JP2013096021A - Flame retardant and method for producing flame retardant aliphatic polyester fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart hydrolysis resistance and flame retardancy to an aliphatic polyester fiber structure.SOLUTION: There is provided a flame retardant used for subjecting an aliphatic polyester fiber structure to flame-retardant processing, in which the flame retardant is obtained by dispersing or emulsifying an aromatic phosphorus-based flame retardant and a carbodiimide terminal blocking agent into water. The aromatic phosphorus-based flame retardant includes both a specified monophosphate and a specified polyphosphate. A method for producing a flame retardant aliphatic polyester fiber structure comprising: feeding step of feeding the aliphatic polyester fiber structure into a treatment liquid including the flame retardant; in-bath processing step of subjecting the structure to in-bath processing while circulating the treatment liquid; cleaning step; dehydrating step; and drying step is also provided.

Description

  The present invention relates to a flame retardant finish and a method for producing a flame retardant aliphatic polyester fiber structure.

  Due to the recent increase in interest in environmental issues, the construction of a recycling-oriented social system is desired. In building a recycling-oriented social system, it is important to increase demand in addition to supplying environmentally friendly products. From this perspective, the Green Purchasing Law has been enacted as a framework for promoting demand for environmentally conscious products. Public institutions are actively introducing products with low environmental impact that meet the standards of the Green Purchasing Law.

  Biodegradable plastic made from natural resources has a low environmental impact and can be said to be a material that complies with the Green Purchasing Law. Under such circumstances, polylactic acid is particularly attracting attention, and it is important how to expand the use of polylactic acid.

  Polylactic acid is said to be a self-extinguishing material that does not have a high degree of flame retardancy but is difficult to continuously burn in the atmosphere. The oxygen index of a polylactic acid fiber fabric not provided with a flame retardant is 24. It is known (see, for example, Non-Patent Document 1). Therefore, taking advantage of the characteristics, it is preferable to deploy to curtains such as blind curtains, roll curtains, partition curtains, and accordion curtains that are compatible with the Green Purchasing Law, and interior products such as wallpaper and shoji paper.

  However, the disadvantage of polylactic acid is that it is very hydrolyzable in room temperature and high temperature water, and it is also decomposed by moisture in the air. Depending on the storage environment and use environment, the product warehouse There are concerns about deterioration due to storage in containers, transport in containers, and actual use.

  By the way, in such an interior textile product, flame retardance is required from the viewpoint of safety when a fire such as a cigarette is accidentally ignited.

  From the above points, if a polylactic acid fiber structure having excellent wet heat durability and excellent flame retardancy can be provided, it can be applied to interior products with a low environmental load that conform to the Green Purchasing Law. Become.

  As a means for suppressing the hydrolysis of polylactic acid, a method of lowering the terminal carboxyl group concentration by adding a terminal blocking agent can be considered. Patent Document 1 and Patent Document 2 exemplify a method of kneading a terminal blocker during spinning, and Patent Document 3 and Patent Document 4 exemplify a method of kneading a terminal blocker and a flame retardant. Yes. However, since these methods are kneaded and added to the polymer chip before spinning, there is a problem that the end-blocking agent generates smoke due to evaporation or decomposition due to a high temperature during spinning, and generates bad odors and toxic gases. For this reason, there is also a problem that an end-capping agent must be added excessively. Furthermore, the spinnability deteriorates and the productivity also decreases. There is also a problem that hydrolysis due to treatment in the bath during dyeing cannot be suppressed.

  Another method for solving this problem is a method in which a terminal blocker is dissolved in a solvent or emulsified with an emulsifier, and directly contacted with the object to be treated to add a terminal blocker to the surface of the object to be treated. 5 is disclosed. However, since this method has a terminal blocking agent only in the vicinity of the treated surface, the amount of the terminal blocking agent applied is not sufficient, and the hydrolysis resistance to long-term wet heat is insufficient.

  As a method for improving the hydrolysis resistance against wet heat over a long period of time, a high-concentration end-blocking agent is applied to the surface of the structure in direct contact with wet heat, and the end-blocking agent is also added to the inside of the structure at a constant concentration. Is desirable. Patent Document 6 discloses a method in which a terminal blocking agent is added at a high concentration near the surface of the structure, and a terminal blocking agent is added to the inside of the structure at a certain concentration or more. However, since the exhaustion efficiency of the end capping agent to the object to be processed is low, there is a problem that the use concentration is high and the cost related to the end capping agent is increased.

  As a method of imparting flame retardancy to a fiber structure, a method of imparting a flame retardant to a woven or knitted fabric or a nonwoven fabric can be considered. Examples of the flame retardant include halogen-based and non-halogen-based flame retardants, and non-halogen-based flame retardants are desirable from the viewpoint of adverse effects on the human body due to gas generated at the time of fire.

  By the way, among the non-halogen flame retardants, the flame retardant itself may be hydrolyzed by wet heat, and a by-product generated therefrom may promote the hydrolysis of the polyester as a base fabric. In that case, since the improvement in wet heat durability of the polylactic acid fiber structure by the end-capping agent is offset, it is necessary to limit the non-halogen flame retardant to an appropriate one.

  As a non-halogen flame retardant, a phosphorous flame retardant used in the present invention is exemplified in Patent Document 7, and paragraph [0019] describes polylactic acid as an example of an aliphatic polyester. Is only polyethylene terephthalate which is an aromatic polyester, and it is not exemplified at all that the same flame retardant performance can be obtained even for a fiber structure containing polylactic acid, and the flame retardant described in the patent document There is no suggestion that does not inhibit the end-capping effect of polylactic acid.

  From the above, it can be said that the present invention cannot be easily achieved from a combination of conventional techniques.

JP 2001-261797 A JP 2002-030208 A JP 2010-254899 A JP 2008-156616 A JP 2009-249450 A JP 2009-263840 A JP 2007-051385 A

Kubogawa and two others, “Flame-retardant of polylactic acid fiber fabrics”, Journal of the Textile Society of Japan, Textile Society of Japan, 1999, vol. 55, no. 7, p. 290-297

  In view of the conventional background, the present invention provides an aliphatic polyester fiber structure having excellent wet heat durability and excellent flame retardancy.

  In order to achieve the above object, the present invention has the following configuration.

(1) A flame-retardant processing agent for flame-retardant processing of an aliphatic polyester fiber structure, wherein an aromatic phosphorus-based flame retardant and a carbodiimide end-blocking agent are dispersed or emulsified in water. A flame retardant processing agent comprising a monophosphate represented by the following general formula (I) or (II) and a polyphosphate represented by the following general formula (III) or (IV).

(In the general formula (I), Ar ₁ and Ar ₂ each represent an aryl group, and R ₁ and R ₂ are each a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, or an aralkyl group. R ₁ and R ₂ are bonded to each other to form a ring together with the nitrogen atom bonded to the phosphorus atom.)

(In the general formula (II), Ar ₁ , Ar ₂ and Ar ₃ represent the same aryl group.)

(In the general formula _{(III), R 1, R} 2, R 3 and _{R 4} represents a hydrogen atom, Y is -CH ₂ - group, -C _{(CH 3) 2} - group, -S- group, - It is any one of SO ₂ — group, —O— group, —C═O— group, —N═N— group, n represents an integer of 0 or more, and m represents an integer of 0 to 4. In the above general formula (III), R ₁ R ₂ R ₃ connected to the benzene nucleus by a line indicates that each of R ₁ , R ₂ and R ₃ is bonded to a different carbon atom in the benzene nucleus. Means that.)

(In the general formula (IV), R ₁ , R ₂ , R ₃ and R ₄ are all phenyl groups, cresyl groups, and xylenyl groups, and Ry is a group represented by the following general formula (V). Indicates one of these.)

(In the general formula (V), A represents any of the groups represented by the following chemical formula (VI), and n is an integer of 1 to 20.)

(2) The carbodiimide end-capping agent is at least selected from the group consisting of N, N′-di-2,6-diisopropylphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide and N, N′-diisopropylcarbodiimide. The flame retardant processing agent according to (1), comprising one compound.

(3) The flame retardant processing agent according to (1), comprising N-alkylphthalimide and a benzoic acid ester.

(4) A charging step of charging the aliphatic polyester fiber structure into the treatment liquid containing the flame retardant processing agent of (1), and a bath while circulating the treatment liquid charged with the aliphatic polyester fiber structure. In-bath processing step for intermediate processing, cleaning step for cleaning the aliphatic polyester fiber structure processed in the bath, dehydration step for dehydrating the washed aliphatic polyester fiber structure, and the dehydrated fat And a drying step of drying the aliphatic polyester fiber structure. A method for producing a flame-retardant aliphatic polyester fiber structure.

(5) The method for producing a flame-retardant aliphatic polyester fiber structure according to (4), wherein a processing temperature in the bath in the processing step in the bath is 80 to 140 ° C.

(6) The method for producing a flame-retardant aliphatic polyester fiber structure according to (4), which has a mixing step of mixing a dye in the treatment liquid before the charging step.

(7) The method for producing a flame-retardant aliphatic polyester fiber structure according to (4), wherein the aliphatic polyester fiber structure includes a polylactic acid fiber.

(8) The flame retardant aliphatic polyester fiber structure according to (4), wherein the aliphatic polyester fiber structure includes a core-sheath composite fiber having a core part made of polylactic acid and a sheath part made of aromatic polyester. Method.

(9) The method for producing a flame-retardant aliphatic polyester fiber structure according to (8), wherein the sheath portion of the core-sheath composite fiber is made of polytrimethylene terephthalate.

  According to the present invention, a flame retardant that does not adversely affect the performance of the end-capping agent is efficiently exhausted to the aliphatic polyester fiber structure together with the end-capping agent, thereby having excellent hydrolysis resistance. In addition, an aliphatic polyester fiber structure having excellent flame retardancy can be provided.

  Hereinafter, preferred embodiments of the invention will be described.

(About treated fibers)
The term “aliphatic polyester fiber structure” as used in the present invention means that the polyester main chain contains an aliphatic polyester in at least a part of the fiber structure, and polylactic acid is preferably used from the viewpoint of versatility.

  Polylactic acid is obtained by condensing an aliphatic dicarboxylic acid and an aliphatic diol, poly (D-lactic acid), poly (L-lactic acid), a copolymer of D-lactic acid and L-lactic acid, D A copolymer of lactic acid and hydroxycarboxylic acid, a copolymer of L-lactic acid and hydroxycarboxylic acid, a polymer selected from a copolymer of DL-lactic acid and hydroxycarboxylic acid, or a blend thereof. Can be mentioned. The polylactic acid may be partially blocked with a terminal carboxyl group by adding a terminal blocking agent during spinning.

  As a method for producing such polylactic acid, a lactide, which is a cyclic dimer, is first produced from lactic acid as a raw material, and then ring-opening polymerization is performed, and direct dehydration condensation is performed in a solvent using lactic acid as a raw material. One-step direct polymerization methods are known. The polylactic acid used in the present invention may be obtained by any production method.

  The aliphatic polyester fiber structure may contain fibers other than polylactic acid, and fragrance such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polytrimethylene naphthalate, and polybutylene naphthalate. A group polyester may be included. Moreover, these aromatic polyesters may contain other copolymerization components, and are not limited to the above polyesters.

  As the form of the aliphatic polyester fiber forming the aliphatic polyester fiber structure, in addition to a normal flat yarn, a filament yarn such as a false twisted yarn, a strongly twisted yarn, a taslan processed yarn, a thick yarn, and a mixed yarn can be used. It may be a fiber structure of various forms such as staple fiber, tow, spun yarn, or fabric.

  The aliphatic polyester fiber may form an alloy with another polymer such as polyamide, or may form a core-sheath structure with another polymer.

  Natural fibers, recycled fibers, semi-synthetic fibers, synthetic fibers, and the like may be mixed with the aliphatic polyester fibers as long as flame retardancy is not impaired. The composite form may be any form such as mixed spinning, union, knitting. Examples of the fiber structure include, but are not limited to, filaments, spun yarns, and fiber structures such as woven fabrics, knitted fabrics, nonwoven fabrics, and products obtained therefrom.

  Examples of the natural fiber include cotton, kapok, hemp, flax, cannabis, hemp, wool, alpaca, cashmere, mohair, silk, and the like. Examples of the regenerated fiber include viscose, cupra, polynosic, high wet modulus rayon, and solvent-spun cellulose fiber. Examples of the semi-synthetic fiber include acetate, diacetate, and triacetate. Examples of the synthetic fiber include polyamide, acrylic, vinylon, polypropylene, polyurethane, polyvinyl chloride, polyethylene, and promix.

  The aliphatic polyester fiber and other fibers may be mixed by any method. However, since the effect of the present invention is reduced if the mixing ratio of the aliphatic polyester fiber is small, the mixing ratio of the aliphatic polyester fiber is 30% by weight or more. Is preferable, and 50% by weight or more is more preferable.

(About processing method)
The aliphatic polyester fiber structure is treated with a treatment liquid in which a flame retardant and a terminal blocking agent are emulsified or dispersed in water or a solvent using a surfactant.

  When the processing in the bath is performed while circulating the treatment liquid, examples of the form of the aliphatic polyester fiber structure that is the object to be treated include cloth, yarn, product, tow, cotton, and the like, but are not limited thereto. It is not a thing. As processing equipment for processing in the bath, equipment such as Wins dyeing machine, jigger dyeing machine, paddle dyeing machine, drum type dyeing machine, liquid dyeing machine, airflow dyeing machine, beam dyeing machine, cheese dyeing machine, and overmeyer are used. However, it is not limited to these.

  It is preferable to immerse the fabric in the treatment liquid and treat it at 80 to 140 ° C. for 20 to 60 minutes under normal pressure or pressure. At this time, the flame retardant and the end-capping agent adhere to the fiber and are exhausted and diffused inside the fiber. When the treatment time is short, exhaustion and diffusion of the end-capping agent and the flame retardant into the fiber are not sufficient, and satisfactory hydrolysis resistance and flame resistance cannot be obtained. Moreover, when processing time is too long, hydrolysis of polylactic acid will advance during processing.

  In such a method, after treatment in liquid, dehydration and drying are performed. The drying conditions are preferably 90 to 130 ° C. and 30 seconds to 5 minutes. After drying, it is preferable to perform a heat treatment at 90 to 130 ° C. for 30 seconds to 5 minutes. As a heat treatment apparatus, a tenter, a short loop, a shrink surfer, a steamer, a cylinder dryer, or the like can be used. However, the apparatus is not limited to these as long as the apparatus can uniformly apply heat to the fiber.

  When a hydrophobic dye typified by a disperse dye is mixed with a treatment liquid containing an end-capping agent and a flame retardant, dyeing can be performed together with the end-capping treatment. By performing the end-capping treatment and the flame retardant treatment at the same time as the dyeing, the number of passes through the wet heat treatment step is reduced, so hydrolysis of the aliphatic polyester is suppressed. As the hydrophobic dye, vat dyes, indigo dyes, naphthol dyes, and the like can also be used.

(About end blocker)
Examples of the carbodiimide compound used as the end-capping agent include compounds having at least one carbodiimide group, such as N, N′-di-o-tolylcarbodiimide, N, N′-diphenylcarbodiimide, N, N ′. -Dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'- Di-2,6-di-tert. -Butylphenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di -Cyclohexylcarbodiimide, N, N'-di-p-tolylcarbodiimide, p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, ethylene-bis- Diphenylcarbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide Diimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'-di-o-isopropylphenylcarbodiimide N, N'-di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6 -Diethylphenylcarbodiimide, N, N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4 6-trimethylphenylcarbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbo Imide, N, N'- di-2,4,6-isobutylphenyl carbodiimide, N, etc. N'- diisopropyl carbodiimide. Further, one or more compounds may be arbitrarily selected from these carbodiimide compounds to block the carboxyl terminal of the polyester.

  As commercially available carbodiimide compounds, N, N′-di-2,6-diisopropylphenylcarbodiimide (TIC), N, N′-dicyclohexylcarbodiimide (DCC), N, N′-diisopropylcarbodiimide (DIC) These can be preferably used. Furthermore, in TIC, “STABAKZOL” I, “STABAKZOL” I-LF, “STABAKZOL” P, and “STABAKZOL” P-100, which are sold by Rhein Chemie Japan Co., Ltd. under the trade name “STABAKZOL”, are suitable. Illustrated.

  As a method of emulsifying or dispersing the above end-blocking agent in water or a solvent using a surfactant, a known method may be used. When emulsifying or dispersing the end-blocking agent in water or a solvent using a surfactant, a compound that is compatible with the end-blocking agent and has an affinity for polyester is dissolved in the end-blocking agent. It is desirable to use it as an agent.

  When a carrier agent is used as the solubilizer, an effect of swelling the molecular chain of the polyester can be expected, and the dye, end-capping agent and flame retardant can be exhausted into the polyester fiber from a low temperature of 100 ° C. or lower. The treatment temperature in the bath can be lowered. Thereby, hydrolysis of the aliphatic polyester due to the treatment in the bath can be suppressed. However, if the carrier component remains, it may cause poor flame retardancy or poor fastness depending on the dye concentration.

  As the carrier component, trichlorobenzene, methylnaphthalene and the like have been conventionally used. However, since the odor is strong and a carrier spot is easily generated, there is a concern about the odor and quality of the final product as the working environment deteriorates. In order to solve such a problem, it is desirable to use a phthalimide compound and a benzoic acid compound as a carrier agent.

  The phthalimide compound is a compound having a phthalimide group, and an N-substituted phthalimide having an aliphatic or aromatic alkyl group in the N group of phthalimide is preferable. Examples of substituents include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, benzyl group, naphthal group, etc., but residual amount in processed products, odor, safety, handling workability From these points, an N-alkylphthalimide having a low molecular weight aliphatic alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group is more preferable. Among these, N-butylphthalimide is preferably used because it is excellent in compatibility with the carbodiimide compound.

  The benzoic acid compound refers to a benzoic acid derivative, and a benzoic acid ester composed of benzoic acid and an aliphatic or aromatic alcohol is preferable. Examples of benzoic acid esters include ethyl benzoate, methyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate, phenyl benzoate, etc., compatibility with carbodiimide compounds and swelling effect of polyester chain, etc. From this point, benzyl benzoate, phenyl benzoate and the like are more preferable. Among them, benzyl benzoate, which has a molecular weight close to that of TIC which is a terminal blocking agent and is available at low cost, is preferably used.

  The mixing ratio of the phthalimide compound and the benzoic acid compound is preferably 10 parts by weight to 50 parts by weight of the benzoic acid compound, more preferably 15 parts by weight to 40 parts by weight of the benzoic acid compound, with respect to 50 parts by weight of the phthalimide compound. 20 to 30 parts by weight is more preferable. Further, two or more phthalimide compounds and two or more benzoic acid compounds may be used.

  On the other hand, when an aliphatic hydrocarbon solvent is used as a solubilizer, the swelling effect of the polyester chain is inferior to that of the carrier agent, so that the treatment temperature in the bath is as high as 110 to 140 ° C. Fastness can be maintained.

  Examples of the aliphatic hydrocarbon-based compatibilizer include normal paraffin, isoparaffin, liquid paraffin, and naphthene. Furthermore, you may mix and use 1 type, or 2 or more types of compatibilizer out of these aliphatic hydrocarbon type compatibilizers.

  As the normal paraffin, for example, “Normal Paraffin SL, L, M, H” manufactured by Nippon Petrochemical Co., Ltd. can be used. As isoparaffins, for example, “Isopar G, H, L, M” manufactured by ExxonMobil, “IP Solvent 1620, 2028” manufactured by Idemitsu Petrochemical Co., Ltd., and the like can be used. As the liquid paraffin, for example, “Moresco White”, “Mosco Bioless” manufactured by Matsumura Oil Research Institute, etc. can be used. Further, as naphthene, for example, “Exsol D110, D130” manufactured by ExxonMobil Corporation can be used.

  The addition amount of the aliphatic hydrocarbon-based compatibilizer is usually 1.0 to 15.0 parts by weight, preferably 1.5 to 10.0 parts by weight, more preferably 3 parts per 10 parts by weight of the carbodiimide compound. 0.0 to 8.0 parts by weight.

(About flame retardant)
As one of the flame retardants, a liquid phosphate ester such as resorcinol bis (diphenyl phosphate) is known, but the flame retardancy is not sufficient for dry cleaning resistance and easily causes poor dyeing fastness. . In addition, those which are easily hydrolyzed and easily generate chemical species such as protons and phenols have a problem of offsetting the effect of the end-capping agent.

  As a result of intensive studies to solve such problems, an aliphatic polyester fiber structure having excellent wet heat durability and excellent flame retardancy was produced by using the following flame retardant.

  That is, a flame retardant containing a monophosphate represented by the following general formula (I) or (II) and a polyphosphate represented by the following general formula (III) or (IV) is used in combination with a terminal blocking agent.

(In the above general formula (I), Ar ₁ and Ar ₂ each represent an aryl group, and R ₁ and R ₂ each represent a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, or an aralkyl group. Or R ₁ and R ₂ are bonded together to form a ring with the nitrogen atom bonded to the phosphorus atom.)

（上記一般式（ＩＩ）中、Ａｒ_１、Ａｒ_２およびＡｒ_３は、同一のアリール基を示す。）

(In the general formula (II), Ar ₁ , Ar ₂ and Ar ₃ represent the same aryl group.)

(In the general formula _{(III), R 1, R} 2, R 3 and _{R 4} represents a hydrogen atom, Y is -CH ₂ - group, -C _{(CH 3) 2} - group, -S- group, - It is any one of SO ₂ — group, —O— group, —C═O— group, —N═N— group, n represents an integer of 0 or more, and m represents an integer of 0 to 4. In the above general formula (III), R ₁ R ₂ R ₃ connected to the benzene nucleus by a line indicates that each of R ₁ , R ₂ and R ₃ is bonded to a different carbon atom in the benzene nucleus. Means that.)

(In the above general formula (IV), R ₁ , R ₂ , R ₃ and R ₄ are all phenyl groups, cresyl groups, and xylenyl groups, and Ry is any of the following general formula (V) Indicates the group.)

(In the general formula (V), A is any group represented by the following chemical formula (VI), and n is an integer of 1 to 20.)

  Specific examples of the compound represented by the general formula (I) include, for example, 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-cresylphenylaminophosphate, diphenyl (methylphenylamino) phosphate Diphenyl (ethylphenol) Arylamino) phosphate, benzylamino diphenyl phosphate, can be mentioned morpholino diphenyl phosphate and the like.

  Specific examples of the compound represented by the general formula (II) include tri-o-cresyl phosphate, tri-m-cresyl phosphate, tri-p-cresyl phosphate, trixyl phosphate, trinaphthyl phosphate, and the like. be able to.

  Specific examples of the compound represented by the general formula (III) include tetra (2,6-dimethylphenyl) -m-phenylene phosphate, tetra (2,6-dimethylphenyl) -p-phenylene phosphate, and 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.

  Specific examples of the compound represented by the general formula (IV) 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, phenylresorcin polyphosphate, bisphenol Compounds such as orthophosphoric acid ester and the oligomers, such as Nord A polyphenyl phosphate.

The phosphoric acid amide represented by the general formula (I) is reacted with a diaryl phosphorochloridate in an organic solvent in the presence of an amine catalyst as described in JP-A No. 2000-154277. Can be obtained. In particular, according to the present invention, in the phosphoric acid amide represented by the above general formula (I), Ar ₁ and Ar ₂ are preferably phenyl or tolyl groups, and R ₁ and R ₂ are preferably one of hydrogen atoms. And the other is a phenyl or cyclohexyl group. Examples of such phosphoric amides include anilinodiphenyl phosphate, di-o-cresylphenylamino phosphate, and cyclohexylaminodiphenyl phosphate.

  The phosphate ester represented by the general formula (II) can be obtained as a commercial product.

  The aromatic polyphosphate represented by the general formula (III) is described in, for example, JP-A-63-227632, and can be obtained as a commercial product.

  The aromatic polyphosphate represented by the general formula (IV) is a crystalline powder and is described in, for example, JP-A-5-1079, and can be obtained as a commercial product.

  The flame retardant is used by emulsifying or dispersing it in water or a solvent using a surfactant in the same manner as the end-capping agent. As a method for emulsifying or dispersing in water or a solvent, a known method may be used.

  As the emulsifier used when emulsifying or dispersing the end-capping agent and the flame retardant in water or a solvent, at least one surfactant selected from nonionic surfactants or anionic surfactants may be used in combination. preferable. Examples of the nonionic surfactant include a higher alcohol alkylene oxide adduct, an alkylphenol alkylene oxide adduct, a styrenated phenol alkylene oxide adduct, a fatty acid alkylene oxide adduct, a polyhydric alcohol aliphatic ester alkylene oxide adduct, and a higher alcohol. List polyoxyalkylene type nonionic surfactants such as alkylamine alkylene oxide adducts and fatty acid amide alkylene oxide adducts, and polyhydric alcohol type nonionic surfactants such as alkylglycoxides and sucrose fatty acid esters. Can do. These nonionic surfactants may be used alone or in combination of two or more as required.

  On the other hand, examples of the anionic surfactant include carboxylates such as fatty acid soaps, higher alcohol sulfates, higher alkyl polyalkylene glycol ether sulfates, sulfate esters of styrenated phenol alkylene oxide adducts, and alkylphenols. Sulfuric acid ester salts of alkylene oxide adducts, sulfated oils, sulfated fatty acid esters, sulfated fatty acids, sulfated olefins such as sulfated olefins, alkylbenzenesulfonates, alkylnaphthalenesulfonates, naphthalenesulfonates, naphthalenesulfonates Formalin condensates such as, sulfonates such as α-olefin sulfonates, paraffin sulfonates, sulfosuccinate diester salts, higher alcohol phosphate ester salts, and the like. These anionic surfactants may be used alone or in combination of two or more as required. Moreover, you may combine a nonionic surfactant and an anionic surfactant as needed.

  Solvents used for emulsifying the flame retardant include aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and ethyl cellosolve, amides such as dimethylformamide, And sulfoxides such as dimethyl sulfoxide and mixtures of two or more thereof.

  Although the usage-amount of a terminal blocker should just be determined according to the quantity of the terminal carboxyl group of the target aliphatic polyester fiber structure, it is 0.5-5. With respect to 100 weight part of aliphatic polyester fiber structures. The amount is preferably 0 part by weight, more preferably 1.0 to 3.0 parts by weight.

  The blending ratio of the monophosphate represented by the general formula (I) or (II) and the polyphosphate represented by the general formula (III) or (IV) is 1: 0.25 to 1: 1 by weight. It is preferable that the ratio is 1: 0.25 to 1: 0.75.

  The content of the flame retardant is such that the total of the monophosphate represented by the general formula (I) or (II) and the polyphosphate represented by the general formula (III) or (IV) is a fiber structure before processing. 0.5 parts by weight or more, preferably 2 parts by weight or more, and more preferably 3 to 20 parts by weight with respect to 100 parts by weight.

  Since the aliphatic polyester fiber structure obtained by the present invention has excellent hydrolysis resistance and good flame retardancy, curtains such as blind curtains, roll curtains, partition curtains, and accordion curtains, wallpaper, It is preferably used for interior products such as shoji paper.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The method for measuring physical properties in the fabrics and examples used in the present invention are as follows.

(Production of polylactic acid fabric)
An L-polylactic acid (PLA) chip having a melting point of 166 ° C. was dried for 12 hours in a vacuum dryer set at 105 ° C. The dried chip was put into a melt spinning machine and melt-spun at a melting temperature of 210 ° C. to obtain an undrawn yarn having a variety of 100 dtex-26 filaments at a spinning temperature of 220 ° C. and a spinning speed of 4500 m / min. The undrawn yarn was drawn at a preheating temperature of 100 ° C. and a heat setting temperature of 130 ° C. at a draw ratio of 1.2 times to obtain a drawn yarn of 84 dtex-26 filament. After weaving taffeta with the obtained drawn yarn and scouring at 80 ° C., dry heat setting was performed at 130 ° C. for 1 minute to obtain a PLA fabric.

(Production of polylactic acid / polytrimethylene terephthalate core-sheath fabric)
Poly L lactic acid (optical purity 97% L lactic acid) (PLA) having a weight average molecular weight of 16,000, a melting point of 170 ° C. and a residual lactide amount of 0.085% by weight is the core A, and the average secondary particle size is 0.4 μm. Polytrimethylene terephthalate (PTT) (melting point 228 ° C.) containing 0.3% by weight of titanium oxide was melted separately as a sheath part, and the core-sheath composite ratio (% by weight) 70:30 at a spinning temperature of 250 ° C. An undrawn yarn having a core-sheath composite structure of 110 dtex and 36 filaments was obtained at a spinning speed of 3000 m / min. Further, the undrawn yarn was drawn at a drawing speed of 800 m / min, a draw ratio of 1.3 times, a drawing temperature of 90 ° C., and a heat setting temperature of 130 ° C. to obtain a drawn yarn of 84 dtex and 48 filaments. The obtained drawn yarn was used to weave taffeta and scoured at 80 ° C. for 20 minutes, and then set at 130 ° C. for 2 minutes to obtain a PLA / PTT woven fabric.

(Measurement of various physical properties)
(1) Hydrolysis resistance The strength of the yarn constituting the processed fabric is A, and the fabric is hydrolyzed for 7 days under conditions of 70 ° C. and 90% RH using a constant temperature and humidity tester THN064PB manufactured by Toyo Manufacturing Co., Ltd. When the strength of the yarn after the decomposition treatment was defined as B, the strength retention of the yarn obtained from the following formula was defined as hydrolysis resistance. Yarn strength was measured using Shimadzu Autograph AG-1S under the conditions of a sample length of 20 cm and a tensile speed of 20 cm / min.
Strength retention (%) = {(Strength A after hydrolysis treatment) / (Strength B after end-capping treatment)} × 100

(2) Flame Retardant Performance A fabric subjected to flame retardant processing and a fabric washed five times under the following condition (i) or dry-cleaned five times under the condition (ii), the JIS L 1091D method (coil method) and JIS Flame retardancy was evaluated by the L 1091A-1 method (45 ° micro burner method). In the coil method, (i) the number of times of flame contact for clearing the label defined in the curtain application was passed 3 times or more, and the 45 ° micro burner method was accepted as a flame time within 3 seconds and a fire spread area within 40 cm2.

(I) Washing in water According to JIS K 3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, and a bath ratio of 1:40 was washed for 15 minutes at 60 ° C. ± 2 ° C., and then 40 ° C. ± 2 ° C. Then, 5 minutes of rinsing was performed 3 times, centrifugal dehydration was performed for 2 minutes, and then 1 cycle of drying with hot air at 60 ° C. ± 5 ° C. was performed 5 cycles.

(Ii) Dry cleaning For each 1 g of sample, 12.6 mL of tetrachloroethylene and 0.265 g of charge soap (the weight composition of the charge soap is a nonionic surfactant (10 mol adduct of nonylphenyl ether with ethylene oxide) / anionic surfactant ( Dioctyl succinate sodium salt) / water = 10/10/1) was treated at 30 ° C. ± 2 ° C. for 15 minutes as one cycle, and this was performed for 5 cycles.

(3) Fastness Various fastnesses were tested based on JIS as shown below.
(I) Fastness to washing: A test was conducted based on the JIS L 0860A-1 method (dry cleaning) and the JIS L 0844A-2 method (water washing).
(Ii) Light fastness: Based on JIS L 0842 method, quaternary irradiation was performed, and the determination was made on a blue scale.
(Iii) Fastness to friction: Based on JIS L0846 method, a flame-retardant processed fabric was tested by dyeing fastness test method B, and measured with a gray scale for contamination. A Gakushin type was used as the friction tester.

  Moreover, the terminal blocker and the flame retardant were emulsified or dispersed by the following method and used in the present invention.

(Preparation of terminal blocking agent 1)
20.0 parts by weight of bis (2,6-diisopropylphenyl) carbodiimide (Stavaxol I-LF; Rhein Chemie Japan), 5.0 parts by weight of benzyl benzoate (Nacalai Tesque), N-butylphthalimide (Nacalai Tesque) Co., Ltd.) 10.0 parts by weight, sulfated castor oil (Rohto oil; Miyoshi Oil & Fat Co., Ltd.) 2.0 parts by weight, polyoxyethylene tridecyl ether phosphate (EO addition mole number 4) 2.5 parts by weight, water An emulsion containing 47.5 parts by weight was used as the end-capping agent 1.

(Preparation of terminal blocking agent 2)
15.0 parts by weight of bis (2,6-diisopropylphenyl) carbodiimide, 10.0 parts by weight of liquid paraffin {Molesco White P-350P (Matsumura Oil)}, 1.8 parts by weight of stearyl alcohol ethylene oxide 7 mol adduct, An emulsified product containing 0.4 parts by weight of sorbitan monostearate ethylene oxide 20 mol adduct and 72.8 parts by weight of water at 70 ° C. was used as end-capping agent 2.

(Preparation of flame retardant 1)
An aqueous dispersion containing a compound (anilinodiphenyl phosphate) represented by the following chemical formula (1) at a concentration of 40% by weight was used as the flame retardant 1.

(Preparation of flame retardant 2)
An aqueous dispersion containing a compound (monophosphate) represented by the following general formula (2) at a concentration of 50% by weight was used as the flame retardant 2.

(Preparation of flame retardant 3)
An aqueous dispersion containing a compound (monophosphate) represented by the following chemical formula (3) at a concentration of 50% by weight was used as the flame retardant 3.

(Preparation of flame retardant 4)
An aqueous dispersion containing a compound (bisphosphate) represented by the following chemical formula (4) at a concentration of 40% by weight was used as the flame retardant 4.

(Preparation of flame retardant 5)
An aqueous dispersion containing a compound (bisphosphate) represented by the following chemical formula (5) at a concentration of 40% by weight was used as the flame retardant 5.

(Preparation of flame retardant 6)
An aqueous dispersion containing a compound (bisphosphate) represented by the following chemical formula (6) at a concentration of 45% by weight was used as the flame retardant 6.

(Preparation of flame retardant 7)
An aqueous dispersion containing a compound (bisphosphate) represented by the following chemical formula (7) at a concentration of 37% by weight was used as the flame retardant 7.

(Preparation of flame retardant 8)
An aqueous dispersion containing a compound (bisphosphate) represented by the following chemical formula (8) at a concentration of 37% by weight was used as the flame retardant 8.

(Preparation of flame retardant 9)
An aqueous dispersion containing a compound (phosphine oxide) represented by the following chemical formula (9) at a concentration of 40% by weight was used as the flame retardant 9.

(Preparation of flame retardant 10)
An aqueous dispersion containing a compound (phosphaphenanthrene) represented by the following chemical formula (10) at a concentration of 40% by weight was used as the flame retardant 10.

(Preparation of flame retardant 11)
An aqueous dispersion containing a compound (monophosphate) represented by the following chemical formula (11) at a concentration of 40% by weight was used as the flame retardant 11.

Example 1
Using a high-pressure dyeing tester, the PLA fabric is 2% owf as the solid content of the end-capping agent 1 and 5.6% owf as the solid content of the flame retardant 1 and flame retardant 4 as the flame retardant. 2.4% owf as solid content, 0.01% owf as kiwalon Polyester Blue AP-696 as dye, 0.02% owf as kiwalon Polyester Red, 0.1% owf as kiwalon Polyester Yellow YL-SE Colored and immersed in a processing solution with a bath ratio of 1:20, and processed using UR / MINI-COLOR (Infrared Mini Color (manufactured by Texam Giken)) while circulating the processing solution at 110 ° C. for 30 minutes. went. Furthermore, nonionic surfactant Gran Up US-20 (Sanyo Kasei Kogyo Co., Ltd.) 0.5 g / L, soda ash 1.5 g / L, hydrosulfite 2.0 g / L, bath ratio 1:20 Then, reduction cleaning was performed at 60 ° C. for 20 minutes. After centrifugal dehydration, drying was performed in a pin tenter set to 110 ° C., and finishing setting was performed in the pin tenter set to 130 ° C. each time. The sample after finishing set was subjected to hydrolysis treatment for 7 days under conditions of 70 ° C. and 90% RH using a constant temperature and humidity tester THN064PB manufactured by Toyo Manufacturing Co., Ltd., and various physical properties before and after the hydrolysis treatment were measured. .

(Example 2)
Except for changing the flame retardant 4 to the flame retardant 6, the same treatment and measurement as in Example 1 were performed.

(Example 3)
Except for changing the flame retardant 4 to the flame retardant 7, the same treatment and measurement as in Example 1 were performed.

Example 4
Except for changing the flame retardant 4 to the flame retardant 8, the same treatment and measurement as in Example 1 were performed.

(Example 5)
The conditions relating to the type and concentration of the flame retardant were changed to the conditions that 7.0% owf was used as the solid content of the flame retardant 11 and 3.0% owf was used as the solid content of the flame retardant 4 The same processing and measurement as in Example 1 were performed.

(Example 6)
The conditions regarding the type and concentration of the flame retardant were changed to the conditions that 7.0% owf was used as the solid content of the flame retardant 11 and 3.0% owf as the solid content of the flame retardant 6 except that the flame retardant 11 was used as the solid content of the flame retardant. The same processing and measurement as in Example 1 were performed.

(Example 7)
The conditions regarding the type and concentration of the flame retardant were changed to the condition that 7.0% owf was used as the solid content of the flame retardant 11 and 3.0% owf was used as the solid content of the flame retardant 7 The same processing and measurement as in Example 1 were performed.

(Example 8)
The conditions regarding the type and concentration of the flame retardant were changed to the conditions that 7.0% owf was used as the solid content of the flame retardant 11 and 3.0% owf was used as the solid content of the flame retardant 8 except that the flame retardant 11 was used as the solid content of the flame retardant. The same processing and measurement as in Example 1 were performed.

Example 9
The same treatment and measurement as in Example 1 were performed except that the end blocker 1 was changed to the end blocker 2.

(Example 10)
The end-blocking agent 1 is changed to the end-blocking agent 2 and the conditions regarding the type and concentration of the flame retardant are 7.0% owf with the flame retardant 11 as the solid content of the flame retardant and the flame retardant 4 as the solid content of the flame retardant. The same processing and measurement as in Example 1 were performed except that the condition was changed to 3.0% owf.

(Comparative Example 1)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 1.

(Comparative Example 2)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 2.

(Comparative Example 3)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 3.

(Comparative Example 4)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 4.

(Comparative Example 5)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 5.

(Comparative Example 6)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 6.

(Comparative Example 7)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 7.

(Comparative Example 8)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 8.

(Comparative Example 9)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 9.

(Comparative Example 10)
The same treatment and measurement as in Example 1 were performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 10.

(Comparative Example 11)
The same treatment as in Example 1 was performed except that the conditions regarding the type and concentration of the flame retardant were changed to the condition that 8.0% owf was used as the solid content of the flame retardant 11.

(Comparative Example 12)
Except for changing the flame retardant 4 to the flame retardant 2, the same treatment and measurement as in Example 1 were performed.

(Comparative Example 13)
Except for changing the flame retardant 4 to the flame retardant 3, the same treatment and measurement as in Example 1 were performed.

(Comparative Example 14)
Except for changing the flame retardant 4 to the flame retardant 5, the same treatment and measurement as in Example 1 were performed.

(Comparative Example 15)
Except for changing the flame retardant 4 to the flame retardant 9, the same treatment and measurement as in Example 1 were performed.

(Comparative Example 16)
Except for changing the flame retardant 4 to the flame retardant 10, the same treatment and measurement as in Example 1 were performed.

  As shown in Examples 1 to 8, a monophosphate represented by the general formula (I) or (II) and the general formula (III) or (IV) represented by the general formula (I) or (II) as a flame retardant is used. It can be seen that by including both of the polyphosphates, both good flame retardancy and excellent wet heat durability can be imparted (Table 1).

  In addition, as shown in Examples 9 and 10, even when the end-blocking agent 1 is changed to the end-blocking agent 2, both good flame retardancy and excellent wet heat durability are achieved as in Examples 1-8. It can be seen that it can be given (Table 1).

  On the other hand, as shown in Comparative Examples 1, 4, 6, 7, 8, and 11, as the flame retardant, the monophosphate represented by the general formula (I) or (II), the general formula (III) or (IV In the case where only one of the polyphosphates represented by) is contained, the flame retardancy is insufficient or the wet heat durability is lowered (Table 2).

  In addition, as shown in Comparative Examples 2, 3, 5, 9, and 10, as the flame retardant, a flame retardant that does not belong to any of the general formulas (I) to (IV) is also used as a flame retardant. Performance is insufficient or wet heat durability is reduced (Table 2).

Furthermore, as shown in Comparative Examples 12 to 16, the monophosphate represented by the general formula (I) or (II) is included, but the polyphosphate represented by the general formula (III) or (IV) is not included. In some cases, the flame retardancy is insufficient or the wet heat durability is reduced (Table 3). Furthermore, as shown in Comparative Examples 12 and 13, as monophosphates that do not fall under the formula (II), that is, when Ar ₁ , Ar ₂ , and Ar ₃ in the formula (II) are different, flame retardancy There is a shortage or the wet heat durability is reduced (Table 3).

  From the above results, both a monophosphate represented by the general formula (I) or (II) and a polyphosphate represented by the general formula (III) or (IV) are included as a flame retardant, including a terminal blocking agent. By containing the flame retardant, it is possible to produce a flame retardant polylactic acid fiber structure excellent in wet heat durability, and shows the inventive step of the present invention.

(Example 11)
In Example 1, the fiber structure to be treated was changed from a PLA fabric to a PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 12)
In Example 2, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 13)
In Example 3, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 14)
In Example 4, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 15)
In Example 5, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 16)
In Example 6, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 17)
In Example 7, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 18)
In Example 8, the fiber structure to be treated was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 19)
In Example 9, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Example 20)
In Example 10, the fiber structure to be treated was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 17)
In Comparative Example 1, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 18)
In Comparative Example 2, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 19)
In Comparative Example 3, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 20)
In Comparative Example 4, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 21)
In Comparative Example 5, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 22)
In Comparative Example 6, the fiber structure to be treated was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 23)
In Comparative Example 7, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 24)
In Comparative Example 8, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 25)
In Comparative Example 9, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 26)
In Comparative Example 10, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 27)
In Comparative Example 11, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 28)
In Comparative Example 12, the fiber structure to be treated was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 29)
In Comparative Example 13, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 30)
In Comparative Example 14, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 31)
In Comparative Example 15, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

(Comparative Example 32)
In Comparative Example 16, the treated fiber structure was changed from PLA fabric to PLA / PTT fabric, and the same treatment and measurement were performed.

  The results of Examples 11 to 20 and Comparative Examples 17 to 32 also have the same tendency as the PLA fabrics shown in Examples 1 to 10 and Comparative Examples 1 to 16 (Tables 4 to 6).

  That is, the PLA / PTT fabric also contains a terminal blocker and is represented by a monophosphate represented by general formula (I) or (II) and a general formula (III) or (IV) as a flame retardant. By containing both polyphosphates, excellent wet heat durability flame retardancy and good flame retardancy can be imparted, and the effects of the present invention are exhibited.

  According to the present invention, an aliphatic polyester fiber structure having excellent hydrolysis resistance and good flame retardancy can be provided. Such a flame-retardant aliphatic polyester fiber structure can be used for any application, and in particular, it can be suitably used for interior products that have severe demands for wet heat durability, flame retardancy, and environmental load reduction.

Claims (9)

An aromatic phosphorus-based flame retardant and a carbodiimide end-blocking agent, which are dispersed or emulsified in water, are flame-retardant processing agents for flame-retardant processing of aliphatic polyester fiber structures, wherein the aromatic phosphorus-based flame retardant is A flame retardant processing agent comprising a monophosphate represented by the following general formula (I) or (II) and a polyphosphate represented by the following general formula (III) or (IV):

(In the general formula (I), Ar ₁ and Ar ₂ each represent an aryl group, and R ₁ and R ₂ are each a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, or an aralkyl group. R ₁ and R ₂ are bonded to each other to form a ring together with the nitrogen atom bonded to the phosphorus atom.)

(In the general formula (II), Ar ₁ , Ar ₂ and Ar ₃ represent the same aryl group.)

(In the general formula _{(III), R 1, R} 2, R 3 and _{R 4} represents a hydrogen atom, Y is -CH ₂ - group, -C _{(CH 3) 2} - group, -S- group, - It is any one of SO ₂ — group, —O— group, —C═O— group, —N═N— group, n represents an integer of 0 or more, and m represents an integer of 0 to 4. In the above general formula (III), R ₁ R ₂ R ₃ connected to the benzene nucleus by a line indicates that each of R ₁ , R ₂ and R ₃ is bonded to a different carbon atom in the benzene nucleus. Means that.)

(In the general formula (IV), R ₁ , R ₂ , R ₃ and R ₄ are all phenyl groups, cresyl groups, and xylenyl groups, and Ry is a group represented by the following general formula (V). Indicates one of these.)

(In the general formula (V), A represents any of the groups represented by the following chemical formula (VI), and n is an integer of 1 to 20.)

  The carbodiimide end-capping agent is at least one compound selected from the group consisting of N, N′-di-2,6-diisopropylphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide and N, N′-diisopropylcarbodiimide. The flame retardant processing agent according to claim 1, comprising:   The flame-retardant processing agent of Claim 1 containing N-alkyl phthalimide and a benzoic acid ester.   An injecting step of injecting the aliphatic polyester fiber structure into the treatment liquid containing the flame retardant processing agent according to claim 1, and a bath while circulating the treatment liquid in which the aliphatic polyester fiber structure is infused. A processing step in the bath to be processed, a cleaning step to wash the aliphatic polyester fiber structure processed in the bath, a dehydration step to dehydrate the washed aliphatic polyester fiber structure, and the dehydrated aliphatic A method for producing a flame-retardant aliphatic polyester fiber structure, comprising a drying step of drying the polyester fiber structure.   The manufacturing method of the flame-retardant aliphatic polyester fiber structure of Claim 4 whose processing temperature in a bath in the said processing process in a bath is 80-140 degreeC.   The manufacturing method of the flame-retardant aliphatic polyester fiber structure of Claim 4 which has the mixing process which mixes dye in the said process liquid in the front | former stage of the said injection | throwing-in process.   The method for producing a flame-retardant aliphatic polyester fiber structure according to claim 4, wherein the aliphatic polyester fiber structure contains polylactic acid fibers.   The method for producing a flame-retardant aliphatic polyester fiber structure according to claim 4, wherein the aliphatic polyester fiber structure includes a core-sheath composite fiber having a core part made of polylactic acid and a sheath part made of aromatic polyester. .   The method for producing a flame-retardant aliphatic polyester fiber structure according to claim 8, wherein the sheath portion of the core-sheath composite fiber is made of polytrimethylene terephthalate.