CN101631910A - Flameproofing agent, flame-retardant fiber and method for producing the same - Google Patents

Abstract

Disclosed is a flameproofing agent which is used for imparting a fiber material with flame retardancy and capable of providing good flame retardancy even in a small amount. This flameproofing agent enables to suppress deterioration of other physical properties, while having excellent product stability. Specifically disclosed is a flameproofing agent containing a phosphorus compound (A), a surfactant (B) composed of an anionic surfactant and/or a nonionic surfactant and water, which is used for imparting a fiber material with flame retardancy. The phosphorus compound (A) has a median particle size (D50) of not more than 1 [mu]m.

Description

Flame retardant and flame retardant textile material and preparation method thereof

technical field

The invention relates to a flame retardant, a flame retardant textile material and a preparation method thereof.

Background technique

In conventional methods, flame retardants prepared by dispersing or emulsifying halogen compounds such as hexabromocyclododecane in water are generally used to impart flame retardant properties to textile materials. Although textile materials coated with halogen compounds have flame-retardant properties, toxic gases may be generated when the materials are burned. For this reason and for the growing movement away from halogen compounds based on environmental considerations, there is a tendency to avoid the use of halogen compounds as much as possible.

Although organophosphorus compounds are used as substitutes for halogen compounds, they cannot impart sufficient flame-retardant properties due to the small amount of phosphorus contained in each molecule of those compounds. Therefore, large amounts of organophosphorus compounds must be applied to textile materials to impart sufficient flame retardant properties. Applying such large amounts of organophosphorus compounds on textile materials leads to problems such as poor textile hand and reduced color fastness of dyed textile materials caused by rubbing and exposure to light. Furthermore, the molecular weight of organophosphorus compounds is too small to be resistant to heat, so that said compounds sometimes cause fogging of transparent articles around textile materials coated with them. In order to solve these problems, diphosphoric acid having a high molecular weight has been proposed as a flame retardant. Patent References 1 to 3 disclose methods of imparting flame-retardant properties to textile materials using resorcinol bis(diphenyl phosphate) as an example of a phosphorus-containing flame retardant.

Patent Reference 4 discloses a method of imparting flame-retardant properties to textile materials using a flame retardant by introducing tetrakis(2,6-dimethylphenyl)-m- - A solution prepared by dispersing phenylene phosphate. Patent Reference 5 discloses a method of imparting flame-retardant properties to textile materials using a flame retardant, which is a solution prepared by dispersing naphthyl diphenyl phosphate as a phosphorus-containing flame retardant.

[Patent Reference 1] JP A 2000-328445

[Patent Reference 2] JP A 2002-88368

[Patent Reference 3] JP A 2005-15947

[Patent Reference 4] JP A 2001-254268

[Patent Reference 5] JP A 2006-70417

However, resorcinol bis(diphenyl phosphate) disclosed in Patent References 1 to 3 is easily hydrolyzed due to the phosphorus-oxygen single bond (phosphate group) contained in its chemical structure, and in Phosphoric acid produced in hydrolysis degrades textile materials. Furthermore, resorcinol bis(diphenyl phosphate) deteriorates the color fastness of dyed textile materials, such as loss of color fastness due to rubbing, since this compound is liquid at normal temperatures. The flame retardant disclosed in Patent Reference 3 is less prone to hydrolysis due to the use of self-emulsifiable resorcinol bis(diphenyl phosphate). However, when a flame retardant is applied to a textile material, it becomes more prone to hydrolysis and thus degrades the textile material over time. For the purpose of making the properties of the flame retardant durable to washing and dry cleaning, the flame retardant is usually applied to the textile material in a dye bath. In this process, resorcinol bis(diphenyl phosphate) cannot impart sufficient flame-retardant properties to the textile material, since due to its high molecular weight the substance cannot be adequately applied to the textile material. Although the tetrakis(2,6-dimethylphenyl)-m-phenylene phosphate contained in the flame retardant disclosed in the above Patent Reference 4 is resistant to hydrolysis, the high molecular weight and The steric bulk property prevents it from being applied adequately to textile materials and inhibits the attainment of durable flame retardant properties. Naphthyl diphenyl phosphate contained in the flame retardant disclosed in Patent Reference 5 has a melting point of about 60° C., and when the textile material coated with the flame retardant is processed into articles such as car seats , the flame retardant may melt to reduce the color fastness of the textile material to rubbing. In addition, this flame retardant has poor light resistance and is not practical.

As mentioned above, conventional flame retardants have both advantages and disadvantages in their performance.

Contents of the invention

technical problem

The object of the present invention is to provide a flame retardant for imparting flame retardant properties to textile materials, which achieves sufficient flame retardant properties with a small amount of flame retardant, minimizes deterioration of other textile properties, and has excellent stability ; A method of preparing a flame-retardant textile material, said method comprising the step of applying a flame retardant to the textile material; and a flame-retardant textile material prepared by said method.

technical solution

The inventors of the present invention have studied intensively to achieve the above objects, and found that reducing the particle size of certain phosphorus compounds used as flame retardant components helps to minimize the deterioration of other textile properties without deteriorating flame retardant properties. Under optimized conditions, the amount of flame retardant coated on the textile material can be reduced, and the surfactant added to the flame retardant can improve the stability of the flame retardant, so as to achieve the above-mentioned purpose. Therefore, the present inventors have arrived at the present invention.

The flame retardant of the present invention comprises a phosphorus compound (A), a surfactant (B) represented by the following formula (1), and water, and the surfactant (B) includes an anionic surfactant and/or nonionic surfactants; and the flame retardant of the present invention is used to impart flame retardant properties to textile materials, wherein the phosphorus compound (A) has a median particle size (D ₅₀ ) of 1 micron or less.

[chemical formula 1]

(wherein R ¹ , R ² and R ³ may be the same or different from each other, and represent C _1-24 alkyl, C _2-22 alkenyl, C _5-6 alicyclic, and aromatic group or aralkyl group.)

The flame retardant of the present invention should preferably satisfy at least one of the following conditions 1) to 5).

1) The surfactant (B) contains at least one selected from the group consisting of: polyoxyalkylene alkylaryl ether sulfates, alkylaryl sulfonates, alkylaryl ether disulfonates Alkylaryl oxide disulfonates, aromatic sulfonate-formalin condensates, polyoxyalkylene alkylaryl ethers, polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers and Polyoxyalkylene fatty acid esters.

2) The surfactant (B) contains at least one selected from the group consisting of aromatic sulfonate-formaldehyde condensates, polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers and polyoxyalkylene fatty acid esters.

3) The ratio of the phosphorus compound (A) is in the range of 20 to 70% by weight of the flame retardant as a whole, and the ratio of the surfactant (B) is in the range of 3 to 20% by weight of the flame retardant as a whole, respectively , and the phosphorus compound (A) is dispersed in water by the surfactant (B).

4) The ratio of the phosphorus compound (A) is in the range of 30 to 60% by weight of the flame retardant as a whole, and the ratio of the surfactant (B) is in the range of 5 to 15% by weight of the flame retardant as a whole, respectively , and the phosphorus compound (A) is dispersed in water by the surfactant (B).

5) The textile material contains at least fibers having a relatively high ratio of crystalline domains, and may also contain fibers having a relatively high ratio of non-crystalline domains.

The method for preparing a flame-retardant textile material of the present invention includes a method of applying the above-mentioned flame retardant to the textile material.

The method for preparing a flame-retardant textile material of the present invention should preferably satisfy the following conditions A) and/or B).

A) The textile material includes at least fibers having a relatively high ratio of crystalline domains, and may also include fibers having a relatively high ratio of non-crystalline domains.

B) The above coating is carried out by immersing the textile material in a solution containing a flame retardant at a temperature above 80° C. for 2 to 120 minutes.

The flame-retardant textile material of the present invention is obtained by the above-mentioned preparation method.

beneficial effect

The flame retardants of the present invention are used to impart flame retardant properties to textile materials, and sufficient flame retardant properties are achieved with small amounts of flame retardants. This small amount contributes to the minimization of the deterioration of other textile properties caused by phosphorus compounds in the flame retardant. The application of the flame retardants of the present invention to textile materials is less likely to cause deterioration of the textile materials, their feel and their color fastness, including color fastness to rubbing or light. The flame retardant achieves flame retardant properties durable to washing and dry cleaning, reduces burdens on the environment and the human body, and has excellent stability.

As described above, the method of preparing the flame-retardant textile material of the present invention treats the textile material with a flame retardant, thereby obtaining sufficient flame-retardant properties and minimizing deterioration of other textile properties caused by phosphorus compounds.

Best Mode for Carrying Out the Invention

(flame retardant)

The flame retardants of the present invention are compositions for imparting flame retardant properties to textile materials.

There are no particular limitations on the textile material to be coated with the flame retardant, and preferred are textile materials containing at least fibers having a high ratio of crystalline domains, for example, aromatic polyester, cationic-dyeable polyester, aramid, aramid Polyimide, diacetate, triacetate and copolymers of their monomers, because these textile materials fully absorb triphenylphosphine oxide contained in flame retardants to obtain improved flame retardant properties. Among the materials, a textile material comprising at least an aromatic polyester or a cation-dyeable polyester is more preferred because it absorbs the high performance of the phosphorus compound (A) described below.

Examples of aromatic polyesters and cationic-dyeable polyesters include: polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate ester, polybutylene naphthalate, polyethylene terephthalate/isophthalate, and polyethylene terephthalate/5-(sodium sulfo)isophthalate ester.

Textile materials may contain both fibers having a higher ratio of crystalline regions as described above and fibers having a higher ratio of non-crystalline regions as described above (for example, natural fibers include cotton, linen, wool; and nylon).

The crystalline regions referred to here are, for example, fiber regions formed during physical processing such as drawing during the production of synthetic fibers, in which the polymer chains constituting the fibers are relatively oriented in a regular state, while the non-crystalline regions are the opposite of the former. A region of a fiber in which the polymer chains that make up the fiber are relatively oriented in a random state.

A textile material may contain one fiber variety or several fiber varieties. Textile materials comprising both fibers containing a higher proportion of crystalline regions and fibers containing a higher proportion of amorphous regions can be formed by blending or combined weaving. The form of the textile material is not limited, and yarns, woven fabrics, knitted fabrics, non-woven fabrics, ropes, and codes can be used.

The flame retardant of the present invention comprises a phosphorus compound (A), a surfactant (B) including an anionic surfactant and/or a nonionic surfactant, and water. The components do not contain halogen, thereby minimizing the burden on the environment and the human body.

The phosphorus compound (A) used in the present invention is applied to textile materials to improve their flame-retardant properties. The phosphorus compound (A) has a molecular structure that is less likely to be hydrolyzed, and does not cause the deterioration of the textile material found in the textile material coated with the phosphate ester flame retardant as described in the background art. The phosphorus compound (A) is a solid having a melting point of not lower than 130°C, and this property allows the compound to maintain stable dispersion in a solution for imparting flame-retardant properties at temperatures above 80°C. In addition, the phosphorus compound (A) applied to the textile material does not cause the dye to migrate out of the textile material, thus contributing to excellent color fastness such as color fastness to rubbing.

The molecular weight of the phosphorus compound (A) is not particularly limited, but should preferably be in the range of 250 to 500, more preferably 250 to 400, in order to impart durable flame retardant properties to washing and dry cleaning.

The phosphorus compound (A) is represented by the above chemical formula (1). In the chemical formula (1), at least one of R ¹ , R ² and R ³ should preferably be an aryl group or an aralkyl group in order to sufficiently apply the compound to the textile material. More preferably R ¹ , R ² and R ³ are all aryl or aralkyl. Such phosphorus compounds (A) include, for example, triphenylphosphine oxide, tris(2-methylphenyl)phosphine oxide, tris(4-methylphenyl)phosphine oxide, tris(2,6-dimethyl phenylphosphine, tris(2,6-dimethoxyphenyl)phosphine oxide, tribenzylphosphine oxide and 2-(diphenylphosphinyl)hydroquinone.

The median particle size (D ₅₀ ) of the phosphorus compound (A) should be 1 μm or less, preferably 0.8 μm or less, more preferably 0.2 to 0.6 μm, in order to obtain the above-mentioned excellent long-term stability and more unique effects of the present invention. A phosphorus compound (A) having a median particle diameter (D ₅₀ ) larger than 1 micron is not preferable because such a compound cannot obtain the effect of the present invention and has poor long-term stability.

The median particle diameter (D ₅₀ ) mentioned in the present invention represents the median value of the particle diameters of all particles constituting the entire volume of the phosphorus compound (A).

The ratio of the phosphorus compound (A) contained in the flame retardant of the present invention is not particularly limited, but should preferably be in the range of 20 to 70% by weight, more preferably 30 to 60% by weight of the flame retardant as a whole. A ratio of the phosphorus compound (A) of less than 20% by weight may cause problems in preparation, storage, stability and performance of the flame retardant due to excessive ratios of water and other ingredients. On the other hand, a ratio of the phosphorus compound (A) higher than 70% by weight may not produce a stable flame retardant.

The surfactant (B) includes anionic surfactants and/or nonionic surfactants, and improves the dispersibility of the phosphorus compound (A). Phosphorus compound (A) is generally easy to agglomerate and difficult to be made into fine particles. The surfactant (B) functions to lower the surface tension between the phosphorus compound (A) and water and to moisten the phosphorus compound (A), thereby effectively micronizing the phosphorus compound (A). In addition, the surfactant (B) controls the agglomeration of the fine particles of the phosphorus compound (A) over time, thereby improving the stability of the resulting flame retardant. The surfactant (B) contained in the flame retardant of the present invention allows the phosphorus compound (A) to be finely divided and dispersed in water.

Anionic surfactants are not particularly limited, and may include, for example: alkyl sulfates, alkylaryl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkylaryl ether sulfates (polyoxyalkylene alkylaryl ether sulfates) Oxyalkylene tris(2-phenylethyl)phenyl ether sulfates, polyoxyalkylene bis(2-phenylethyl)phenyl ether sulfates, polyoxyalkylene 2-phenylethylphenyl ether sulfates salts, polyoxyalkylene nonylphenyl ether sulfates, etc.), polyoxyalkylene alkyl polyol ether sulfates, alkyl sulfonates, alkylaryl sulfonates (xylene sulfonate , toluene sulfonate, cumene sulfonate, etc.), alkyl aryl ether disulfonates (alkyl diphenyl ether disulfonates, etc.), alkyl sulfosuccinates, alkyl phosphates Classes, alkyl aryl phosphates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl aryl ether phosphates, polyoxyalkylene alkyl polyol ether phosphates, aromatic sulfonates- Formaldehyde condensate salts (naphthalenesulfonate-formaldehyde condensate salts, etc.), polyoxyalkylene alkyl ether carboxylates, polycarboxylates, Turkish red oil, and lignosulfonate. In case the anionic surfactant is selected from salts, alkali metal salts, alkaline earth metal salts, ammonium salts and organic amine salts are preferred. One kind or at least two kinds of anionic surfactants may be used.

Among the anionic surfactants, polyoxyalkylene alkylaryl ether sulfates, alkylaryl sulfonates, alkylaryl ether disulfonates and aromatic Sulfonate-formaldehyde condensate salts, and in addition to their excellent dispersibility, due to their ability to effectively microparticleize the phosphorus compound (A) in the preparation of flame retardants, more preferably polyoxyalkylene alkylaryl base ether sulfates, alkylaryl sulfonates and aromatic sulfonate-formaldehyde condensate salts. Aromatic sulfonate-formaldehyde condensate salts are still more preferred because they control the agglomeration of fine particles of the phosphorus compound (A) over time, thereby improving the stability of the flame retardant.

Nonionic surfactants are not particularly limited, and include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers (polyoxyalkylene tris(2-phenylethyl)phenyl ether, polyoxyalkylene Bis(2-phenylethyl)phenyl ether, polyoxyalkylene (2-phenylethyl)phenyl ether, polyoxyalkylene nonylphenyl ether, etc.), polyoxyalkylene alkylamines, polyoxyalkylene Alkyl amides, polyoxyalkylene fatty acid esters, polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers and polyoxyalkylene polyol ethers. One or at least two of the nonionic surfactants may be used.

Among the nonionic surfactants, polyoxyalkylene alkylaryl ethers, polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers, and polyoxyalkylene fatty acid esters are preferred because of their excellent dispersibility and improve flame retardant stability due to their excellent dispersibility and their effective microparticles of phosphorus compound (A) and control of agglomeration of phosphorus compound (A) particles over time in the preparation of flame retardants performance, more preferably polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers and polyoxyalkylene fatty acid esters.

The nonionic surfactant contained in the flame retardant of the present invention should preferably have an HLB in the range of 11 to 15 determined by Griffin's method as a whole, and form a clouding point of not lower than 10°C 1% aqueous solution, because this nonionic surfactant has excellent performance of dispersing the phosphorus compound (A).

The ratio of the surfactant (B) in the flame retardant of the present invention is not particularly limited, and should preferably be in the range of 3 to 20% by weight, more preferably 5 to 15% by weight of the flame retardant. A ratio of the surfactant (B) of less than 3% by weight may fail to formulate a stable flame retardant. On the other hand, a ratio higher than 20% by weight may deteriorate the color fastness of the flame retardant-coated textile material or accelerate the dye-inhibiting effect when the flame retardant is added to a dye bath.

The formulation of the flame retardant of the present invention is not particularly limited as long as it contains phosphorus compound (A), surfactant (B) and water. The flame retardant may contain other components that do not adversely affect the effect of the present invention.

Components other than those described above include, for example: solvents (methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, butanediol, benzyl alcohol, 3-methoxy-3-methyl-1-butanol alcohol, butyl carbitol, polyalkylene glycol, etc.), water-soluble polymers (polyvinyl alcohol, polyacrylate, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl Cellulose, xanthan gum, gum arabic, gelatin, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, polystyrene sulfonate, polystyrene-maleic acid copolymer, methoxyethylene-maleic acid anhydride copolymers, soluble starches, cationized starches, carboxymethyl starches, etc.); carriers (aromatic halides, N-alkylphthalimides, aromatic carbonates, methyl Naphthalene, biphenyl, diphenyl ester, naphthol ester, phenol ether, hydroxybiphenyl, etc.); other flame retardants (phosphoric acid esters, including triphenyl phosphate, trihydroxycresyl phosphate, trixylyl phosphate, phosphoric acid Cresyl phenyl, xylyl phenyl phosphate, hydroxy cresyl xylyl phosphate, phenyl o-biphenyl phosphate and naphthyl phosphate, condensed phosphates including resorcinol bis(diphenyl phosphate) , bisphenol A bis(diphenyl phosphate) and resorcinol bis(xylyl phosphate), phosphite, hypophosphite, phosphine oxide, phosphate amidoester, chlorine-containing phosphates, chlorine-containing condensation Phosphate esters, phosphorus-containing polyester resins, phospharazine, brominated flame retardants including hexabromocyclododecane, decabromodiphenyl ether, ethylene bis(pentabromobiphenyl), ethylene bis( Tetrabromophthalimide) and tris(tribromophenoxy)triazine); and UV absorbers, including benzotriazole UV absorbers (2-(2'-hydroxy-3'-tert-butyl -5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole), benzophenone UV absorber (2 -Hydroxy-4-methoxybenzophenone and 2,2'4,4'-tetrahydroxybenzophenone), triazine UV absorber (2-(4,6-diphenyl-1,3 , 5-triazin-2-yl)-5-(hexyloxy)-phenol and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxyl-4-octyloxy phenyl)-1,3,5-triazine), benzoxazinone UV absorber (2,2'-(p-phenylene)di-3,1-benzoxazin-4-one), Cyanoacrylate UV absorbers (ethyl-2-cyano-3,3-diphenylacrylate and (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate) and Salicylate UV absorber (p-tert-butylphenyl salicylate).

The ratio of the above components is not particularly limited. A small ratio of solvent reduces the viscosity of the flame retardant to improve work efficiency, stability at low temperature, dispersibility and emulsifiability. However, a larger ratio of solvent may cause problems in preparing and storing the flame retardant, and the ratio should preferably be below 20% by weight of the flame retardant.

The flame retardant of the present invention is prepared by mixing the phosphorus compound (A), the surfactant (B) and water, and the method and order for mixing the components are not particularly limited. The method for producing the flame retardant of the present invention includes, for example, a method in which the phosphorus compound (A) having a median diameter (D ₅₀ ) of not more than 1 µm is prepared in advance, and is mixed with the surfactant (B) and water mixing (Method 1); and a method wherein the phosphorus compound (C) is mixed with the surfactant (B) and water, the phosphorus compound (C) except that the median particle size (D ₅₀ ) is greater than 1 micrometer , having the same properties as those of the phosphorus compound (A), and then dispersing the phosphorus compound (C) into fine particles using a micronization device (method 2). In Method 2, the phosphorus compound (A) may be used instead of the phosphorus compound (C) so that the median particle diameter (D ₅₀ ) of the phosphorus compound is smaller.

In method 2, micronization equipment includes a grain mill, a sand mill, and an attritor (grinder). In addition, some additives such as non-drying agent, antifoaming agent and viscosity improving agent may be optionally added in method 2. Commercially available phosphorus compounds can be used as the phosphorus compound (C), and they can be coarsely finely divided before mixing.

The above method 1 or method 2 can be used as a method for preparing the flame retardant of the present invention, and method 2 is preferable because in method 1, the agglomerated fine particles of the phosphorus compound (A) having a particle diameter of 1 micron or less may not be separated, and may This leads to unstable dispersion in the resulting flame retardant.

The flame retardants of the present invention are used to impart flame retardant properties to textile materials. The form of the flame retardant used is not particularly limited, and it is usually diluted in water and applied.

[flame-retardant textile material and its preparation method]

The method of producing the flame-retardant textile material of the present invention includes a step of applying the above-mentioned flame retardant to the textile material (finishing step).

In the finishing step, the flame retardant and the textile material are brought into contact with each other to apply the phosphorus compound (A) in the flame retardant to the textile material. The finishing step includes, for example, a step (step 1) in which the textile material is immersed in a bath containing a flame retardant at a temperature above 80° C. for 2 to 120 minutes; and another method in which the flame retardant is applied to On the textile material, the textile material is then heated at 100 to 220° C. to infiltrate the phosphorus compound (A) into the textile material (step 2).

In step 1, the phosphorus compound (A) is generally applied to the textile material by immersing the textile material in a bath prepared by diluting the flame retardant with water, thereby applying the phosphorus compound (A) to the textile material and heat the textile material dipped in a bath at a temperature above 80° C. for 2 to 120 minutes to make the flame retardant properties durable. The dilution ratio of the flame retardant is not particularly limited, but is usually 10 to 10000 times water. The treatment temperature of the textile material in the bath should preferably be 80°C or higher, more preferably 90°C to 150°C, because the non-crystalline regions of the textile material relax or expand, thereby accelerating the application of the phosphorus compound (A) to the textile material. Step 1 can be performed using a device such as a jet dyeing machine, a beam dyeing machine, and a cheese dyeing machine.

In step 2, the phosphorus compound (A) is applied to the textile material by dipping the textile material in a bath prepared by diluting the flame retardant with water, and the textile material, which is sometimes dried after dipping, is heated to The phosphorus compound (A) is made to penetrate into the textile material, thereby making the flame-retardant properties durable. The heating temperature should preferably be in the range of 100 to 220°C, more preferably 160 to 200°C, because the non-crystalline regions of the textile material relax or expand, thereby accelerating the application of the phosphorus compound (A) to the textile material. A heating temperature lower than 100° C. is not preferred because such a low temperature cannot obtain sufficient penetration of the phosphorus compound (A) into the textile material, thus sometimes imparting poor durability of flame-retardant properties. On the other hand, a heating temperature higher than 220° C. is not preferred because excessive heat may deteriorate the textile material, thereby reducing the toughness of the textile material. Flame retardants can be applied to textile materials using dip dyeing, spraying or coating. Heating can be done by dry heat or moist heat. Such coating and heating methods include spray and dry cure systems, dip and dry steam systems, dip and steam systems, and dip and dry cure systems.

The preparation method of the flame-retardant textile material of the present invention may comprise at least one of the above-mentioned step 1 and step 2. Repeating the same steps or combining steps 1 and 2 can give textile materials better flame retardant properties. In addition, the method for preparing the flame-retardant textile material of the present invention may further include another finishing step using a flame retardant different from the flame retardant of the present invention.

In the preparation method of the flame-retardant textile material of the present invention, fiber finishing agents and fiber finishing assistants other than the flame retardant of the present invention can be used for finishing the textile material. Other fiber finishing agents and fiber finishing auxiliaries include, for example, flame retardants other than the phosphorus compound (A), dyes (basic dyes and disperse dyes), carriers (aromatic halides, N-alkylbenzene Phthalimide, aromatic carbonate, methylnaphthalene, biphenyl, biphenyl ester, naphthol ester, phenol ether, hydroxybiphenyl, etc.), deodorant, antibacterial agent, softener, antistatic agent, Water repellant, oil repellant, hardener, UV absorber, antifouling agent and hydrophilic agent. One or at least two of the agents may be used.

In the method for producing a flame-retardant textile material of the present invention, the flame retardant on the textile material, i.e., the amount (pickup) of the phosphorus compound (A) is not particularly limited because it varies depending on the following conditions, such as, Variations and structures of textile materials and variations and acquisitions of other fiber finishes applied to textile materials. The preferred pick-up should be in the range of 0.1 to 30% by weight, more preferably 1 to 20% by weight of the textile material. A take-up amount of the phosphorus compound (A) of less than 1% by weight may not be able to impart sufficient flame-retardant properties to the textile material. On the other hand, an pick-up of more than 30% by weight may degrade the hand of the resulting flame-retardant textile material and may also be uneconomical, since beyond a certain pick-up the flame retardant does not further improve the flame-retardant effect.

Example

The present invention is specifically explained with the following Examples and Comparative Examples, although the present invention is not limited within the scope of the Examples.

[Test Methods]

(1) Median particle diameter (D ₅₀ ) and average volume diameter

The flame retardant prepared by micronization was sampled and analyzed using a laser diffraction and scattering particle size analyzer LA-910 (manufactured by Horiba Co., Ltd.) to determine a median particle diameter (D ₅₀ ) and an average volume diameter.

(2) Product stability

The appearance of the flame retardant stored at 40°C for 1 month was visually inspected. A flame retardant showing no precipitation or separation was evaluated as "good", and a flame retardant showing precipitation or separation was evaluated as "poor".

(3) Flame retardant properties

Woven fabrics are finished with flame retardants in a flame retardant finish. The flame retardant properties of the finished fabric and two fabric samples were tested according to JIS L-1091 A-1 (microburner method) and JIS L 1091 D (coil method), which One of the two fabric samples was prepared by washing the finished fabric 5 times with water, and the other of the two fabric samples was prepared by dry cleaning the finished fabric 5 times in the following method.

In the "micro-lamp method", the fabric is heated in two ways: heating with a micro-lamp for 1 minute, and heating with a micro-lamp for 3 seconds after the fabric is burned. In both cases, fabrics on which the flame was maintained for no longer than 3 seconds after heating, the afterglow was maintained for no longer than 5 seconds after heating, and A carbonized area of not more than 30 cm ² was produced, while fabrics exhibiting flammability exceeding the limit were evaluated as "poor". In the "coil method", fabrics that burn to a predetermined distance when exposed to flames more than 3 times are evaluated as "good", and fabrics that are burned to a predetermined distance when exposed to flames less than 2 times are evaluated as "poor".

wash in water

Fabrics are washed according to JIS K 3371, wherein the fabrics are first placed in a detergent solution containing 1 g/liter of weakly alkaline (group 1) detergent at a fabric to detergent solution ratio of 1:40 at a temperature of 60 ± Wash at 2°C for 15 minutes, then rinse in water at 40±2°C for 5 minutes three times, dehydrate with a centrifugal dehydrator for 2 minutes, and dry in hot air at 60±5°C. The washing process was carried out 5 times in total.

dry cleaning

Use 12.6 milliliters of tetrachloroethane and 0.265 g of charged soap (charge soap) (containing 10:10:1 weight ratio of nonionic surfactant, anionic surfactant) to 1 gram of woven fabric coated with flame retardant and water) at 30±2°C for 15 minutes. Treatments were performed 5 times in total.

(4) Color fastness to friction

A flame retardant finished dyed polyester woven fabric was prepared by adding the flame retardant to a dye bath, and tested with a rub tester II according to JIS L 0849. The results are evaluated by rating, with higher rating numbers indicating better colorfastness to rubbing.

(5) Color fastness to light

According to the method defined in JIS L 0842, the dyed polyester fabric prepared in the above method was exposed to a carbon arc lamp for 100 hours, and evaluated by rating. Higher rating numbers indicate better colorfastness to light.

[Example 1 to 4]

The components of each formulation shown in Table 1 were placed in a blender and stirred to fully disperse. The resulting slurry was then processed into fine particles with a particle mill ZRS (manufactured by Ashizawa Finetech Co., Ltd.) for 4 hours to prepare a flame retardant. Sodium POE(20) tris(2-phenylethyl)phenyl ether sulfate described in Table 1 is polyoxyethylene tris(2-phenylethyl)phenyl ether sodium sulfate containing 20 oxyethylene repeating units .

The median particle diameter and average volume diameter of the obtained flame retardants were determined, and the stability of the flame retardants was visually inspected. The textile material is then finished in a flame retardant finish with the resulting flame retardant and the following parameters (including dyeing and soaping) and the flame retardant properties of the resulting flame retardant textile material, resistance to friction Excellent color fastness and color fastness to light.

[flame-retardant finishing]

Using a small dyeing machine (manufactured by Texam Co., Ltd.), undyed polyester 100% thin fabric was treated in a dye bath at 130° C. for 30 minutes at a fabric-to-bath ratio of 1:15 and a bath pH of 4.5, The dye bath contained 6 fiber weight % of Kayalon Polyester Black AL 167 (a disperse dye produced by Nippon Kayaku Co., Ltd.) and each of the flame retardants described in Table 1 (in their %owf in Table 1). kind. Then in the soaping, the fabric was soaked in a solution containing 1 g/liter of soaping agent (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.), 2 g/liter of bisulfite and 2 g/liter of caustic soda at a ratio of 1:15. The ratio of the fabric to the solution was treated at 80°C for 20 minutes, rinsed in water, and dried at 170°C for 1 minute to prepare a flame-retardant polyester fabric.

Table 1

Comparative Examples 1 to 6

A flame retardant was prepared in the same manner as in Examples 1 to 4 except that the components described in Table 2 were used. Each of the obtained comparative flame retardants was then used for flame retardant finishing (including dyeing and soaping) in the same manner as in Examples 1 to 4. The flame retardancy properties, color fastness to rubbing and color fastness to light of the obtained textile materials were determined.

Table 2

The flame retardants of Examples 1 to 4 resulted in textile materials after flame retardant finishing, textile materials washed 5 times in water after flame retardant finishing, and textile materials dry cleaned 5 times after flame retardant finishing. The material has highly durable flame retardant properties; excellent color fastness to rubbing of the finished textile material; and excellent stability. On the contrary, the flame retardants of Comparative Examples 1 to 6 had poor stability and separated. Although, as in the case of Comparative Example 3, the flame-retardant property imparted by the flame retardant of Comparative Example was improved to a degree similar to the improvement of Examples 1 to 4 by increasing the amount of the flame retardant taken in, the flame retardant properties of Comparative Example 3 Burning agents lead to poor color fastness to rubbing and poor color fastness to light of wet textiles. The flame retardants of Comparative Examples 4 and 5 resulted in poor flame retardancy properties and color fastness to rubbing. The flame retardant of Comparative Example 6 resulted in poor color fastness to light.

Industrial applicability

The flame retardants of the invention are suitable for imparting flame retardant properties to textile materials. The flame retardants of the present invention applied to textile materials are least prone to degrade the textile material, its feel and its color fastness, including fastness to rubbing and to light. The flame retardant can obtain flame retardant properties durable to washing and dry cleaning with minimal burden on the environment and human body, and has excellent stability.

Claims (as amended under Article 19 of the Treaty)

Amendment statement pursuant to Article 19 of the PCT Treaty

Claim 1 is amended as follows: said surfactant (B) includes an anionic surfactant as a main component, and said anionic surfactant contains at least one selected from the group consisting of polyoxygen Alkenyl aryl ether sulfates, alkyl aryl ether disulfonates, and aromatic sulfonate-formaldehyde condensate salts. Therefore, it was shown that the flame retardant contains the specific phosphorus compound (A) and the specific anionic surfactant. Said anionic surfactant and said nonionic surfactant are further defined in claims 2 and 3.

Existing Document 1 neither discloses nor suggests these anionic surfactants. On the other hand, existing documents 2 and 3 do not disclose flame retardants. Furthermore, the function of the surfactant used is completely different from the function of the surfactant used in the present invention to further exhibit flame retardant properties. Therefore, existing documents 1 to 3 neither disclose nor suggest the use of these specific anionic surfactants together with a specific phosphorus compound (A) represented by chemical formula (1) and having a melting point of not lower than 130° C., and existing documents No revelation was given.

1. (Modification) A flame retardant for imparting flame retardant properties to textile materials, said flame retardant comprising:

a phosphorus compound (A) represented by the chemical formula (1) shown below and having a melting point of not lower than 130°C;

Surfactants (B) comprising anionic surfactants; or anionic surfactants and nonionic surfactants; and

water;

wherein the phosphorus compound has a median particle diameter (D ₅₀ ) of not greater than 1 micrometer; and wherein the anionic surfactant is at least one selected from the group consisting of polyoxyalkylene alkylaryl ether Sulfates, alkylaryl ether disulfonates, and aromatic sulfonate-formaldehyde condensate salts.

(where R ¹ , R ² and R ³ may be the same or different from each other, and represent C _1-24 alkyl, C _2-22 alkenyl, C _5-6 alicyclic, and aryl that may have substituents or aralkyl.)

2. (Modification) The flame retardant according to claim 1, wherein the anionic surfactant contains the aromatic sulfonate-formaldehyde condensate salt as a main component.

3. (Modification) The flame retardant according to claim 1 or 2, wherein the nonionic surfactant contains at least one selected from the group consisting of polyoxyalkylene alkylaryl ethers , polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers and polyoxyalkylene fatty acid ethers.

4. The flame retardant according to any one of claims 1, 2 and 3, wherein the ratio of the phosphorus compound (A) and the surfactant (B) is respectively at 20% of the whole of the flame retardant to 70% by weight and 3 to 20% by weight, and the phosphorus compound (A) is dispersed in water by the surfactant (B).

5. The flame retardant according to any one of claims 1, 2, 3 and 4, wherein the ratio of the phosphorus compound (A) and the surfactant (B) is respectively in the overall ratio of the flame retardant 30 to 60% by weight and 5 to 15% by weight, and the phosphorus compound (A) is dispersed in water by the surfactant (B).

6. The flame retardant according to any one of claims 1, 2, 3, 4 and 5, wherein said textile material comprises at least one fiber having a higher ratio of crystalline domains, and may further comprise another Fibers with a higher ratio of amorphous domains.

7. A method of preparing a flame retardant textile material, said method comprising the step of finishing the textile material with a flame retardant according to any one of claims 1, 2, 3, 4, 5 and 6.

8. The method for preparing a flame-retardant textile material according to claim 7, wherein said textile material comprises at least one fiber having a higher ratio of crystalline domains, and may further comprise another fiber having a higher ratio of non-crystalline domains of fiber.

9. The method for preparing a flame retardant textile material according to claim 7 or 8, wherein said finishing step is performed by immersing said textile material in a bath containing said flame retardant at a temperature above 80°C 2 to 120 minutes.

10. A flame-retardant textile material prepared by the method according to any one of claims 7, 8 and 9.

Claims (10)

1. A flame retardant, said flame retardant is used to give a textile material a flame retardant property, said flame retardant comprising: a phosphorus compound (A) represented by the chemical formula (1) shown below and having a melting point of not lower than 130°C; Surfactants comprising anionic surfactants and/or nonionic surfactants; and water; wherein the phosphorus compound has a median particle size ( _D50 ) of no greater than 1 micron.

(where R ¹ , R ² and R ³ may be the same or different from each other, and represent C _1-24 alkyl, C _2-22 alkenyl, C _5-6 alicyclic, and aryl that may have substituents or aralkyl.) 2. The flame retardant according to claim 1, wherein the surfactant (B) contains at least one selected from the group consisting of: polyoxyalkylene alkyl aryl ether sulfates, alkanes Alkylaryl sulfonates, alkylaryl ether disulfonates, aromatic sulfonate-formaldehyde condensate salts, polyoxyalkylene alkylaryl ethers, polyoxyalkylene castor oil ethers, polyoxyalkylene Hydrogenated castor oil ethers and polyoxyalkylene fatty acid ethers. 3. The flame retardant according to claim 1 or 2, wherein the surfactant (B) contains at least one selected from the group consisting of: aromatic sulfonate-formaldehyde condensate salts , polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers and polyoxyalkylene fatty acid ethers. 4. The flame retardant according to any one of claims 1, 2 and 3, wherein the ratio of the phosphorus compound (A) and the surfactant (B) is respectively at 20% of the whole of the flame retardant to 70% by weight and 3 to 20% by weight, and the phosphorus compound (A) is dispersed in water by the surfactant (B). 5. The flame retardant according to any one of claims 1, 2, 3 and 4, wherein the ratio of the phosphorus compound (A) and the surfactant (B) is respectively in the overall ratio of the flame retardant 30 to 60% by weight and 5 to 15% by weight, and the phosphorus compound (A) is dispersed in water by the surfactant (B). 6. The flame retardant according to any one of claims 1, 2, 3, 4 and 5, wherein said textile material comprises at least one fiber having a higher ratio of crystalline domains, and may further comprise another Fibers with a higher ratio of amorphous domains. 7. A method of preparing a flame retardant textile material, said method comprising the step of finishing the textile material with a flame retardant according to any one of claims 1, 2, 3, 4, 5 and 6. 8. The method for preparing a flame-retardant textile material according to claim 7, wherein said textile material comprises at least one fiber having a higher ratio of crystalline domains, and may further comprise another fiber having a higher ratio of non-crystalline domains of fiber. 9. The method for preparing a flame retardant textile material according to claim 7 or 8, wherein said finishing step is performed by immersing said textile material in a bath containing said flame retardant at a temperature above 80°C 2 to 120 minutes. 10. A flame-retardant textile material prepared by the method according to any one of claims 7, 8 and 9.