JP4668728B2 - Flame retardant polyester fiber structure - Google Patents

Description

  The present invention relates to a polyester synthetic fiber structure excellent in flame retardancy and durability.

  Conventionally, various methods for imparting flame retardancy to polyester fiber structures, particularly fabrics, by post-processing are known.

  For example, as a flame retardant, a halogen compound, typically, for example, brominated cycloalkane such as 1,2,5,6,9,10-hexabromocyclododecane is used as a flame retardant in water with a dispersant. A method is known in which a flame retardant processing agent dispersed is adhered to a polyester fiber fabric (see, for example, Patent Document 1).

  However, according to the method for imparting flame retardancy by attaching a halogen compound to the polyester fiber structure, harmful halogenated gas is generated when the polyester fiber structure burns, There are problems such as harmful effects on

  Thus, in the past, in place of such a halogen-based compound, a phosphoric ester not containing a halogen has been used as a flame retardant to impart flame retardancy to a polyester-based fiber structure.

  For example, a method is known in which a flame retardant processing agent obtained by emulsifying and dispersing a liquid phosphate ester such as resorcinol bis (diphenyl phosphate) in water with a surfactant is attached to a polyester-based synthetic fiber fabric (for example, Patent Documents 2 and 3).

  However, such phosphate ester, which is conventionally known as a flame retardant, can impart flame retardant performance excellent in washing resistance to a polyester fiber structure, but its flame retardant is dry resistant. Not cleanable.

  Furthermore, in order to obtain the desired flame retardant performance by using such phosphate ester as a flame retardant and attaching it to the polyester fiber structure, a large amount of flame retardant is attached to the polyester fiber structure. It is necessary to make it. If a large amount of flame retardant is attached to the polyester fiber structure in this way, these flame retardants gradually move to the surface of the polyester fiber structure with the passage of time, and in that case, the polyester fiber structure Disperse dyes and the like used for dyeing materials also move to the surface together in a state dissolved in a phosphoric acid ester which is a flame retardant, and so-called bleed out occurs.

As described above, the dye transferred to the surface of the polyester-based synthetic fiber structure has problems such as contaminating other products and significantly reducing the dyeing fastness of the polyester-based fiber structure itself.
Japanese Patent Publication No.53-8840 JP 2000-328445 A JP 2000-154465 A

  As a result of earnest research to solve the above-described problems in the flame-retardant processing of conventional polyester fiber structures, the present inventors have arrived at the present invention. The object is to provide a novel polyester fiber structure having excellent durability.

  According to the present invention, the fibers constituting the polyester-based synthetic fiber structure are added to the phosphoric acid amide represented by the following general formula 1, the phosphoric acid ester-based difficulty represented by the following general formula 2, the general formula 3 and the general formula 4. And at least one compound selected from the group consisting of flammable compounds.

  According to the present invention, a polyester fiber structure excellent in flame retardancy and durability can be stably supplied.

  The fiber structure having the function of the present invention can be effectively used for general clothing use, bedding use, industrial use and the like.

  In the present invention, the polyester fiber structure refers to a fiber containing at least a polyester fiber and a yarn, string, cotton, knitted fabric or nonwoven fabric containing such a fiber, preferably a polyester fiber, This refers to fabrics such as yarn, string, cotton, knitted fabric and non-woven fabric.

  Examples of the polyester fibers used in the present invention include polyester fibers containing an aromatic component and aliphatic polyester fibers. Examples of the polyester containing an aromatic component include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, or those and a third component such as isophthalic acid, isophthalic acid sulfonate, adipic acid, and polyethylene glycol. be able to. Examples of the aliphatic polyester include poly L lactic acid, poly D lactic acid and a homopolymer composed of D and L lactic acid, or a polylactic acid-glycolic acid copolymer.

  The polyester fiber used in the present invention may contain various commonly used additives in order to improve productivity and characteristics in the production process and processing process of the raw yarn. For example, additives such as heat stabilizers, antioxidants, light stabilizers, UV absorbers, antistatic agents, colorants, smoothing agents, plasticizers, antibacterial agents, fungicides, and deodorants are added to polyester fibers. It can be included.

  In the present invention, these polyester fibers can be used alone or in admixture of two or more, and short fibers, long fibers or these may be mixed.

  The flame-retardant polyester fiber structure according to the present invention is suitably used for, for example, general clothing, seat sheets, sheets, covers, curtains, wallpaper, ceiling cloths, carpets, notebooks, architectural curing sheets, tents, canvases, and the like. .

  The flame-retardant polyester fiber structure according to the present invention includes a phosphoramide represented by the following general formula 1, the following general formula 2, the general formula 3 and the general formula as a flame retardant for the fibers constituting the polyester-based fiber structure. And at least one compound selected from the group consisting of phosphoric acid ester-based flame retardant compounds represented by 4.

  Specific examples of the compound represented by the general formula 1 include aminodiphenyl phosphate, methylaminodiphenyl phosphate, dimethylaminodiphenyl phosphate, ethylaminodiphenyl phosphate, diethylaminodiphenyl phosphate, propylaminodiphenyl phosphate, dipropylaminodiphenyl phosphate, Octylaminodiphenyl phosphate, diphenylundecylaminophosphate, cyclohexylaminodiphenyl phosphate, dicyclohexylaminodiphenyl phosphate, allylaminodiphenyl phosphate, anilinodiphenyl phosphate, di-o-cresylphenylamino phosphate, diphenyl (methylphenylamino) phosphate, diphenyl (Ethylphenyl Mino) phosphate, benzylamino diphenyl phosphate, can be mentioned morpholino diphenyl phosphate and the like.

  Such a phosphoric acid amide can be obtained by reacting a diaryl phosphorochloridate with an organic amine compound in an organic solvent in the presence of an amine catalyst, as described in JP-A No. 2000-154277. it can. In particular, according to the present invention, in the phosphoric amide represented by the above general formula 1, Ar1 and Ar2 are preferably phenyl or tolyl groups, one of R1 and R2 is a hydrogen atom, and the other is phenyl or cyclohexyl group It is what is. Examples of such phosphoric amides include anilinodiphenyl phosphate, di-o-cresylphenylamino phosphate, and cyclohexylaminodiphenyl phosphate.

  Specific examples of the compound represented by the general formula 2 include tetra (2,6-dimethylphenyl) -m-phenylene phosphate, tetra (2,6-dimethylphenyl) -p-phenylene phosphate, bisphenol A bis [ Di (2,6-dimethylphenyl)] phosphate, bisphenol S bis [di (2,6-dimethylphenyl)] phosphate, biphenylbis [di (2,6-dimethylphenyl)] phosphate, diphenyl ether bis [di (2, 6-dimethylphenyl)] phosphate and the like. Among these, in particular, tetra (2,6-dimethylphenyl) -m-phenylene phosphate, tetra (2,6-dimethylphenyl) -p-phenylene phosphate or bisphenol A bis [di (2,6-dimethylphenyl) Phosphate is preferably used. Such aromatic diphosphate is described in, for example, JP-A-63-227632, and can be obtained as a commercial product.

  Specific examples of the compound represented by the above general formula 3 include, for example, tetraphenyl-m-phenylene phosphate, tetraphenyl-p-phenylene phosphate, bisphenol A bis (diphenyl phosphate), bisphenol S bis (diphenyl phosphate), tetracresyl- m-phenylene phosphate, tetracresyl-p-phenylene phosphate, bisphenol A bis (dicresyl phosphate), bisphenol S bis (dicresyl phosphate), tetraxylenyl-m-phenylene phosphate, tetraxylenyl-p-phenylene phosphate, bisphenol A bis (dixylenyl) Phosphate, bisphenol S bis (dixylenyl) phosphate, phenyl resorcin polyphosphate, bisphenol Compounds such as orthophosphoric acid ester and the oligomer and A polyphenyl phosphate. Such an aromatic diphosphate is a crystalline powder and is described in, for example, JP-A-5-1079, and can be obtained as a commercial product.

Specific examples of the compound represented by the general formula 4 include t-butylphenyl diphenyl phosphate, phenyl [di (t-butylphenyl)] phosphate, tris (t-butylphenyl) phosphate, and mixtures thereof. It is done. It can obtain as a commercial item It is preferable that the compounding ratio of the said phosphoric acid amide in the present invention and the said phosphate ester type flame retardant compound is 1: 0.25 to 1: 1 by weight ratio, More preferably 1: 0.25 to 1: 0.75. If the blending ratio is more than this, sufficient flame retardancy cannot be obtained.

  In the flame-retardant polyester fiber structure of the present invention, the total content of phosphoric acid amide and phosphate ester-based flame retardant compound does not include a flame retardant, that is, 0. 0% with respect to the fiber weight before processing. It is 5% by weight or more, preferably 2% by weight or more, and more preferably 3 to 20% by weight.

  The flame retardant compound in the present invention is preferably used as a dispersion or an emulsion.

  The flame retardant compound is usually used by being dispersed in water or an organic solvent. The dispersion method is a normal method, for example, the flame retardant compound and a surfactant such as a nonionic surfactant or an anionic surfactant are mixed and dissolved uniformly, and gradually added with hot water to emulsify and disperse. Is used.

  Nonionic surfactants include polyoxyalkylene type nonionic surfactants (higher alcohol alkylene oxide adducts, alkylene phenol alkylene oxide adducts, aliphatic alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, higher Alkylamine alkylene oxide adducts, aliphatic amide alkylene oxide adducts, etc.), polyhydric alcohol type nonionic surfactants (alkyl glycosides, sucrose fatty acid esters, etc.).

  Anionic surfactants include sulfate esters (higher alcohol sulfates, higher alkyl ether sulfates, sulfated fatty acid esters, etc.), sulfonates (alkylenebenzene sulfonates, alkylnaphthalene sulfonates, etc.), phosphorus Acid ester salts (higher alcohol phosphate salts, alkylene oxide adduct phosphate esters of higher alcohols, etc.).

  Examples of organic solvents include aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane ethyl cellosolve, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and the like. The mixture of 2 or more types of these is mentioned.

  As a method for incorporating the phosphoric acid amide and the flame retardant compound into the polyester fiber structure, for example, the fiber structure is immersed in an aqueous dispersion of the phosphoric acid amide and the flame retardant compound. After being squeezed with mangle or the like so as to have a content, it is dried at 110 to 130 ° C. and heat treated in a range of 170 to 210 ° C., preferably 180 to 200 ° C., or immersed in an aqueous dispersion. Although well-known methods, such as the method of heating to -130 degreeC and making a flame-retardant compound adsorb | suck to the fiber surface or exhausting inside a fiber, can be employ | adopted, It is not limited to these.

  In the present invention, a treatment liquid such as a dispersion or an emulsion is difficult to use as a protective colloid agent such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, starch paste, or the like in order to increase the storage stability as necessary. It may contain a flame retardant aid for enhancing flammability, an ultraviolet absorber for enhancing light fastness, an antioxidant, and the like. Furthermore, other flame retardants conventionally known may be included as necessary.

  In the present invention, the treatment liquid can be used in combination with other conventionally known fiber finishing agents. Examples of such fiber finishing agents include softeners, antistatic agents, water and oil repellents, hard finishes, and texture modifiers.

  The polyester fiber structure of the present invention has excellent flame retardancy, and is excellent in durability of the flame retardancy, particularly dry cleaning resistance. Therefore, bedding, curtains, roll curtains, sheets including clothing. , Sheet covers, notebooks, wall cloths, ceiling cloths, carpets, tents, and curing sheets. In particular, it is optimal for applications where frequent washing and cleaning are performed.

  Examples The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The sample polyester fiber fabrics used in the examples are as follows, and their flame retardancy and durability were evaluated as follows.
(1) Flame Retardant Performance JIS L 1091 A-1 method (micro burner method) and JIS L 1091D for fabrics subjected to flame retardancy and those washed 5 times with water or 5 times dry-cleaned (DC) under the following conditions: Flame retardancy was evaluated by the method (coil method). In the micro-burner method, if the after flame is within 3 seconds, the residual dust is within 5 seconds, and the carbonization area is within 30 cm ^{2 for} both 1 minute heating and 3 second heating after flame, the coil method is passed. In, when the number of flame contact is 3 times or more, it is a category 2 pass.

(Water washing)
According to JIS K 3371, a weak alkaline first-class detergent is used at a rate of 1 g / L, and a bath ratio of 1:40 is washed with water at 60 ° C. ± 2 ° C. for 15 minutes, and then rinsed at 40 ° C. ± 2 ° C. for 5 minutes. Was performed 3 times, centrifugal dehydration was performed for 2 minutes, and then 5 cycles of 1 cycle of drying with hot air at 60 ° C. ± 5 ° C. were performed.
(DC)
1 g of sample, 12.6 mL of tetrachloroethylene, 0.265 g of charge soap (weight composition of charge soap is nonionic surfactant (10 mol adduct of nonylphenyl ether with ethylene oxide) / anionic surfactant (dioctyl succinate sodium salt) ) / Water = 10/10/1), the treatment at 30 ° C. ± 2 ° C. for 15 minutes was defined as one cycle, and this was performed for 5 cycles.
(2) Fastness to dyeing In accordance with JIS L 0846, a flame-retardant processed fabric was tested by the dyeing fastness test method B, and measured with a gray scale for contamination. A Gakushin type was used as the friction tester.
(Sample polyester fiber fabric)
Using 90 decitex 48 filaments sulfonated aromatic dicarboxylic acid modified polyethylene terephthalate as the warp yarn, 150 decitex 48 filament polyester fiber as the weft and scouring and presetting the plain woven fabric by the usual method The applied one was used as a sample polyester fiber fabric.
(Flame retardant compounds)
Compound A: An aqueous dispersion containing a compound represented by formula 5 (anilinodiphenyl phosphate) at a concentration of 40% by weight was used.

  Compound B: An aqueous dispersion containing a compound of formula 6 (tetraphenyl-m-phenylene phosphate) at a concentration of 40% by weight was used.

  Compound C: An aqueous dispersion containing a compound of formula 7 (tetraxylenyl-m-phenylene phosphate) at a concentration of 40% by weight was used.

  Compound D: An aqueous dispersion containing a compound of formula 8 (t-butylphenyl diphenyl phosphate) at a concentration of 40% by weight was used.

(Processing method)
Under the conditions shown below, using a liquid dyeing machine, treatment is performed at 130 ° C. for 45 minutes at a bath ratio of 1:20, followed by normal reduction washing, water washing, drying, and 170 ° C. for 1 minute. Heat treatment was performed.

  As the flame retardant, the compounds A, B, C and D were added.

  The dye used was a disperse dye (Sumicaron Blue E-RPD) at a concentration of 0.3% owf.

  In addition, about the measuring method of content of a flame retardant, it calculated using the following formula based on the fiber weight before and after a flame retardant process.

Content(%)
= {(Fiber weight after processing−fiber weight before processing) / (fiber weight before processing)} × 100
According to Example 1 to Example 6, good flame retardancy and durability can be imparted by any one combination of phosphoric acid amide and a flame retardant compound.

  According to Comparative Example 1 to Comparative Example 4, any of the flame retardant compounds of Comparative Example 1 to Comparative Example 4 failed in flame retardancy alone.

Claims (3)

The fiber constituting the polyester fiber structure comprises at least one compound selected from the group consisting of a phosphoric acid amide of formula 1 and a phosphate ester flame retardant compound of formulas 2, 3 and 4. A flame-retardant polyester fiber structure characterized by containing.

  The mixing ratio of the phosphoric acid amide and the phosphoric acid ester-based flame retardant compound is 1: 0.25 to 1: 1 by weight, and the phosphoric acid amide and the phosphoric acid ester-based flame retardant compound The flame retardant polyester fiber structure according to claim 1, wherein the total content is 0.5% by weight or more based on the polyester fiber structure.   The use of the flame retardant polyester fiber structure is any one selected from clothing, bedding, curtains, roll curtains, sheets, seat covers, notebooks, wall cloths, ceiling cloths, carpets, tents, and curing sheets The flame-retardant polyester fiber structure according to claim 1 or 2, wherein: