JP2012241299A - Method for producing flame retardant polyester-based fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a flame retardant polyester-based fiber and fiber product in which whitening by tris(2,3-dibromopropyl)isocyanurate is suppressed.SOLUTION: The production method for obtaining a flame retardant polyester-based fiber product includes the following steps. A dispersion liquid of polyurethane resin is obtained by reacting an isocyanate group terminated prepolymer obtained by reacting an organic polyisocyanate compound, a high molecular weight polyol having a number average molecular weight of 400-5000 and a carboxyl group with at least one kind of chain extender selected from the group consisting of water soluble polyamine, water soluble hydrazine and derivatives thereof in water. Then, an aqueous dispersion liquid of tris(2,3-dibromopropyl)isocyanurate is obtained. Using the dispersion liquid of the polyurethane resin and the dispersion liquid of the tris(2,3-dibromopropyl)isocyanurate, the polyurethane resin and the tris(2,3-dibromopropyl)isocyanurate are attached to a polyester-based fiber.

Description

  The present invention relates to a method for producing a flame-retardant polyester fiber product.

  Conventionally, as a flame retardant processing method of polyester fiber, hexabromocyclododecane (hereinafter abbreviated as HBCD), which is a typical halogen flame retardant compound, is applied to a fiber, and the HBCD is heated by applying it to the fiber. The mainstream is a processing method that permeates and fixes to the polyester fiber. However, since the HBCD is designated as a first-class monitoring chemical substance because it is a hardly degradable and highly accumulative substance, the automobile industry will be the end of December 2010 and the textile industry will be the end of March 2014. A policy to abolish the use of HBCD has been announced.

  In recent years, therefore, tris (2,3-dibromopropyl) isocyanurate, which has excellent adhesion to the polyester fiber (exhaustability) and flame retardant effect, has been used as a flame retardant component in place of the HBCD. Expected to be used for fuel processing. However, when this compound is applied to the polyester fiber by a continuous treatment such as padding or coating, the tris (2,3-dibromopropyl) isocyanurate is formed on the surface of the resulting fiber product over time. There was a problem of bleeding out and whitening.

  In Japanese Patent Application Laid-Open No. 2007-284830 (Patent Document 1), tris (2,3-dibromopropyl) isocyanurate and a bisphenol bromine compound are used as flame retardants for the purpose of suppressing the whitening. A flame retardancy imparting agent for polyester fabrics containing the above is disclosed. However, in the method using the flame retardant imparting agent described in Patent Document 1, in addition to tris (2,3-dibromopropyl) isocyanurate, a specific flame retardant such as the bisphenol bromine compound is further added. It has a problem that it is necessary to use it together, and further, the whitening resistance in the obtained polyester fiber product is still insufficient. Further, when a binder resin such as an acrylic resin is used for the purpose of improving the adhesion amount of tris (2,3-dibromopropyl) isocyanurate to the polyester fiber, there is a problem that the friction fastness is lowered. It was.

JP 2007-284830 A

  This invention is made | formed in view of the subject which the said prior art has, and is a method for producing a flame-retardant polyester fiber product by attaching tris (2,3-dibromopropyl) isocyanurate to a polyester fiber. Thus, it is difficult to obtain a flame-retardant polyester fiber product having high friction fastness and to sufficiently suppress whitening of the fiber product surface by tris (2,3-dibromopropyl) isocyanurate. It aims at providing the manufacturing method of a flammable polyester fiber product.

  As a result of intensive studies to achieve the above object, the present inventors have made tris (2,3-dibromopropyl) isocyanurate adhere to a polyester fiber to produce a flame-retardant polyester fiber product. A polyurethane resin dispersion obtained from a specific isocyanate group-terminated prepolymer and a specific chain extender is used in combination with the tris (2,3-dibromopropyl) isocyanurate dispersion to form the polyurethane resin and the tris ( By attaching 2,3-dibromopropyl) isocyanurate to the polyester fiber, a flame-retardant polyester fiber product having high friction fastness can be obtained, and tris (2,3-dibromopropyl) Discovered that whitening of textile surface by isocyanurate is sufficiently suppressed and completed the present invention It came to that.

That is, the production method of the flame-retardant polyester fiber product of the present invention,
An organic polyisocyanate compound (a), a high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, and a compound (c) having a carboxyl group and / or a carboxylate group and at least two active hydrogens are reacted. Isocyanate group-terminated prepolymer and / or organic polyisocyanate compound (a), high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, carboxyl group and / or carboxylate group and at least two activities A compound (c) having hydrogen, and an isocyanate group-terminated prepolymer obtained by reacting a chain extender (d);
A step of reacting in water with at least one chain extender (e) selected from the group consisting of a water-soluble polyamine, a water-soluble hydrazine, and derivatives thereof to obtain a polyurethane resin dispersion;
A step of dispersing tris (2,3-dibromopropyl) isocyanurate in water to obtain a dispersion of tris (2,3-dibromopropyl) isocyanurate; and a dispersion of the polyurethane resin and the tris (2,3- A flame retardant processing step of obtaining a flame retardant polyester fiber product by attaching the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate to a polyester fiber using a dispersion of dibromopropyl) isocyanurate;
It is characterized by including.

  In the method for producing a flame-retardant polyester fiber product of the present invention, in the polyurethane resin, a carboxyl group derived from the compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens, and The carboxylate group content is preferably 0.5 to 2% by mass.

  In the flame retardant processing step, after the tris (2,3-dibromopropyl) isocyanurate is attached to the polyester fiber using the dispersion of tris (2,3-dibromopropyl) isocyanurate, The polyurethane resin is adhered to the polyester fiber using a polyurethane resin dispersion, or a treatment liquid containing the polyurethane resin dispersion and the tris (2,3-dibromopropyl) isocyanurate dispersion. It is preferable that the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate are attached to a polyester fiber by using a polyester. Moreover, it is more preferable that the treatment liquid further contains at least one compound selected from the group consisting of a water-dispersible polycarbodiimide compound, a water-dispersible oxazoline compound, and a water-dispersible polyisocyanate compound.

  The reason why the object is achieved by the present invention is not necessarily clear, but the present inventors infer as follows. That is, in the production method of the present invention, a polyurethane resin dispersion obtained from a specific isocyanate group-terminated prepolymer and a specific chain extender is used in combination with a tris (2,3-dibromopropyl) isocyanurate dispersion. As a result, tris (2,3-dibromopropyl) isocyanurate is efficiently attached to impart excellent flame retardancy to the polyester fiber, and a polyurethane resin film is formed on the surface of the polyester fiber. The present inventors speculate that (2,3-dibromopropyl) isocyanurate is suppressed from bleed-out on the fiber surface to cause whitening.

  According to the present invention, a method for producing a flame-retardant polyester fiber product by attaching tris (2,3-dibromopropyl) isocyanurate to a polyester fiber, the flame-retardant polyester having high friction fastness A method for producing a flame-retardant polyester fiber product capable of obtaining a fiber product and sufficiently suppressing whitening of the fiber product surface by tris (2,3-dibromopropyl) isocyanurate Is possible.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  The method for producing a flame-retardant polyester fiber product of the present invention includes a step of obtaining a polyurethane resin dispersion by obtaining an isocyanate group-terminated prepolymer, a step of obtaining a dispersion of tris (2,3-dibromopropyl) isocyanurate, The polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate are attached to the polyester fiber using the polyurethane resin dispersion and the tris (2,3-dibromopropyl) isocyanurate dispersion. It is characterized by including a flame retardant processing step.

(Step of obtaining isocyanate group-terminated prepolymer)
The isocyanate group-terminated prepolymer according to the present invention is
An organic polyisocyanate compound (a), a high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, and a compound (c) having a carboxyl group and / or a carboxylate group and at least two active hydrogens are reacted. Isocyanate group-terminated prepolymer and / or organic polyisocyanate compound (a), high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, carboxyl group and / or carboxylate group and at least two activities This is an isocyanate group-terminated prepolymer obtained by reacting a compound (c) having hydrogen and a chain extender (d).

  The organic polyisocyanate compound (a) may be any organic compound having two or more isocyanate groups, such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds, and the isocyanate groups of these compounds. A blocked polyisocyanate compound blocked with a blocking agent can be used.

  Specific examples of the aliphatic diisocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate.

  Specific examples of the alicyclic diisocyanate compound include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, and norbornane diisocyanate. It is done.

  Specific examples of the aromatic diisocyanate compound include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-. Diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate and xylylene Range isocyanate is mentioned.

  As the blocked polyisocyanate compound, the isocyanate group of the aliphatic diisocyanate compound, the alicyclic diisocyanate compound and the aromatic diisocyanate compound was blocked with a blocking agent such as phenol, alcohol, ethyl malonate, ethyl acetoacetate or the like. Examples thereof include blocked polyisocyanate compounds.

  As said organic polyisocyanate compound (a), you may use individually by 1 type or in combination of 2 or more types. Among these organic polyisocyanate compounds (a), the use of an alicyclic diisocyanate compound is easy because a reaction with water is slow and a dispersion is easy to obtain and less discoloration is caused by ultraviolet rays or nitrogen oxide gas. Preferably, it is more preferable to use isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate.

  The high molecular weight polyol (b) having a number average molecular weight of 400 to 5000 is a compound having two or more hydroxyl groups and having a number average molecular weight of 400 to 5000. In addition, the compound (c) which has the following carboxyl group and / or carboxylate group and at least 2 active hydrogen is not contained. When the number average molecular weight is less than the lower limit, it becomes difficult to sufficiently suppress the whitening of the polyester fiber product. On the other hand, when the number average molecular weight exceeds the upper limit, the viscosity of the polyurethane resin is increased, and thus handling is difficult. It becomes difficult. Further, the number average molecular weight is particularly preferably 1000 to 4000 from the viewpoint that the whitening suppression effect and the ease of handling are further improved. The number average molecular weight is measured by using gel permeation chromatography (GPC), and is obtained by conversion using a calibration curve obtained from a measurement result by GPC of a standard substance having a known number average molecular weight.

  Examples of the high molecular weight polyol (b) having a number average molecular weight of 400 to 5000 include polyester diol, polyether diol, polycarbonate diol, and dimer diol having a number average molecular weight of 400 to 5000 (preferably 1000 to 4000). Be mentioned.

  Specific examples of the polyester diol include polyethylene adipate diol, polyethylene propylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polydiethylene adipate diol, polyethylene terephthalate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene Aliphatic polyester diols such as sebacate diol, polybutylene sebacate diol, poly-ε-caprolactam diol, polyethylene isophthalate diol and poly (3-methyl-1,5-pentylene adipate), polyhexamethylene iso Phthalate diol, 3-methyl-1,5-pentaneisophthalate diol and 3-methyl-1,5-pe Aromatic polyester diols such as Tan terephthalate diol.

  Specific examples of the polyether diol include polyoxytetramethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, and polyoxyethylene / propylene glycol.

  Specific examples of the polycarbonate diol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, 3-methyl-1,5-pentane carbonate diol, and poly-1,4-cyclohexanedimethylene carbonate diol.

  Specific examples of the dimer diol include those mainly composed of a diol obtained by reducing a polymerized fatty acid. Examples of such polymerized fatty acids include polymerized unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid; drying oil fatty acids; semi-drying oil fatty acids; and lower monoalcohol esters of these compounds by Diels-Alder reaction. The reaction product obtained is obtained. As the polymerized fatty acid, various types of commercially available fatty acids are commercially available. For example, typical fatty acids include 0 to 5% by mass of a monocarboxylic acid having 18 carbon atoms and a dimer acid having 36 carbon atoms. A polymerized fatty acid that is 70 to 98% by mass and whose trimer acid having 54 carbon atoms is 0 to 30% by mass is exemplified.

  As the high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, one kind may be used alone, or two or more kinds may be used in combination. Among these high molecular weight polyols (b) having a number average molecular weight of 400 to 5000, polycarbonate diol and aromatic polyester diol are preferred from the viewpoint of excellent hydrolysis resistance, light resistance and heat resistance of the resulting polyurethane resin. Is preferably used.

  The compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens has a carboxyl group and / or a carboxylate group, and further, the carboxyl group and / or the carboxylate group Apart from that, it is a compound having at least two active hydrogens. When the compound (c) has a carboxylate group (c), the carboxylate group can form a carboxylate. In the present invention, by using such a compound (c) as a raw material for the polyurethane resin according to the present invention, a hydrophilic carboxyl group can be introduced into the polyurethane resin, so that it has stable water dispersibility. A polyurethane resin can be obtained. A water-dispersible polyurethane resin can also be obtained by introducing a sulfone group into the polyurethane resin. However, since the polyurethane resin introduced with a sulfone group has a strong affinity for water, It tends to be inferior in washing resistance compared to polyurethane resin.

  Specific examples of the compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2 -Dimethylol heptanoic acid and their ammonium, organic amine or alkali metal salts. Examples of the organic amine constituting the organic amine salt include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, N, N-dimethyldiethanolamine and N, N-diethylethanolamine, and the alkali Examples of the alkali metal constituting the metal salt include sodium and potassium. As the compound (c) having such a carboxyl group and / or carboxylate group and at least two active hydrogens, one kind may be used alone, or two or more kinds may be used in combination.

  As the chain extender (d), a compound having two active hydrogens that react with an isocyanate group can be used. The compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens is not included. As such a chain extender (d), it is preferable to use a low molecular weight polyol having 10 or less carbon atoms and a low molecular weight polyamine having 10 or less carbon atoms. Specific examples of the low molecular weight polyol having 10 or less carbon atoms include ethylene glycol, diethylene glycol, propylene glycol 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol and sorbitol. It is done. Specific examples of the low molecular weight polyamine having 10 or less carbon atoms include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine and triethylenetetramine. As such chain extender (d), one kind may be used alone, or two or more kinds may be used in combination, and among these chain extenders (d), the reactivity to isocyanate groups is moderate. From the viewpoint of being, it is particularly preferable to use a low molecular weight polyol having 10 or less carbon atoms.

  The isocyanate group-terminated prepolymer according to the present invention comprises at least 2 of the organic polyisocyanate compound (a), the high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, and the carboxyl group and / or carboxylate group. Compound (c) having 1 active hydrogen and / or the organic polyisocyanate compound (a), the high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, the carboxyl group and / or the carboxylate group And the compound (c) having at least two active hydrogens, and the chain extender (d) are mixed and subjected to a polyaddition reaction between an isocyanate group and an active hydrogen that reacts with the isocyanate group.

  As the method for the polyaddition reaction, a conventionally known method can be appropriately employed, and it may be a one-stage one-shot method or a multi-stage method. The temperature of such a polyaddition reaction is preferably 40 to 150 ° C., and the reaction time is preferably 90 to 120 minutes. When the temperature and reaction time are less than the lower limit, it tends to be difficult to sufficiently suppress whitening of the polyester fiber product. On the other hand, when the upper limit is exceeded, the viscosity of the polyurethane resin increases. Therefore, it tends to be difficult to handle. In the polyaddition reaction, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine; phosphoric acid, You may add reaction inhibitors, such as sodium hydrogenphosphate and p-toluenesulfonic acid.

  Furthermore, in the said polyaddition reaction, you may add the organic solvent which does not react with an isocyanate group at the time of reaction or after completion | finish of reaction. Examples of such an organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, and butyl acetate. Among these organic solvents, methyl ethyl ketone, toluene, and ethyl acetate are preferably used from the viewpoint of easy removal by heating under reduced pressure.

  Moreover, in the said polyaddition reaction, as mixing ratio of each raw material in a reaction composition, the isocyanate group derived from the said organic polyisocyanate compound (a) and the high molecular weight polyol (b) whose said number average molecular weights are 400-5000. ), The compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens, and the molar ratio of active hydrogens derived from the chain extender (d) (number of moles of isocyanate groups / activity) The number of moles of hydrogen is preferably adjusted to 1.1 / 1.0 to 1.7 / 1.0, and preferably 1.2 / 1.0 to 1.5 / 1.0. It is more preferable to adjust. When the molar ratio is less than the lower limit, it tends to be difficult to obtain the isocyanate group-terminated prepolymer according to the present invention. On the other hand, when the molar ratio exceeds the upper limit, the viscosity of the polyurethane resin increases. It tends to be difficult to handle.

  As an isocyanate group terminal prepolymer concerning this invention, it is preferable that content of the free isocyanate group with respect to the isocyanate group terminal prepolymer whole quantity is 0.8-5.0 mass% at the time of completion | finish of the said polyaddition reaction. When the content of the free isocyanate group is less than the lower limit, the viscosity at the time of reaction is remarkably increased, so that it tends to be necessary to reduce the viscosity using a large amount of an organic solvent. Tends to be difficult to emulsify and disperse. On the other hand, when the content exceeds the upper limit, the temporal stability of the obtained dispersion of the flame-retardant polyurethane resin tends to be lowered.

  Further, the polyaddition reaction further has the carboxyl group and / or carboxylate group remaining in the reaction product containing the isocyanate group-terminated prepolymer thus obtained and at least two active hydrogens. It is preferable to neutralize the carboxyl group of the compound (c) with ammonium, organic amine, alkali metal salt or the like.

  In the production method of the present invention, the reaction product containing the isocyanate group-terminated prepolymer thus obtained is emulsified and dispersed in water to obtain a dispersion of the isocyanate group-terminated prepolymer, and this dispersion is used. It is preferable to obtain the polyurethane resin according to the present invention. Examples of the emulsification dispersion method include a method in which water is added to the reaction product containing the isocyanate group-terminated prepolymer and the mixture is stirred with a device such as a homomixer or a homogenizer. Depending on the situation, an emulsifier may be further added.

  A conventionally well-known thing can be suitably employ | adopted as said emulsifier, A nonionic surfactant and an anionic surfactant are mentioned. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers and fatty acid esters or aromatic carboxylic acid esters thereof; polyoxyalkylene glycols such as polyethylene glycol and polyoxyethylene polyoxypropylene block polymers, and fatty acids thereof. Esters; aromatic polyoxyalkylene ether derivatives such as polyoxyethylene alkylphenyl ether and polyoxyethylene allyl ether, and fatty acid esters thereof. Examples of the anionic surfactant include the nonionic surfactant. And sulfuric acid esters and salts thereof, phosphoric acid esters and salts thereof, and aromatic sulfonic acids. When using such an emulsifier, it is preferable that the addition amount is 5 mass% or less with respect to the said isocyanate group terminal prepolymer. When the usage-amount of an emulsifier exceeds the said upper limit, it exists in the tendency for the flame retardance and friction fastness of a flame-retardant polyester fiber product to fall. By such a method, a dispersion of an isocyanate group-terminated prepolymer in which an isocyanate group-terminated prepolymer is emulsified and dispersed in water can be obtained.

(Process for obtaining a dispersion of polyurethane resin)
The polyurethane resin dispersion according to the present invention can be obtained by reacting the isocyanate group-terminated prepolymer and the chain extender (e) in water. The chain extender (e) according to the present invention is at least one selected from the group consisting of water-soluble polyamines, water-soluble hydrazines, and derivatives thereof.

  The water-soluble polyamine may be a water-soluble compound having two or more amino groups in one molecule, such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2 -The compound illustrated as said chain extenders (d), such as methyl piperazine, isophorone diamine, diethylenetriamine, and triethylenetetramine, hydrazine, tolylenediamine, xylylenediamine, norbornanediamine are mentioned. The derivative of the water-soluble polyamine is not particularly limited as long as it becomes the water-soluble polyamine by hydrolysis reaction or the like in the chain extension reaction solution, and a compound having two primary amines is reacted with a monocarboxylic acid. And monoketiminated products of compounds having two primary amines.

  Examples of the water-soluble hydrazine include 1,1′-ethylenedihydrazine and 1,1′-trimethylenedihydrazine, which are aliphatic compounds having 2 or more hydrazino groups and having 2 to 4 carbon atoms. 1,1 ′-(1,4-butylene) dihydrazine, and the water-soluble hydrazine derivative may be any one that becomes the water-soluble hydrazine by a hydrolysis reaction or the like in the chain extension reaction solution. Well, it is a dihydrazide compound of a dicarboxylic acid having 2 to 10 carbon atoms. And other dihydrazide compounds. As the chain extender (e) according to the present invention, one kind may be used alone, or two or more kinds may be used in combination. The water solubility in the present invention is not limited as long as it can be visually confirmed that it is completely dissolved in water, but the degree thereof is usually 1% by mass or more, preferably 5% by mass or more in pure water. More preferably, it means dissolution of 30% by mass or more.

  In the reaction, the isocyanate group-terminated prepolymer dispersion, the chain extender (e), and, if necessary, water are further mixed, and the isocyanate group-terminated prepolymer and the chain extension in the dispersion are mixed. It is preferable to carry out chain extension reaction with the agent (e). The chain extension reaction can be completed by, for example, reacting at a temperature of 20 to 50 ° C. for 30 to 120 minutes. The mixing ratio of the dispersion of the isocyanate group-terminated prepolymer and the chain extender (e) is such that the amino group and hydrazino group in the chain extender (e) with respect to the free isocyanate group in the isocyanate group-terminated prepolymer The mixing ratio is preferably a chemical equivalent of 0.9 to 1.1 equivalents. When the chemical equivalent is less than the lower limit, it tends to be difficult to sufficiently suppress whitening of the polyester fiber product. On the other hand, when the chemical equivalent exceeds the upper limit, the viscosity of the polyurethane resin increases. It tends to be difficult to handle.

  In the chain extension reaction, the concentration of the polyurethane resin in the resulting dispersion (the concentration of the nonvolatile content of the polyurethane resin in the dispersion) is not particularly limited, but is 1 to 50 from the viewpoint that handling properties are further improved. It is preferably about mass%. Moreover, in the said chain extension reaction, it is preferable to suppress reaction of the isocyanate group in the said isocyanate group terminal prepolymer and water as much as possible. As a method for suppressing such a reaction, specifically, a method of setting the reaction temperature of the isocyanate group-terminated prepolymer and the chain extender (e) to 40 ° C. or less, or a dispersion of the isocyanate group-terminated prepolymer And a method of suppressing the chain extender (e) by further adding a reaction inhibitor such as phosphoric acid or sodium hydrogenphosphate.

  By such a method, a polyurethane resin dispersion in which the polyurethane resin is dispersed in water can be obtained. As the polyurethane resin according to the present invention, the carboxyl group and / or carboxylate group content derived from the compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens is 0.5 to It is preferable that it is 2 mass%. When the content is less than the lower limit, it becomes difficult to disperse the polyurethane resin in water, and there is a tendency that a stable aqueous dispersion cannot be obtained. On the other hand, when the content exceeds the above upper limit, the hydrophilicity of the polyurethane resin is increased, so that the friction fastness of the obtained flame-retardant polyester fiber product is lowered or the viscosity of the polyurethane resin dispersion is increased. Tend to be difficult to handle. Such content of the said carboxyl group and carboxylate group can be adjusted by selecting the kind of said compound (c), and its content suitably. In addition, the content of the carboxyl group and the carboxylate group is determined by diluting the polyurethane resin dispersion with N, N-dimethylformamide or the like, and the acid per total mass of the non-volatile content of the polyurethane resin in the dispersion. It can be determined by measuring the value.

(Step of obtaining a dispersion of tris (2,3-dibromopropyl) isocyanurate)
In the production method of the present invention, tris (2,3-dibromopropyl) isocyanurate is dispersed in water to obtain a dispersion of tris (2,3-dibromopropyl) isocyanurate.

  Examples of the dispersion method include a method in which a mixed solution obtained by adding water and a dispersant to the tris (2,3-dibromopropyl) isocyanurate is wet-dispersed with a bead mill or a homogenizer. Examples of the dispersant include nonionic surfactants and anionic surfactants.

  The nonionic surfactant is not particularly limited, and examples thereof include polyoxyalkylene ether, polyoxyalkylene alkyl ether, polyoxyalkylene allyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl polyhydric alcohol ether, and the like. Can be mentioned.

  The anionic surfactant is not particularly limited, and examples thereof include alkylbenzene sulfonates, α-olefin sulfonates, polyoxyalkylene ether sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene allyl ether sulfates. Sulfate salts such as ester salts, polyoxyalkylene alkyl allyl ether sulfates, polyoxyalkylene alkyl polyhydric alcohol ether sulfates, alcohol sulfates; polyoxyalkylene ether phosphates, polyoxyalkylene alkyl ether phosphates Ester, polyoxyalkylene allyl ether phosphate ester, polyoxyalkylene alkyl allyl ether phosphate ester salt, polyoxyalkylene alkyl poly ester Alcohol ether phosphate, phosphoric acid esters and salts thereof, such as alcohol phosphate esters, and the like. Examples of the salt of the sulfate esterified product and the phosphate esterified product include an alkali metal salt or an amine salt. Examples of the alkali metal constituting the alkali metal salt include lithium, sodium, potassium, and the like. Examples of the amine constituting the salt include primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine, and allylamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, and diallylamine; trimethylamine, Tertiary amines such as triethylamine, tripropylamine, and tributylamine; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Among these, sodium sulfate, potassium salt, and ammonium salt are preferable as the salt of the sulfate esterified product and the salt of the phosphate esterified product from the viewpoint that flame retardance is reduced.

  As the dispersant, one kind may be used alone, or two or more kinds may be used in combination, and the nonionic surfactant and the anionic surfactant may be used simultaneously. The addition amount of such a dispersant is preferably 20% by mass or less with respect to the tris (2,3-dibromopropyl) isocyanurate. In addition, as the amount of water added, the tris (2,3-dibromopropyl) isocyanurate dispersion is obtained from the viewpoint of improving the handleability of the tris (2,3-dibromopropyl) isocyanurate dispersion. It is preferable that the concentration of tris (2,3-dibromopropyl) isocyanurate in the liquid is 10 to 50% by mass.

  Moreover, in the manufacturing method of this invention, you may add protective colloid agents, such as polyvinyl alcohol, carboxymethylcellulose, and starch, to the dispersion liquid of the said tris (2, 3- dibromopropyl) isocyanurate. By using such a protective colloid agent, the dispersibility of tris (2,3-dibromopropyl) isocyanurate dispersed in water can be stabilized. Further, in the production method of the present invention, for the purpose of further stabilizing the dispersion state, methanol, ethanol, 1-propanol, 2-propanol is added to the tris (2,3-dibromopropyl) isocyanurate dispersion. Organic solvents such as alcohols such as 3-methoxy-3-methylbutanol; glycol ethers such as ethylene glycol, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether may be further added.

  In the dispersion of tris (2,3-dibromopropyl) isocyanurate according to the present invention, the particle size of the tris (2,3-dibromopropyl) isocyanurate dispersed in the dispersion is the cumulative volume particle size. The median diameter (d50) at which the integrated volume is 50% from the small diameter side in the distribution is preferably 1.0 μm or less, and more preferably 0.6 μm or less. When the median diameter (d50) exceeds the upper limit, the dispersion state stability tends to decrease. Further, in the cumulative volume particle size distribution, the 90% particle size (d90) at which the cumulative volume is 90% from the small diameter side is more preferably 1.0 μm or less, and particularly preferably 0.8 μm or less. When the 90% particle size (d90) is less than or equal to the upper limit, the dispersed state tends to be more stable. The cumulative volume particle size distribution of the tris (2,3-dibromopropyl) isocyanurate particles in the dispersion can be measured, for example, by a dynamic light scattering method.

(Flame retardant process)
In the flame retardant processing step according to the present invention, the polyurethane resin and the tris (2,3-dibromopropyl) are obtained using the polyurethane resin dispersion and the tris (2,3-dibromopropyl) isocyanurate dispersion. ) Adhere isocyanurate to polyester fiber to obtain a flame retardant polyester fiber product. The polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate may be separately attached to the polyester fiber, or may be attached simultaneously.

  As a method of separately attaching the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate to a polyester fiber, a first dispersion containing a dispersion of the tris (2,3-dibromopropyl) isocyanurate may be used. A step of attaching the tris (2,3-dibromopropyl) isocyanurate to the polyester fiber using a treatment liquid, and a second treatment liquid containing a dispersion of the polyurethane resin before or after the step. And a method including a step of attaching the polyurethane resin to the polyester fiber.

  As the flame retardant processing step according to the present invention, the tris (2,3-dibromopropyl) isocyanurate is used from the viewpoint that the flame retardant effect of the tris (2,3-dibromopropyl) isocyanurate can be further exhibited. The tris (2,3-dibromopropyl) isocyanurate is attached to the polyester fiber using a dispersion liquid, and then the polyurethane resin is attached to the polyester fiber using the polyurethane resin dispersion liquid. Preferably, after the step of attaching the first treatment liquid to the polyester fiber and drying the first treatment liquid, the second treatment liquid is attached to the polyester fiber, and the second treatment is performed. More preferably, the method includes a step of drying the liquid.

  Furthermore, as a flame retardant processing step according to the present invention, from the viewpoint that a flame retardant polyester fiber product having higher friction fastness tends to be obtained, the first treatment liquid is made into a polyester fiber. After the step of adhering and drying, and before the step of adhering the second treatment liquid to the polyester fiber and drying, the polyester fiber obtained by drying the first treatment liquid is reduced and washed. It is preferable to include a step of soaping treatment. As such a soaping treatment, a polyester fiber heated in a bath containing a soaping agent such as Esucudo FRN, Esucudo FZ (manufactured by Nikka Chemical Co., Ltd.) and heated at 80 to 90 ° C. for 10 to 20 minutes is heated. The method of drying (setting) for 3 to 5 minutes at 160-190 degreeC after washing | cleaning and water washing is mentioned.

  The polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate are attached to the polyester fiber at the same time. The polyurethane resin dispersion and the tris (2,3-dibromopropyl) isocyanurate dispersion The polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate are attached to polyester fibers using a treatment liquid (third treatment liquid) containing selenium, and the third treatment liquid is dried. Is mentioned.

  In the production method of the present invention, the adhesion amount of the polyurethane resin to the polyester fiber is not particularly limited, but is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the polyester fiber. More preferably, it is 2 to 5 parts by mass. When the adhesion amount is less than the lower limit, it tends to be difficult to sufficiently suppress whitening of the polyester fiber product, and when it exceeds the upper limit, the flame retardancy of the polyester fiber product tends to decrease. It is in. The concentration of the polyurethane resin in the second treatment liquid and the third treatment liquid is not particularly limited, but is preferably about 1 to 30% by mass. When the concentration is less than the lower limit, it tends to be difficult to sufficiently suppress whitening of the polyester fiber product. On the other hand, when the concentration exceeds the upper limit, the flame retardancy of the polyester fiber product is lowered. There is a tendency.

  In the production method of the present invention, the amount of the tris (2,3-dibromopropyl) isocyanurate attached to the polyester fiber is not particularly limited, but is 0.1 to 20 with respect to 100 parts by mass of the polyester fiber. It is preferable that it is a mass part, and it is more preferable that it is 0.3-10 mass parts. When the adhesion amount is less than the lower limit, a sufficient flame retardant effect tends not to be obtained, and when it exceeds the upper limit, the texture of the polyester fiber product tends to be cured. Further, the concentration of the tris (2,3-dibromopropyl) isocyanurate in the first treatment liquid and the third treatment liquid is not particularly limited, but is preferably about 10 to 50% by mass. When the concentration is less than the above lower limit, the flame retardancy of the polyester fiber product tends to decrease, whereas when it exceeds the above upper limit, the dispersant used for obtaining the dispersion stability (interface) The amount of the active agent) tends to increase, and the flame retardancy of the polyester fiber product tends to be inhibited.

  When the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate are attached to the polyester fiber at the same time, the polyurethane resin and the tris (2,3-dibromopropyl) in the third treatment liquid are used. ) The mass ratio with isocyanurate is preferably 0.1 to 50 parts by mass of the polyurethane resin with respect to 100 parts by mass of the tris (2,3-dibromopropyl) isocyanurate, and 0.5 to 30 parts by mass. More preferably, it is a part. When the content of the polyurethane resin is less than the lower limit, it tends to be difficult to sufficiently suppress whitening of the polyester fiber product. On the other hand, when the content exceeds the upper limit, Flame retardancy tends to decrease.

  In the production method of the present invention, the second treatment liquid and the third treatment liquid are each selected from the group consisting of a water-dispersible polycarbodiimide compound, a water-dispersible oxazoline compound, and a water-dispersible polyisocyanate compound. It is preferable to further contain at least one compound. By containing these compounds, the polyurethane resin is cross-linked and the urethane coating is reinforced, and therefore there is a tendency that a flame-retardant polyester fiber product having better whitening resistance and friction fastness can be obtained. .

  The water-dispersible polycarbodiimide compound is not particularly limited as long as it is a water-dispersible compound having two or more carbodiimide groups. For example, a hydroxyl group or amino group capable of reacting with a polyisocyanate compound and an isocyanate group. And polycarbodiimide resins obtained by reacting a compound having one active hydrogen such as hydrogen in the presence of a carbodiimidization catalyst. Examples of the polyisocyanate compound include hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. Examples of the compound having one active hydrogen that can react with the isocyanate group include monoalkyl ether of polyethylene glycol; monoalkyl ether of random or block copolymer of polyethylene glycol-polypropylene glycol. As such a water-dispersible polycarbodiimide compound, a commercially available NK assist CI (manufactured by Nikka Chemical Co., Ltd.) or the like may be used.

  As the water-dispersible oxazoline compound, a water-dispersible compound having two or more oxazolinyl groups can be used. Examples of such compounds include a copolymer of 2-isopropenyl-2-oxazoline, ethyl acrylate, and methyl methacrylate, a copolymer of 2-isopropenyl-2-oxazoline, and styrene, And a copolymer of propenyl-2-oxazoline, styrene, and acrylonitrile, a copolymer of 2-isopropenyl-2-oxazoline, styrene, butyl acrylate, and divinylbenzene.

  The water-dispersible polyisocyanate compound can be obtained by introducing an alkylene oxide chain as a hydrophilic dispersion chain into the polyisocyanate compound or by blocking the isocyanate group of the polysocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and derivatives thereof.

  The aromatic polyisocyanate is not particularly limited, and for example, tolylene diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate can be used. The aliphatic polyisocyanate is not particularly limited, and for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate can be used. The alicyclic polyisocyanate is not particularly limited, and for example, isophorone diisocyanate and hydrogenated xylylene diisocyanate can be used. For polyester fibers dyed in very dark colors such as black, any of aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates may be used. For polyester fibers dyed in light colors On the other hand, it is preferable to use an aliphatic polyisocyanate or an alicyclic polyisocyanate from the viewpoint of little yellowing. The aromatic polyisocyanate, the aliphatic polyisocyanate, or the alicyclic polyisocyanate derivative is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, biuret structure, isocyanurate A polyisocyanate having a structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure or the like, an adduct of an aliphatic isocyanate of trimethylolpropane, or the like can be used.

  When the water-dispersible polyisocyanate compound is a compound obtained by introducing an alkylene oxide chain as a hydrophilic dispersion chain into the polyisocyanate compound, the average added mole number of alkylene oxide in the alkylene oxide chain is It is preferable that it is 5-50, and it is more preferable that it is 10-30. When the average added mole number of alkylene oxide is less than the lower limit, the self-emulsifying property of the water-dispersible polyisocyanate compound tends to be insufficient, and when it exceeds the upper limit, the water-dispersible polyisocyanate compound There is a tendency that the crystallinity of the material increases and solidifies.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. These may be used alone or in combination of two or more, but it is preferable that 70% by mass or more of the alkylene oxide chain is an ethylene oxide unit. Examples of the compound used for introducing the alkylene oxide chain include polyethylene glycol monoalkyl ether, and monoalkyl ether of a random or block copolymer of ethylene oxide and propylene oxide.

  The proportion of the alkylene oxide chain introduced into the polyisocyanate compound is preferably 2 to 50 parts by mass, and 5 to 30 parts by mass with respect to 100 parts by mass of the obtained water-dispersible polyisocyanate compound. More preferred. When the proportion of the alkylene oxide chain is less than the lower limit, the dispersibility tends to be insufficient because the effect of reducing the interfacial tension of the alkylene oxide chain is weakened. On the other hand, when the above upper limit is exceeded, the reactivity between the isocyanate group of the water-dispersible polyisocyanate compound and water tends to be too high and unstable.

  When the water-dispersible polyisocyanate compound is a compound obtained by blocking an isocyanate group of a polysocyanate compound (hereinafter sometimes referred to as a blocked polyisocyanate compound), the blocking agent Although it does not restrict | limit in particular, For example, a secondary alcohol, a tertiary alcohol, an active methylene compound, a phenol compound, an oxime compound, a lactam compound, and a bisulfite can be used. Examples of the secondary alcohol include sec-butyl alcohol, examples of the tertiary alcohol include t-butyl alcohol, and examples of the active methylene compound include ethyl malonate and acetoacetate. Ethyl acetate is mentioned. Examples of the phenol compound include phenol and m-cresol. Examples of the oxime compound include acetooxime, methyl ketoxime, methyl amyl ketoxime, and diisobutyl ketoxime. Examples of the lactam compound include For example, epsilon caprolactam is mentioned, As said bisulfite, sodium bisulfite and potassium bisulfite are mentioned, for example. As such a blocked polyisocyanate compound, a commercially available NK assist FU (manufactured by Nikka Chemical Co., Ltd.) or the like may be used.

  The blocked polyisocyanate compound can be used stably in an aqueous solution for a long time while maintaining high reactivity of the isocyanate group, and is excellent in dispersibility in water. It can be made to adhere to a polyester fiber in the state of.

  As the water-dispersible polycarbodiimide compound, the water-dispersible oxazoline compound and the water-dispersible polyisocyanate compound, one kind may be used alone, or two or more kinds may be used in combination, but flame retardant From the viewpoint of further improving the fastness to friction in the water-soluble polyester fiber product, it is preferable to use at least one compound selected from the group consisting of a water-dispersible polycarbodiimide compound and a water-dispersible polyisocyanate compound. It is more preferable to use a combination of a water-soluble polycarbodiimide compound and a water-dispersible polyisocyanate compound. When these compounds are contained, the content thereof is preferably 30 parts by mass or less with respect to 100 parts by mass of the polyurethane resin in the second treatment liquid or the third treatment liquid, and 15 parts by mass. The following is more preferable. When the content exceeds the upper limit, the amount of polyurethane resin fixed to the polyester fiber increases, and the flame retardancy of the polyester fiber tends to be inhibited. The water dispersibility in the present invention refers to the property of the compound that can be formed without phase separation of a homogeneous mixture of the compound and water when the compound is mixed in water. The property can be enhanced by a nonionic surfactant or an anionic surfactant as described above as long as the effects of the present invention are not impaired.

  In the manufacturing method of the present invention, the first processing liquid, the second processing liquid, and the third processing liquid (hereinafter, collectively referred to as a flame retardant processing processing liquid) are used. As long as the effect is not impaired, a flame retardant compound other than tris (2,3-dibromopropyl) isocyanurate and other polyester fiber processing agents may be further contained. Examples of the fiber processing agent include an antistatic agent, a water / oil repellent agent, an antifouling agent, a hard finish agent, a texture adjusting agent, a softening agent, an antibacterial agent, a water absorbing agent, an anti-slip agent, and a light fastness improving agent. Etc.

  The method for adhering the flame-retardant processing solution is not particularly limited, and any method can be appropriately employed. For example, a method of immersing polyester fiber in the flame-retardant processing solution (padding method), a spray method A coating method or the like can be used.

  Examples of the padding method include a method in which a polyester fiber product immersed in the flame-retardant processing solution is squeezed with a mangle and the pickup rate is adjusted. Examples of the spray method include an air spray method in which the flame-retardant processing solution is sprayed on a polyester fiber product with compressed air, and an air spray method in which the fluid is sprayed by a hydraulic atomization method. Examples of the coating method include a method using an air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse coater, transfer coater, gravure coater, kiss roll coater, cast coater, curtain coater, calendar coater, etc. And a method using a roller printing machine, a flat screen printing machine, a rotary screen printing machine, and the like.

  Moreover, in the said coating method, you may adjust a viscosity suitable for a process by adding a viscosity modifier to the said flame-retardant processing liquid, respectively. The viscosity modifier is not particularly limited, and examples thereof include polyvinyl alcohol, methyl cellulose, propyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, xanthan gum, starch paste and the like. Furthermore, in the coating method, a foaming agent composed of an anionic surfactant and / or a nonionic surfactant is added to the flame retardant processing solution, and the flame retardant processing solution is foamed and attached to the fiber. A foam processing coating method may be used. According to the foam processing coating method, the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate can be used without waste, and the energy and time required for drying tend to be greatly shortened. In this case, since the adhesion rate may be lowered by the action of the foaming agent, it is important to minimize the amount of the foaming agent used.

  The conditions for drying the flame retardant processing solution are not particularly limited, but are each dried (dried) at 120 to 150 ° C. for 3 to 5 minutes, and then heat treated (cured) at 160 to 190 ° C. for 30 to 90 seconds. It is preferable to do. The curing may be either a dry heat method or a wet heat method. By drying and heat-treating in this manner, the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate tend to be more fixed to the polyester fiber.

  Furthermore, as a flame retardant processing step according to the present invention, from the viewpoint that a flame retardant polyester fiber product having higher friction fastness tends to be obtained, the second treatment liquid is made into a polyester fiber. After the step of adhering and drying and after the step of adhering the third treatment liquid to the polyester fiber and drying, it is preferable that the obtained polyester fiber is subjected to the soaping process described above.

  The polyester fiber according to the present invention is not particularly limited. For example, a polyester fiber such as a regular polyester fiber, a cationic dyeable polyester fiber, and a recycled polyester fiber; a fiber composed of two or more of the polyester fibers; the polyester Fibers composed of fibers and natural fibers such as cotton, hemp, and silk wool; fibers composed of the polyester fibers and semi-synthetic fibers such as rayon and acetate; composed of the polyester fibers and synthetic fibers such as nylon, acrylic, and polyamide. Fiber. Examples of the shape of the polyester fiber according to the present invention include tow, top, casset, woven fabric, knitted fabric, nonwoven fabric, rope, and the like. These include the polyester fiber, carbon, glass, ceramics, asbestos, and metal. It may be a tow, top, casserole, woven fabric, knitted fabric, nonwoven fabric, rope, etc. obtained by blending with inorganic fibers such as.

  In the production method of the present invention, the polyester fiber may be dyed or undyed. When the polyester fiber is dyed, the production method of the present invention preferably includes a step of soaping the polyester fiber in advance by reduction washing before the flame retardant processing step. Generally, the friction fastness of the dyed polyester fiber is not sufficient as it is, and is improved by reduction cleaning. Therefore, before the flame-retardant processing step according to the present invention, the above-mentioned polyester fiber is used. By performing the soaping treatment, a flame-retardant polyester fiber product having higher friction fastness tends to be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(1) Preparation of polyurethane resin dispersion (Synthesis Example 1)
First, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 247.4 g of polyhexamethylene carbonate diol (number average molecular weight 2000), 12.2 g of 2,2-dimethylolbutanoic acid, 0.005 g of dibutyltin dilaurate and 142 g of methyl ethyl ketone were added and mixed uniformly. Next, 72.0 g of 4,4′-dicyclohexylmethane diisocyanate was further added and stirred at 80 ° C. for 240 minutes, so that the content of free isocyanate groups with respect to the total amount of isocyanate group-terminated prepolymer was 1.7% by mass. A methyl ethyl ketone solution of the prepolymer was obtained. This solution was neutralized with 8.3 g of triethylamine and transferred to another container, and an emulsion dispersion of an isocyanate group-terminated prepolymer was obtained using a disper blade while gradually adding 670 g of water at 30 ° C. or lower. A mixed solution composed of 8.8 g of isophoronediamine, 1.0 g of diethylenetriamine and 30 g of water was added to this emulsified dispersion, and the mixture was reacted at 40 ° C. for 90 minutes to synthesize a polyurethane resin. Subsequently, this was heated to 50 ° C. under reduced pressure to remove methyl ethyl ketone, thereby obtaining a polyurethane resin dispersion (nonvolatile content: 35.0 mass%). In the polyurethane resin in the obtained dispersion, the carboxyl group content was 1.47% by mass.

(Synthesis Example 2)
First, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 250.6 g of 3-methyl-1,5-pentaneterephthalate diol (number average molecular weight 2000), 2,2-dimethylol 13.7 g of butanoic acid, 1.2 g of trimethylolpropane, 0.005 g of dibutyltin dilaurate and 143 g of methyl ethyl ketone were added and mixed uniformly. Next, 68.7 g of isophorone diisocyanate was further added and stirred at 80 ° C. for 180 minutes to prepare a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.9% by mass based on the total amount of the isocyanate group-terminated prepolymer. Obtained. This solution was neutralized with 9.3 g of triethylamine and transferred to another container, and an emulsion dispersion of an isocyanate group-terminated prepolymer was obtained using a disper blade while gradually adding 662 g of water at 30 ° C. or lower. A mixed solution composed of 14.7 g of piperazine hexahydrate and 30 g of water was added to this emulsified dispersion and reacted at 40 ° C. for 90 minutes to synthesize a polyurethane resin. Subsequently, this was heated to 50 ° C. under reduced pressure to remove methyl ethyl ketone, thereby obtaining a polyurethane resin dispersion (nonvolatile content: 35.0 mass%). In the polyurethane resin in the obtained dispersion, the carboxyl group content was 1.65% by mass.

(Synthesis Example 3)
First, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 113.8 g of 3-methyl-1,5-pentane terephthalate diol (number average molecular weight 2000), polyhexamethylene carbonate diol ( Number average molecular weight 3000) 142.2 g, 2,2-dimethylolbutanoic acid 12.6 g, dibutyltin dilaurate 0.005 g and methyl ethyl ketone 145 g were added and mixed uniformly. Subsequently, 37.3 g of 4,4′-dicyclohexylmethane diisocyanate and 31.6 g of isophorone diisocyanate were further added and stirred at 80 ° C. for 200 minutes, so that the content of free isocyanate groups relative to the total amount of isocyanate group-terminated prepolymer was 1.8 mass. % Methyl ethyl ketone solution of isocyanate group-terminated prepolymer was obtained. This solution was neutralized with 8.6 g of triethylamine and transferred to another container, and an emulsion dispersion of an isocyanate group-terminated prepolymer was obtained using a disper blade while gradually adding 680 g of water at 30 ° C. or lower. To this emulsified dispersion, a mixed solution consisting of 2.7 g of hydrazine hydrate, 1.1 g of diethylenetriamine and 20 g of water was added and reacted at 40 ° C. for 90 minutes to synthesize a polyurethane resin. Subsequently, this was heated to 50 ° C. under reduced pressure to remove methyl ethyl ketone, thereby obtaining a polyurethane resin dispersion (nonvolatile content: 35.0 mass%). In the polyurethane resin in the obtained dispersion, the carboxyl group content was 1.52% by mass.

(Synthesis Example 4)
First, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 200.0 g of polyhexamethylene carbonate diol (number average molecular weight 2000), 12.2 g of 2,2-dimethylolbutanoic acid, 0.005 g of dibutyltin dilaurate and 142 g of methyl ethyl ketone were added and mixed uniformly. Next, 72.0 g of 4,4′-dicyclohexylmethane diisocyanate was further added and stirred at 80 ° C. for 120 minutes, and then 1.5 g of ethylene glycol was further added and stirred at 80 ° C. for 120 minutes to obtain an isocyanate group-terminated prepolymer. A methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.7% by mass relative to the total amount was obtained. This solution was neutralized with 8.3 g of triethylamine and transferred to another container, and an emulsion dispersion of an isocyanate group-terminated prepolymer was obtained using a disper blade while gradually adding 670 g of water at 30 ° C. or lower. A mixed solution composed of 8.8 g of isophoronediamine, 1.0 g of diethylenetriamine and 30 g of water was added to this emulsified dispersion, and the mixture was reacted at 40 ° C. for 90 minutes to synthesize a polyurethane resin. Subsequently, this was heated to 50 ° C. under reduced pressure to remove methyl ethyl ketone, thereby obtaining a polyurethane resin dispersion (nonvolatile content: 35.0 mass%). In the polyurethane resin in the obtained dispersion, the content of carboxyl groups was 1.70% by mass.

(2) Preparation of test cloth First, disperse dye (Dianix Black HF-B, manufactured by Dystar Japan Co., Ltd.) was 8% o. w. f. (% Owf: ratio of the mass of the dye to the mass of the fiber), 0.5 g / L of a dispersion leveling agent (Nikkasan Salt (registered trademark) RM-340E, manufactured by Nikka Chemical Co., Ltd.) A dyeing solution containing 0.2 cc / L of acetic acid is placed in a pot of a mini-color dyeing machine (manufactured by Teksam Giken Co., Ltd.) and polyester fiber (weighing 360 g / m ² , polyester 100 mass) at 130 ° C. for 60 minutes %) Jersey knit was dyed black (bath ratio of polyester fiber to dyeing solution 1:15). Subsequently, after the dyeing, the soaping agent (Sanmor (registered trademark) RC-700E, manufactured by Nikka Chemical Co., Ltd.) 1 g / L, hydrosulfite 2 g / L, and caustic soda 1 g / L The jersey knit was put and heated at 80 ° C. for 20 minutes for reduction cleaning. The reduced jersey knit was washed with hot water and then washed with water, and the washed jersey knit was dried at 140 ° C. for 3 minutes to obtain a test fabric which was a polyester jersey dyed fabric.

(3) Production of flame-retardant polyester fiber product (Example 1)
First, 40 parts by mass of tris (2,3-dibromopropyl) isocyanurate, 3 parts by mass of an ethylene oxide 20-mole adduct of tristyrenated phenol, and ammonium sulfate ester salt of an ethylene oxide 10-mole adduct of tristyrenated phenol (50 mass) Dispersion of tris (2,3-dibromopropyl) isocyanurate (tris (2,3-dibromopropyl) isocyanurate) dispersed in water using 2 parts by mass and 55 parts by mass of water using a homomixer (1)) was prepared. For this dispersion, the median diameter (d50) determined from the cumulative volume particle size distribution measured by a laser diffraction / scattering type particle size distribution analyzer (trade name: LA-920, manufactured by HORIBA) was 0.5 μm, 90% particle size ( d90) was 0.7 μm. Next, water was added to this dispersion to obtain a first treatment liquid (tris (2,3-dibromopropyl) isocyanurate: 15% by mass), and the sample cloth was immersed in this to obtain a pickup rate of 60% by mass. Padding processing was performed so that The padded sample cloth was dried at 130 ° C. for 3 minutes and further heated at 180 ° C. for 90 seconds. Next, a soap cloth was subjected to a soaping process to obtain a cloth sample to which the first treatment liquid was attached. The soaping treatment is performed by first putting a test cloth in a soaping treatment solution containing 2 g / L of a soaping agent (Escudo FRN, manufactured by Nikka Chemical Co., Ltd.) and 1 g / L of caustic soda at 80 ° C. for 20 minutes. The reduction cleaning was performed, and then the test cloth after the reduction cleaning was washed with hot water, then washed with water, and dried at 170 ° C. for 1 minute.

  Next, water was added to the polyurethane resin dispersion obtained in Synthesis Example 1 to obtain a second treatment liquid (polyurethane resin: 5% by mass). A test cloth having the first treatment liquid attached thereto was immersed in the second treatment liquid, and padding was performed so that the pickup rate was 60% by mass. This test cloth was dried at 150 ° C. for 5 minutes to obtain a flame-retardant polyester fiber product.

(Example 2)
Example 1 was carried out in the same manner as in Example 1 except that the ethylene oxide 20 mol adduct of tristyrenated phenol was not used, and the ammonium sulfate salt (50 wt% aqueous solution) of the ethylene oxide 10 mol adduct of tristyrenated phenol was changed to 5 parts by mass. A dispersion (2) of tris (2,3-dibromopropyl) isocyanurate was prepared. With respect to this dispersion, the median diameter (d50) determined in the same manner as in Example 1 was 0.5 μm, and the 90% particle diameter (d90) was 0.7 μm. Next, a flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that the drying temperature after washing with water in the soaping process was changed to 180 ° C. instead of 170 ° C.

(Example 3)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that the polyurethane resin dispersion obtained in Synthesis Example 2 was used instead of the polyurethane resin dispersion obtained in Synthesis Example 1. .

Example 4
A flame-retardant polyester fiber product was obtained in the same manner as in Example 1 except that the polyurethane resin dispersion obtained in Synthesis Example 4 was used instead of the polyurethane resin dispersion obtained in Synthesis Example 1. .

(Example 5)
A third treatment was carried out by adding water to the dispersion (2) of tris (2,3-dibromopropyl) isocyanurate obtained in the same manner as in Example 2 and the polyurethane resin dispersion obtained in Synthesis Example 1. A liquid (tris (2,3-dibromopropyl) isocyanurate: 15% by mass, polyurethane resin: 5% by mass) was prepared. The test cloth was immersed in this and padded so that the pick-up rate was 60% by mass. The padded sample cloth was dried at 130 ° C. for 3 minutes and further heat-treated at 180 ° C. for 90 seconds to obtain a flame-retardant polyester fiber product.

(Example 6)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 5 except that the polyurethane resin dispersion obtained in Synthesis Example 3 was used instead of the polyurethane resin dispersion obtained in Synthesis Example 1. .

(Example 7)
Instead of the tris (2,3-dibromopropyl) isocyanurate dispersion (2), the tris (2,3-dibromopropyl) isocyanurate dispersion (1) obtained in the same manner as in Example 1, The composition of the third treatment liquid is 15% by mass of tris (2,3-dibromopropyl) isocyanurate, 5% by mass of polyurethane resin, and a water-dispersible polycarbodiimide compound (NK assist CI, manufactured by Nikka Chemical Co., Ltd.) A padding-treated sample cloth was obtained in the same manner as in Example 5 except that the content was 0.4% by mass. This sample cloth was dried at 150 ° C. for 5 minutes to obtain a flame-retardant polyester fiber product.

(Example 8)
The composition of the third treatment solution is 15% by mass of tris (2,3-dibromopropyl) isocyanurate, 5% by mass of polyurethane resin, and blocked polyisocyanate compound (NK assist FU, manufactured by Nikka Chemical Co., Ltd.) 0 A flame-retardant polyester fiber product was obtained in the same manner as in Example 7 except that the content was 3% by mass.

Example 9
Instead of the dispersion (2) of tris (2,3-dibromopropyl) isocyanurate, the dispersion (1) of tris (2,3-dibromopropyl) isocyanurate obtained in the same manner as in Example 1 was used. A third treatment solution was prepared in the same manner as in Example 5 except that. An undyed cloth of polyester fiber (weighing 220 g / m ² , regular weft regular polyester 100% by mass) was dipped in this and padded so that the pickup rate was 60% by mass. This padded cloth was divided into three to be treated cloth 1 to treated cloth 3.

  First, the treated cloth 1 was subjected to a soaping treatment in the same manner as in Example 1 except that it was dried at 140 ° C. for 4 minutes and then the caustic soda in the soaping treatment liquid was changed to 2 g / L. Got. Next, the treated cloth 2 was dried at 140 ° C. for 4 minutes, further heat-treated at 170 ° C. for 90 seconds, and then subjected to a soaping treatment in the same manner as the treated cloth 1 to obtain a flame-retardant polyester fiber product. Next, the treated cloth 3 was dried at 140 ° C. for 4 minutes, further heat-treated at 190 ° C. for 90 seconds, and then subjected to a soaping treatment in the same manner as the treated cloth 1 to obtain a flame-retardant polyester fiber product from each treated cloth. Got.

(Example 10)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 9, except that the polyurethane resin dispersion obtained in Synthesis Example 2 was used instead of the polyurethane resin dispersion obtained in Synthesis Example 1. .

(Example 11)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 9 except that the third treatment liquid obtained in the same manner as in Example 7 was used.

(Comparative Example 1)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 5 except that the polyurethane resin dispersion obtained in Synthesis Example 1 was not used.

(Comparative Example 2)
The composition of the third treatment liquid is tris (2,3-dibromopropyl) isocyanurate 15% by mass, polyacrylate emulsion dispersion (Casesol (registered trademark) ARS-2, manufactured by Nikka Chemical Co., Ltd.) 3 0.2% by mass of water-dispersible polycarbodiimide compound (NK Assist CI, manufactured by Nikka Chemical Co., Ltd.), and blocked polyisocyanate compound (NK Assist FU, manufactured by Nikka Chemical Co., Ltd.) of 0.2% by mass. A flame-retardant polyester fiber product was obtained in the same manner as in Example 5 except that the content was 2% by mass.

(Comparative Example 3)
The composition of the third treatment liquid is 15% by mass of tris (2,3-dibromopropyl) isocyanurate, 10% by mass of the polyester resin emulsion dispersion (Casesol (registered trademark) ES-9, manufactured by Nikka Chemical Co., Ltd.). A flame retardant polyester fiber product was obtained in the same manner as in Example 5 except that the above was obtained.

(Comparative Example 4)
The test cloth was directly used as a polyester fiber product.

(Comparative Example 5)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 9 except that the third treatment liquid obtained in the same manner as in Comparative Example 2 was used.

(Comparative Example 6)
A flame-retardant polyester fiber product was obtained in the same manner as in Example 9 except that the third treatment liquid obtained in the same manner as in Comparative Example 3 was used.

(4) Flame Retardancy Evaluation Using the flame retardant polyester fiber product obtained in Examples 1 to 8 and Comparative Examples 1 to 3 and the polyester fiber product obtained in Comparative Example 4 as samples, it is difficult to carry out the following method. Flammability was measured. In each measurement, the sample before washing with water was obtained by using the obtained textile product as it was, and the sample after washing with water was washed with water five times by the method described in JIS L 1091: 1999. The sample after dry cleaning was obtained by dry-cleaning the obtained fiber product five times by the method described in JIS L 1018: 1999.
(I) 45 ° Micro Burner Method After flame time and combustion area were measured by the A-1 method described in JIS L 1091: 1999.
(Ii) Coil method (flame contact test)
The number of flame contact was measured by the method D described in JIS L 1091: 1999.
The obtained results are shown in Table 1, respectively.

  As is apparent from the results shown in Table 1, it was confirmed that a flame-retardant polyester fiber product excellent in washing resistance and dry cleaning resistance can be obtained by the production method of the present invention.

(5) Measurement of flame retardant component adhesion amount and calculation of flame retardant component adhesion rate First, water was added to the dispersion (1) of tris (2,3-dibromopropyl) isocyanurate obtained in the same manner as in Example 1. This was added to obtain a dispersion having a content of tris (2,3-dibromopropyl) isocyanurate of 6% by mass. A non-dyed cloth of polyester fiber (weighing 220 g / m ² , regular weft regular polyester 100% by mass) is immersed in this dispersion to perform a padding treatment so that the pickup rate becomes 60% by mass. It was dried for 1 minute, and further heated at 170 ° C. for 1 minute to obtain a reference treated cloth. In this treated cloth, the ratio of the mass of attached tris (2,3-dibromopropyl) isocyanurate to the mass of the polyester fiber (MFR ₀ ) was 3.6% o. w. f. Met.

Next, the fluorescent X-ray intensity I ₀ caused by Br in tris (2,3-dibromopropyl) isocyanurate adhering to the treatment cloth obtained was measured using a fluorescent X-ray analyzer (manufactured by SPECTRO Analytical instrument). It was measured. Further, the flame retardant polyester fiber products obtained in Examples 9 to 11 and Comparative Examples 5 to 6 were similarly measured for the fluorescent X-ray intensity I due to Br, and the mass of the polyester fiber in each sample. The mass ratio (MFR (% owf)) of tris (2,3-dibromopropyl) isocyanurate attached to the following formula (i):
MFR (% ow f) = MFR ₀ (% ow f) × I / I ₀ (i)
Determined by

Next, when the total amount of tris (2,3-dibromopropyl) isocyanurate in the treatment liquid is adhered, the ratio of the mass of adhering tris (2,3-dibromopropyl) isocyanurate to the mass of the polyester fiber is expressed as MFR ₁₀₀ ( (Unit:% owf)), the adhesion rate of the flame retardant component is represented by the following formula (ii):
Flame retardant component adhesion rate (%) = MFR / MFR ₁₀₀ × 100 (ii)
Determined by The obtained results are shown in Table 2, respectively. In Table 2, the sample before washing with water was obtained by using the obtained textile product as it was, and the sample after washing with water was washed with water five times by the method described in JIS L 1091: 1999. The sample after dry cleaning was obtained by dry-cleaning the obtained fiber product five times by the method described in JIS L 1018: 1999.

  As is apparent from the results shown in Table 2, in the flame-retardant polyester fiber product obtained by the production method of the present invention, a polyacrylate resin (Comparative Example 5) or a polyester resin (Comparative Example 6) is used. It was confirmed that the adhesion rate of the flame retardant component was higher than that used in combination. Furthermore, it was confirmed that the flame-retardant polyester fiber product obtained by the production method of the present invention has a high adhesion rate of the flame-retardant component even after washing with water and is excellent in washing resistance.

(6) Whitening (powdering) inhibitory evaluation In Examples 1-8 and Comparative Examples 1-3, the drying conditions in each Example and Comparative Example were unified to obtain a flame-retardant polyester fiber product. Evaluation was performed as a sample. As the drying conditions, the conditions for drying the second treatment liquid in Examples 1 to 4 and the conditions for drying the third treatment liquid in Examples 5 to 8 and Comparative Examples 1 to 3 are as follows:
Condition 1: After drying at 140 ° C. for 4 minutes and further heat-treating at 170 ° C. for 90 seconds, soaping treatment was performed in the same manner as in Example 1 except that the caustic soda in the soaping solution was changed to 2 g / L. Condition 2: After drying at 140 ° C. for 4 minutes, heat treatment was further performed at 170 ° C. for 90 seconds. Condition 3: It was assumed that drying was performed at 140 ° C. for 4 minutes.

Evaluation of the whitening (powdering) inhibitory property was carried out by first cutting the samples obtained in each Example and Comparative Example in half, and sandwiching one of them in a large filter paper, and a constant temperature and humidity chamber (jungle tester, manufactured by ESPEC) , Temperature: 70 ° C., relative humidity: 90% RH), and allowed to stand for 4 weeks. The remaining half was sandwiched between large format filter papers and allowed to stand for 4 weeks in a constant temperature and humidity chamber (Okuno Engineering Laboratory Co., Ltd., temperature: 20 ° C., relative humidity 65% RH). Next, the surface of each sample after standing for 4 weeks was observed for whitening (floating), and the following criteria:
1: Significant whitening is observed.
2: Considerable whitening is observed.
3: Whitening is observed.
4: Slight whitening is observed.
5: Whitening is not recognized.
The whitening (powdering) inhibiting property was evaluated according to the above. The obtained results are shown in Table 3.

  As is apparent from the results shown in Table 3, in all samples, no whitening occurred on the sample surface under normal conditions (temperature: 20 ° C., relative humidity 65% RH, 4 weeks) Under the high-temperature and high-humidity conditions (temperature: 70 ° C., relative humidity: 90% RH, 4 weeks) carried out as an accelerated test, significant whitening or considerable whitening occurred in the samples obtained in Comparative Examples 1 to 3. It was confirmed that the effect of suppressing whitening was inferior. On the other hand, no whitening was observed in any of the samples obtained by the production method of the present invention, and it was confirmed that the effect of suppressing whitening was remarkably excellent.

(7) Friction fastness About the polyester fiber product obtained by each Example and the comparative example, according to JIS L 0849: 2004, a friction tester (made by Daiei Chemical Seiki Seisakusho, load: 9N, friction condition: by cotton-plated width) The test was conducted using 100 times friction). The test is carried out under the dry test and wet test conditions, and the degree of contamination of the cotton band after friction is evaluated as follows:
5th grade: No contamination was observed.
4th grade: Slightly contaminated 3rd grade: Contaminated clearly observed 2nd grade: Slightly noticeable contamination 1st grade: Evaluated according to the markedly recognized contamination. Table 4 shows the obtained results.

  As is clear from the results shown in Table 4, the friction fastness of the flame-retardant polyester fiber products (Examples 1 to 8) obtained by the production method of the present invention is excellent in both dry and wet processes. confirmed. In particular, when a water-dispersible polycarbodiimide compound or a blocked polyisocyanate compound was used in combination (Examples 7 to 8), it was confirmed that the friction fastness was further improved. On the other hand, it was confirmed that the friction fastness is remarkably lowered in the case where a polyacrylic ester resin (Comparative Example 2) or a polyester resin (Comparative Example 3) is used in combination.

As described above, according to the method for producing a flame-retardant polyester fiber product by attaching the tris (2,3-dibromopropyl) isocyanurate of the present invention to a polyester fiber, it is difficult to have high friction fastness. A method for producing a flame-retardant polyester fiber product capable of obtaining a flame-retardant polyester fiber product and sufficiently suppressing whitening of the fiber product surface by tris (2,3-dibromopropyl) isocyanurate It becomes possible to provide.

Claims (5)

An organic polyisocyanate compound (a), a high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, and a compound (c) having a carboxyl group and / or a carboxylate group and at least two active hydrogens are reacted. Isocyanate group-terminated prepolymer and / or organic polyisocyanate compound (a), high molecular weight polyol (b) having a number average molecular weight of 400 to 5000, carboxyl group and / or carboxylate group and at least two activities A compound (c) having hydrogen, and an isocyanate group-terminated prepolymer obtained by reacting a chain extender (d);
A step of reacting in water with at least one chain extender (e) selected from the group consisting of a water-soluble polyamine, a water-soluble hydrazine, and derivatives thereof to obtain a polyurethane resin dispersion;
A step of dispersing tris (2,3-dibromopropyl) isocyanurate in water to obtain a dispersion of tris (2,3-dibromopropyl) isocyanurate; and a dispersion of the polyurethane resin and the tris (2,3- A flame retardant processing step of obtaining a flame retardant polyester fiber product by attaching the polyurethane resin and the tris (2,3-dibromopropyl) isocyanurate to a polyester fiber using a dispersion of dibromopropyl) isocyanurate;
A method for producing a flame-retardant polyester fiber product, comprising:   In the polyurethane resin, the content of the carboxyl group and carboxylate group derived from the compound (c) having the carboxyl group and / or carboxylate group and at least two active hydrogens is 0.5 to 2% by mass. The method for producing a flame-retardant polyester fiber product according to claim 1.   In the flame retardant processing step, after the tris (2,3-dibromopropyl) isocyanurate is attached to the polyester fiber using the dispersion of tris (2,3-dibromopropyl) isocyanurate, the polyurethane The method for producing a flame-retardant polyester fiber product according to claim 1, wherein the polyurethane resin is adhered to the polyester fiber using a resin dispersion.   In the flame retardant processing step, the polyurethane resin and the tris (2,3-dibromo) are treated using a treatment liquid containing the polyurethane resin dispersion and the tris (2,3-dibromopropyl) isocyanurate dispersion. The method for producing a flame-retardant polyester fiber product according to claim 1 or 2, wherein propyl) isocyanurate is adhered to the polyester fiber.   The said processing liquid further contains at least 1 sort (s) of compounds selected from the group which consists of a water-dispersible polycarbodiimide compound, a water-dispersible oxazoline compound, and a water-dispersible polyisocyanate compound. Of flame retardant polyester fiber products.