / flame retardation treatment, the absorption rate of the flame retardant agent is faster than that of the dye and the anti- Which causes a decrease in friction coloring property and fogging property. In order to solve such a problem, in the present invention, an anionic surfactant is added to a flame retardant that has been atomized using a nonionic surfactant to supplement the polyester fiber with the exhaust.

In the step (c), an anionic surfactant is added to a solvent in which the phosphoric acid amide compound is dispersed, and it is preferable to add 5 to 20 parts by weight to 100 parts by weight of the phosphoric acid amide compound . When the amount of the anionic surfactant to be added is more than 20 parts by weight, the flame retardant of the phosphoric acid amide compound may lose its nonionic property and the adsorption property may be decreased.

The anionic surfactant used in the present invention may be at least one selected from the group consisting of sulfuric acid ester salts, alkylsulfonic acid salts, alkylphosphate salts, alkylarylsulfonate salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkyl ester phosphate salts, Alkylene alkyl ether carboxylate salts, polycarboxylate salts, lotus oils, petroleum sulfonates, alkyl diphenyl ether sulfonate salts and tristylylphenyl ethoxylate EO sulfonate ammonium salts. It is preferable to use at least one selected.

Specifically, the anionic surfactants include sulfuric acid ester salts such as higher alcohol sulfate ester salts, higher alkyl ether sulfuric acid ester salts and sulfated fatty acid ester salts; Alkylbenzenesulfonic acid salts, alkylbenzenesulfonic acid salts and alkylnaphthalenesulfonic acid salts, and alkylphosphate salts such as higher alcohol phosphoric acid ester salts and alkylene oxide adducts of higher alcohol with phosphoric acid ester salts. Also included are salts of alkylarylsulfonates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyl ester phosphates, polyoxyalkylene alkyl ether carboxylates, polycarboxylates, lotions, petroleum sulfonates, alkyl Diphenyl ether sulfonate salts and the like. Also, there may be mentioned a lignin sulfonic acid salt, an aliphatic or aromatic sulfonic acid salt, a formalin condensate of an aromatic sulfonic acid salt, a polystyrene sulfonic acid salt, a sulfuric acid ester salt of an ethylene oxide adduct of styrenated phenol or styrenated alkylphenol, a sulfuric acid ester salt of an aliphatic alcohol, A fatty acid or a sulfuric acid ester salt of an ethylene oxide adduct of an aliphatic alcohol. In the present invention, tristylarylphenyl ethoxylate (EO) sulfonate ammonium salt is used, . In addition, water is preferably used as the solvent in the present invention.

Thus, the present invention provides a flame retardant additive that reflects both the advantages of the nonionic surfactant for improving the adsorbability of the flame retardant agent and the advantages of the anionic surfactant for improving the dispersibility.

Further, in the method of manufacturing a flame retardant additive according to the present invention, the method may further include (d) after the step (c), further mixing the second flame retardant. It is preferable to mix 5 to 20 parts by weight of the second flame retardant with respect to 100 parts by weight of the flame retardant manufactured through the steps (a) to (c). When the second flame retardant is less than 5 parts by weight, the flame retardancy and the light fastness improving effect If the amount is more than 20 parts by weight, there is a problem of color yield and color fastness during dyeing. Therefore, it is preferable to use the dye within the above range.

Further comprising the step of mixing the second flame retardant agent prepared by mixing and emulsifying the second flame retardant, the nonionic surfactant, the nonionic surfactant or the anionic surfactant or the mixture thereof, and the solvent after the step (c) (d ').

The second flame retardant used in step (d) or (d ') which may be added at this time may be at least one phosphorus compound selected from the group consisting of phosphine oxide, phosphine, phosphite, and phosphoric ester, But is not limited thereto.

Specifically, the second flame retardant may be a phosphine oxide compound represented by the following chemical formula (4).

(4)

In the above formula (4), R ₁₁ , R ₁₂ and R ₁₃ are each independently a C ₁ -C ₈ alkyl group; Or a hydroxyl group, an amino group, a cyano group, a carboxyl group, a ureido group, C ₁ ~ alkyl group of C _4, di (C ₁ ~ C ₄₎ alkylamino group, a diphenylamino group, a phenoxy group or a C ₁ ~ alkoxy group substituted or unsubstituted in the C ₄ Or a substituted C ₆ -C ₆₀ aryl group.

The second flame retardant used in the present invention may be a phosphine compound represented by the following formula (5).

(5)

R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydroxyl group, an amino group, a cyano group, a carboxyl group, an ureido group, a C ₁ to C ₄ alkyl group, a di (C ₁ to C ₄ ) A diphenylamino group, a phenoxy group or a C ₆ to C ₆₀ aryl group which is unsubstituted or substituted with a C ₁ to C ₄ alkoxy group.

The second flame retardant used in the present invention may be a phosphite compound represented by the following formula (6).

(6)

R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydroxyl group, an amino group, a cyano group, a carboxyl group, an ureido group, a C ₁ to C ₄ alkyl group, a di (C ₁ to C ₄ ) A diphenylamino group, a phenoxy group or a C ₆ to C ₆₀ aryl group which is unsubstituted or substituted with a C ₁ to C ₄ alkoxy group.

The second flame retardant used in the present invention may be a phosphoric acid ester compound represented by the following chemical formula (7).

(7)

Wherein R ₄₁ , R ₄₂ and R ₄₃ are each independently selected from the group consisting of a hydroxyl group, an amino group, a cyano group, a carboxyl group, an ureido group, a C ₁ to C ₄ alkyl group, a di (C ₁ to C ₄ ) A diphenylamino group, a phenoxy group or a C ₆ to C ₆₀ aryl group which is unsubstituted or substituted with a C ₁ to C ₄ alkoxy group.

Specific examples of the compounds represented by the above formulas (4) to (7) are as follows:

In the above formula, Me represents a methyl group, Ph represents a phenyl group, and Et represents an ethyl group.

The compound of the above formula (201) can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2004-43405. This compound is commercially available as TPP (trade name, manufactured by Hokko Chemical Co., Ltd.).

The compound of the above formula (202) can be synthesized, for example, by the method described in JP-A-1987-145095. This compound is commercially available as TPPO (trade name, manufactured by Hokko Chemical Co., Ltd.).

The compound of the above formula (203) is commercially available from Wako Ohshin Kabushiki Kaisha.

The compound of formula (204) is commercially available from Wako Ohshin Kabushiki Kaisha.

The compound of the above formula (205) is commercially available from Wako Ohshin Kabushiki Kaisha.

The compound of the above formula (207) can be synthesized by the method described in JP-A-2006-70417. This compound is commercially available as NDPP (trade name; manufactured by Daihachi Chemical Co., Ltd.).

The compound of the above formula (208) can be synthesized by the method described in JP-A-2004-43405. This compound is commercially available as TCP (trade name; manufactured by Daihachi Chemical Co., Ltd.).

The compound of the above formula (209) is commercially available as # 5 (trade name; manufactured by Daihachi Chemical Co., Ltd.).

The compound of the above formula (211) is commercially available as TPP (trade name, manufactured by Daihachi Chemical Co., Ltd.).

The compound of the above formula (220) is commercially available from Sigma-Aldrich Co.,

The compound of the above formula (221) is commercially available from Sigma-Aldrich Co.,

The compound of the above formula (222) can be prepared by, for example, subjecting a commercially available compound as DPCP (trade name, manufactured by Hokko Chemical Industries Co., Ltd.) to oxidation by air oxidation or hydrogen peroxide.

The compound of the above formula (223) can be prepared by, for example, subjecting a commercially available compound as TPTP (trade name; manufactured by Hokko Chemical Industry Co., Ltd.) to oxidation with air or oxidation using hydrogen peroxide.

The compound of the above formula (224) is commercially available as TOPO (trade name, manufactured by Hokko Chemical Industry Co., Ltd.).

The compound of the above formula (210) is resorcinol bis (diphenylphosphate), which is commercially available as RDP.

Also, in the present invention, cresyldiphenyl phosphate (CDP) may be used as the second flame retardant, and it is very effective in improving various fastness problems and absorption efficiency by adding it to a phosphoric acid amide compound.

The second flame retardant added in the present invention may be emulsified or dispersed in water, and may be emulsified using an emulsifier commonly used in the technical field of the present invention and a conventional emulsification apparatus.

As mentioned in the step (d '), preferably 100 parts by weight of the second flame retardant is mixed with 5 to 20 parts by weight of the nonionic surfactant or the anionic surfactant or the mixture thereof to 100 parts by weight of the solvent, .

Here, the nonionic surfactant or the anionic surfactant may be a nonionic surfactant or an anionic surfactant used in the step (a) or (c), and may be a nonionic surfactant or an anionic surfactant, If the amount of the mixture is less than 5 parts by weight, there is a problem of separation due to the increase in particle size after emulsification. If it exceeds 20 parts, the emulsification stability is good.

In this case, the second flame-retardant additive in the step (d ') is preferably mixed with 10 to 40 parts by weight based on 100 parts by weight of the flame-retardant additive prepared through steps (a) to (c). When the second flame retardant is less than 10 parts by weight, there is no effect of raising the flame retardancy and the absorption rate. When the second flame retardant is more than 40 parts by weight, it is preferable to use within the above range.

In addition, the flame retardancy agent according to the present invention may be a protective colloid agent such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starch paste and the like for enhancing storage stability; Flame retarding agent for enhancing flame retarding effect; An antioxidant and the like may be included if necessary. In addition, it is also possible to use an organic solvent, an organic solvent, a penetration promoter, a polyhydric alcohol, a preservative, a chelating agent, a pH adjuster, a humectant, a defoamer, a fungicide, a pigment, a pigment, an ultraviolet absorber, A dye, an anti-fogging agent, a dye, and the like to the flame retardant mixture.

The flame retardant agent prepared according to the above method is a flame retardant agent having both the advantages of a nonionic surfactant for improving the adsorbability of a flame retardant agent and the advantages of an anionic surfactant for improving dispersibility.

As described above, the present invention provides a method for flame-retarding / flame-retarding polyester-based fibers comprising a method of adhering a flame-retardant additive to a polyester-based fiber by applying the flame retardant additive to polyester-based fibers.

At this time, the adhesion amount of the flame retardant additive to the polyester fiber is preferably 0.05 to 30 wt%, more preferably 0.5 to 20 wt%. If the amount is less than 0.05% by weight, sufficient flame retardancy can not be imparted to the polyester fiber. If the amount is more than 30% by weight, the problem of roughness of the fiber product after the flame retardant / desirable.

The method for imparting a flame retardancy index according to the present invention to a polyester fiber product and performing a flame retardation treatment is not particularly limited. For example, the flame retardancy index is attached to a polyester fiber product and heat-treated at a temperature of 170 to 220 캜, And the flame retardant is absorbed into the fibers.

In this case, for example, a padding method, a spray method, a coating method, or the like may be used in order to attach the flame retardancy agent to the polyester fiber product. Further, as another method of imparting the flame retardancy agent according to the present invention to the polyester fiber product and performing the flame retardant processing, the polyester fiber product is immersed in the flame retardancy agent, and the polyester fiber product is treated in the bath at a temperature of 110 to 140 캜, And a method of sucking in the inside. Further, in the flame retardant transfer agent according to the present invention, other fibers may be used in combination with the transfer agent. Examples of such fibers include a softener, an antistatic agent, a water-repellent emulsion, a hard-finishing agent, a tactile-control agent, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  One: Flame retardancy deduction  A

100 parts by weight of anilino diphenyl phosphate as a phosphoric acid amide type (aminophosphate) compound flame retardant, 13 moles of distylrylphenyl ethoxylate ethylene oxide as a nonionic surfactant and 20.0 g of tridecyl ethoxylate ethylene 5 parts by weight of the adduct of 7 moles of tridecyl ethoxylate ethylene oxide and 0.1 part by weight of the silicone antifoaming agent were mixed in 100 parts by weight of water. This mixture was put into a mill filled with dicloc bean beads having a diameter of 0.6 mm and pulverized until the average particle diameter of the flame retardant became 0.5 μm or less. Thereafter, 10 parts by weight of trisilylarylphenyl ethoxylate ethylene oxide (16 mol) sulfate ammonium salt was added as an anionic surfactant, and after the anion treatment was completed, the resultant was dried at a temperature of 150 DEG C for 30 minutes to give non-volatile Minute was adjusted to be 40% by weight to obtain the flame retardant additive A according to the present invention. The particle size of the flame retardant was 0.48 mu m. Regarding the average particle diameter of the flame retardant, the particle size distribution of the phosphoric acid amide in the flame retardant was measured with a HORIBAR laser diffraction particle size analyzer LA-950, and the median diameter was adopted as the average particle diameter.

Example  2: Flame retardancy deduction  B

90 parts by weight of flame retardant A prepared in Example 1 and 10 parts by weight of Flame Retardant H to be described later were mixed in the same manner as in Example 1 to obtain Flame Retardant B.

Example  3: Flame retardancy deduction  C

The flame retardant transfer agent C obtained in the same manner as in Example 1 was prepared by adding 20 parts by weight of the flame retardant transfer agent H to 80 parts by weight of the flame retardant transfer agent A obtained in the above [Example 1].

Comparative Example  One: Flame retardancy deduction  D ( HBCD , Hexabromocyclododecane )

40 parts by weight of flame retardant 1,2,5,6,9,10-hexabromocyclododecane, 3.5 parts by weight of sodium dioctylsulfo succinate as an anionic surfactant, and 0.1 part by weight of a silicone antifoaming agent were mixed in 25 parts by weight of water. This mixture was put into a mill filled with glass beads having a diameter of 0.8 mm and pulverized until the average particle size of the flame retardant became 0.415 탆 and dried at 150 캜 for 30 minutes to obtain a non-volatile component having a concentration of 40 By weight to obtain a flame retardant transfer agent D according to the comparative example. The average particle diameter of the flame retardant in the flame retardant agent was 0.45 mu m.

Comparative Example  2: Flame retardancy deduction  E ( TPPO , Triphenylphosphine oxide )

, 5 parts by weight of a 13 molar addition product of distylrylphenyl ethoxylate ethylene oxide (nonionic surfactant), 16 parts by weight of an anionic surfactant, tristylarylphenyl ethoxylate ethylene oxide 5 parts by weight of ammonium sulfate and 100 parts by weight of triphenylphosphine oxide which is a flame retardant were simultaneously mixed in 100 parts by weight of water and then pulverized using 0.6 mm zirconia beads so as to be 0.5 microns or less and then dried at 150 DEG C for 30 minutes To adjust the concentration of the non-volatile component to be 40% by weight to obtain a flame retardant additive E according to the comparative example. The average particle diameter of the flame retardant in the flame retardant agent was 0.48 mu m.

Comparative Example  3: Flame retardancy deduction  F ( RDP , Resocynol 피덴 phosphate )

, 5 parts by weight of a 13 molar addition product of distylrylphenyl ethoxylate ethylene oxide (nonionic surfactant), 16 parts by weight of an anionic surfactant, tristylarylphenyl ethoxylate ethylene oxide 5 parts by weight of a sulfate ammonium salt and 100 parts by weight of a flame retardant resorcinol diphenyl phosphate (RDP) were emulsified and dispersed in 100 parts by weight of water, followed by drying at a temperature of 150 DEG C for 30 minutes to obtain a non-volatile component having a concentration of 40 By weight to obtain a flame retardant F according to the comparative example. The average particle diameter of the flame retardant in the flame retardant agent was 2.11 mu m.

Comparative Example  4: Flame retardancy deduction  G

30 parts by weight of flame retardant transfer agent H was added to 70 parts by weight of the flame retardant transfer agent A obtained in the above Example 1 to obtain a flame retardant transfer agent G. [

Comparative Example  5: Flame retardancy deduction  H ( CDP , Cresyldiphenyl phosphate )

5 parts by weight of a 13 molar addition product of distylrylphenyl ethoxylate ethylene oxide as a nonionic surfactant, 16 parts by weight of an anionic surfactant, tristylarylphenyl ethoxylate ethylene oxide (Trisylarylphenyl ethoxylate EO) And 100 parts by weight of cresyldiphenyl phosphate (CDP) as a second flame retardant were simultaneously emulsified and dispersed in 100 parts by weight of water and dried at a temperature of 150 캜 for 30 minutes to obtain a non-volatile component having a concentration of 40 wt% % To obtain a flame retardant transfer agent H according to the comparative example. The average particle diameter of the flame retardant in the flame retardant agent was 1.78 mu m.

Comparative Example  6: Flame retardancy deduction  I

100 parts by weight of anilinodiphenyl phosphate as a phosphoric acid amide-based (aminophosphate-based) flame retardant, 5 parts by weight of distyrylphenyl ethoxylate EO (ethylene oxide) 13-mole adduct as a nonionic surfactant, 5 parts by weight of decyl ethoxylate ethylene oxide (7 parts by weight of ethylene oxide) and 0.1 part by weight of a silicone antifoaming agent were mixed in 100 parts by weight of water. The mixture was mixed with a milky-bean bead mill having a diameter of 0.6 mm And the mixture was pulverized until the average particle diameter of the flame retardant became 0.5 m or less and then dried at 150 DEG C for 30 minutes to adjust the concentration of the non-volatile matter to 40 wt% to obtain a flame retardant transfer product I. The average particle diameter of the flame retardant additive was 0.48 mu m.

Comparative Example  7: Flame retardancy deduction  J

100 parts by weight of anilino diphenyl phosphate as an aminophosphate-based flame retardant, 5 parts by weight of a 13-molar adduct of Distylrylphenyl ethoxylate EO (Ethylene oxide), which is a nonionic surfactant, 5 parts by weight of an anionic surfactant 5 parts by weight of tristylarylphenyl ethoxylate ethylene oxide (EO (ethylene oxide) 16 molar sulfate and 0.1 part by weight of silicone antifoaming agent) were simultaneously mixed in 100 parts by weight of water. This mixture was mixed with diroquinone beads having a diameter of 0.6 mm The resulting mixture was pulverized until the average particle diameter of the flame retardant became 0.5 m or less and then dried at 150 DEG C for 30 minutes to adjust the concentration of the non-volatile matter to 40 wt% J. The average particle diameter of the flame retardant was 0.45 mu m.

Experimental Example : Measurement of physical properties

The polyester-based fibers for automobiles were subjected to flame-retardant / flame-retardant treatment according to the conventional fiber flame retarding method using the flame retardant admixtures A to C prepared in accordance with the present invention and the comparative flame retardant admixtures D to J not according to the present invention. Flame retardant / flame retardant treatment method and physical property measurement method are as follows.

(1) Flame retardant / flame retarding method and flame retardant performance evaluation

15% owf of the disperse dye 3% owf, the dye dispersant (anionic dispersant) 0.5 g / L, the flame retardancy agent of the Example or the flame retardancy agent of the comparative example were blended in a salt bath, the pH was adjusted to 4.6 to 4.8 with acetic acid, 15. The treated fabric was charged into a salt bath, heated from 50 占 폚 to 130 占 폚 at a heating rate of 2 占 폚 per minute, held at that temperature for 60 minutes and then subjected to a bath-soaking treatment, washed with water and dried, The flame retardant performance was evaluated according to the L 1091 D method (coiling method, passed when the number of times of flocking was 3 or more).

(2) Friction Fastness  Measure

The test was carried out according to the rubbing fastness test method according to the technical standard MS300-31.

(3) Hydrolysis test

The flame-retarded fabric is fixed to an autoclave (AUTO CLAVE). After 72 hours at 120 ° C, the color change and pH change are measured on the fabric surface to measure the hydrolytic ability. This is due to the phenomenon that the phosphoric acid ester compounds decompose into phosphoric acid when the hydrolysis is performed and the pH is lowered.

(4) Lightning Fastness  Measure

The light fastness was measured according to the technical standard MS300-31.

(5) Flame Retardant Fastness  Measure

The flame-retardant fastness was determined by the test method according to MS300-31.

* S.E (Self Extinguish): Off within 38 mm from the mark

* Acceptance criteria are: 80 mm / min (ride distance / 60 seconds)

(6) Forgiveness ( fogging ) Measure

It was judged by the fogging test according to MS300-54.

(7) Taring / Dyestuff  Measure

The dyes and the flame retardant were gathered on the surface of the dyeing machine and the fabric.

(8) Weight change of fabric

The greater the weight of the fabric, the higher the adsorption efficiency.

The results of the measurement by the above method are shown in Table 1. Specifically, Table 1 shows the results of evaluation of flame retardancy and flame retardancy of the non-volatile component, the content of the flame retardant, the average particle size of the flame retardant, the texture, the friction generation (dry / wet) Test data for hydrolysis tests, flame retardancy, light fastness, color yield, fogging and taring / dyed yarns.

[Table 1]

Physical property measurement result

* Standard value (target value): Light fastness grade 3 or higher, no taring / dyed yarn, flame retardance 80 mm / min or less, no embrittlement of fabric due to hydrolysis, softness, color yield 95% Standard value.

As shown in Table 1, in the case of [Example 1] in which the phosphorus flame retardant of the present invention was subjected to atomization with a nonionic surfactant and then dispersed into an anionic surfactant, [Comparative Example 1], [Comparative Example 2], [Comparative Example 3] and [Comparative Example 5] in which the nonionic surfactant and the anionic surfactant were simultaneously mixed and atomized, and the nonionic surfactant alone It can be seen that the average particle size is smaller and the color yield is excellent, and the light resistance and the adsorption property are further improved.

In the case of [Example 2] and [Example 3] in which two flame retardant additives were mixed to form a flame retardant additive, when the second flame retardant additive was adjusted to 20% by weight or less, the result that the color yield was 95% or more , Whereas the color yield of Comparative Example 4 in which the mixing ratio was 30% by weight was remarkably decreased to 85%.

Therefore, it can be seen that the flame retardant additive produced by the production process according to the present invention has an effect of greatly increasing flame retardancy and efficiency when used together with the additional second flame retardant additive. Further, it is predicted that the flame-retardant / flame-retardant polyester fiber obtained by using such a flame retardant additive does not generate a halogen compound gas and can satisfy various fastnesses and properties of polyester fiber for automobile interior without being harmful to the environment .

Claims (17)

(a) mixing a phosphoric acid amide compound and a nonionic surfactant in a solvent to prepare a mixture; (b) pulverizing and atomizing the mixture to disperse the phosphoric acid amide compound adsorbed with the nonionic surfactant in the solvent; And (c) a step of adding an anionic surfactant to a solvent in which a phosphoric acid amide compound is dispersed, and then applying the resulting flame retarder to the polyester fiber and attaching the same to the polyester fiber. Flame retarding / flame retarding method of polyester fiber.
2. The flame retardant polyester fiber according to claim 1, wherein the flame retardancy agent comprises a method of mixing polyester fiber with polyester resin, Flame retarding method.
The method according to claim 1, wherein the mixture of step (a) is prepared by mixing 100 parts by weight of a solvent and 100 parts by weight of a phosphoric acid amide compound with 1 to 30 parts by weight of a nonionic surfactant. Flame Retarding / Flame Retarding Method of Fiber.
The method according to claim 1, wherein the phosphoric acid amide compound in step (a) has an average particle diameter of 0.2 to 0.8 占 퐉.
The method according to claim 1, wherein the nonionic surfactant in step (a) is selected from the group consisting of a polyoxyalkylene type nonionic surfactant, a polyhydric alcohol type nonionic surfactant, a polyoxyethylene styrenated phenyl ether type nonionic surfactant, Wherein the polyester fiber is at least one selected from the group consisting of distillylphenyl ethoxylate ethylene oxide adducts and tridecyl ethoxylate ethylene oxide adducts. Flame retardant / flame retarding method.
The flame retarding / flame retarding method for polyester fibers according to claim 1, wherein the pulverization in step (b) is carried out by putting the mixture in a mill filled with beads and pulverizing.
The method according to claim 1, wherein the anionic surfactant in step (c) is added in an amount of 5 to 20 parts by weight based on 100 parts by weight of the phosphoric acid amide compound. .
The method according to claim 1, wherein the anionic surfactant in step (c) is selected from the group consisting of sulfuric acid ester salts, alkylsulfonate salts, alkyl phosphate salts, alkylarylsulfonate salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkyl Ester phosphate salt, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate salt, lotus oil, petroleum sulfonate, alkyl diphenyl ether sulfonate salt, and tristilylphenyl ethoxylate ethylene oxide Wherein the flame retarding agent is at least one selected from the group consisting of an ammonium salt and a nitrate ammonium salt.
The flame retarding / flame retarding method of polyester fiber according to claim 1 or 3, wherein the solvent is water.
The flame retarding / flame retarding method for polyester fibers according to claim 1, further comprising the step (d) of further mixing the second flame retardant after the step (c).
The flame retarding / flame retarding method for polyester fibers according to claim 10, wherein 5 to 20 parts by weight of the second flame retardant is added to 100 parts by weight of the flame retardant additive prepared in claim 1.
The method according to claim 1, further comprising, after the step (c), further mixing a second flame retardant agent prepared by mixing and emulsifying a second flame retardant, a nonionic surfactant or an anionic surfactant or a mixture thereof, (d ') of the flame-retardant polyester fiber.
13. The method according to claim 12, wherein the second flame-retardant additive is prepared by mixing 100 parts by weight of a second flame retardant, 100 to 5 parts by weight of a non-ionic surfactant or an anionic surfactant, A flame retardant / flame retarding method for polyester fibers using a flame retardant additive.
13. The flame retardant / flame retarding method for polyester fibers according to claim 12, wherein the second flame retardant additive comprises 10 to 40 parts by weight of the second flame retardant additive, based on 100 parts by weight of the flame retardant additive prepared according to claim 1. .
The flame retardant agent according to any one of claims 10 to 12, wherein the second flame retardant is at least one phosphorus compound selected from the group consisting of phosphine oxide, phosphine, phosphite and phosphate ester. Flame retardant / flame retarding method for polyester fibers used.
The flame retarding / flame retarding method for polyester fibers according to claim 1, wherein the adhesion amount of the flame retardant additive to the polyester fiber is from 0.05 to 30% by weight.
A polyester-based fiber product for automobiles, which is provided with a flame retardant / flame retardant treated with 0.05 to 30% by weight by the method according to any one of claims 1 to 8, 10 to 14, .