JP2016204528A - Flame retardant aqueous polyurethane resin composition and flame retardant polyester fiber obtained by applying the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based polyurethane resin composition excellent in environmental adaptability, flame retardancy and storage stability and a high flame retardant polyester fiber excellent in environmental adaptability.SOLUTION: There is provided a flame retardant aqueous polyurethane resin composition by dispersing an urethan prepolymer (A) obtained by reacting polyol (a), polyisocyanate (b) and an anionic group introducer (c) and a phosphate ester compound represented by the formula (1) (B) in water and reacting a chain extender (C), with a content of the phosphate ester represented by n=1 of 75 to 85 mass% based on the total amount of the phosphate ester compound (B). (1), where n is an integer of 1 to 5, Rand Rare H or a methyl group, Ris a single bond, O, S, -C(CH)- or -SO-.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a flame retardant aqueous polyurethane resin composition, and in particular, an aqueous polyurethane resin composition containing a specific phosphate ester compound and suitable for flame retardant hard finishing of polyester fibers and the like and flame retardant coating. And a flame-retardant polyester fiber treated with the water-based polyurethane resin composition.

  Backing agent is applied to the fiber surface for the purpose of preventing the falling out of the fiber and improving the strength of the fiber material used for the vehicle interior sheet material such as automobiles and railways and the interior sheet material such as curtains and carpets. A back coat is applied. In particular, sheet materials for automobiles are desired to have flame retardancy from the viewpoint of safety. Conventionally, in order to impart flame retardancy to these sheet materials, hexabromocyclododecane or the like is used. A method of adding a halogen-based flame retardant, an antimony flame retardant such as antimony oxide, or a combination flame retardant to the backing agent has been employed (for example, Patent Document 1). However, while these compounds are excellent in performance as flame retardants, they are recognized as substances that are particularly harmful to ecosystems, so environmentally friendly flame retardant backing agents are required. ing.

  A water-based urethane resin composition in which a phosphorus-based flame retardant is added to a water-based urethane resin has already been proposed as an environmentally friendly backing agent, and this is applied to fibers to obtain a flame-retardant fiber material. (For example, Patent Documents 2 and 3). However, with these methods, although a certain level of flame retardancy is exhibited, it has not been possible to obtain a fiber material having flame retardancy that satisfies market demands. In addition, when the aqueous urethane resin composition is stored for a long period of time, the flame retardant component partially separates and settles, so that there is a disadvantage that the storage stability is insufficient.

  In order to develop flame retardancy, a method of incorporating a phosphorus atom into the main chain of an aqueous urethane resin using a reactive phosphorus-containing compound having a hydroxyl group has also been proposed (for example, Patent Documents 4 and 5). etc). However, in these methods, since phosphorus is incorporated into the resin skeleton, the above storage stability problem is solved, but not only the water resistance when it is made into a fiber material, but also flame retardancy satisfying the market demand. I could not get the fiber material I had.

JP 2009-299199 A JP2013-87122A International Publication No. 2014-045577 JP 2011-236284 A JP 2012-72246 A

As a result of intensive studies to solve the above-described conventional drawbacks, the present inventors have found an aqueous polyurethane resin suitable for stably dispersing a specific phosphorus compound having high flame retardancy in water, and the present invention. Reached.
Accordingly, a first object of the present invention is to provide a water-based polyurethane resin composition excellent in flame retardancy and storage stability using a phosphorus flame retardant excellent in environmental adaptability.
The second object of the present invention is to provide a fiber material that is excellent in environmental adaptability and has high flame retardancy.

但し、上記式（１）におけるｎは１〜５の整数であり、Ｒ^１及びＲ^２は、それぞれ独立して水素原子又はメチル基を表し、Ｒ^３は、単結合、酸素原子、硫黄原子、−Ｃ（ＣＨ_３）_２−、又は−ＳＯ_２−を表す。 That is, the present invention is represented by at least the urethane prepolymer (A) obtained by reacting the polyol (a), the polyisocyanate (b), and the anionic group introducing agent (c) with the following general formula (1). A chain extender (C) is further added to a dispersion obtained by dispersing the phosphoric acid ester compound (B) such that the total amount of the component (A) and the component (B) is 10 to 70% by mass in water. ) And a flame-retardant water-based polyurethane resin composition, and a flame-retardant polyester fiber formed by applying the flame-retardant water-based polyurethane resin composition. However, the content of the phosphate ester represented by n = 1 in the phosphate ester compound (B) is 75 to 85 mass% with respect to the total amount of the phosphate ester compound (B).

Here, n in the formula (1) is an integer from 1 to 5, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or a methyl group, ^{R 3} represents a single bond, an oxygen atom, a sulfur atom, —C (CH ₃ ) ₂ — or —SO ₂ — is represented.

  In the present invention, the polyol (a) is preferably a polyester polyol and / or a polycarbonate diol, and the polyisocyanate (b) is an aliphatic diisocyanate, a dimer of an aliphatic isocyanate, and an aliphatic isocyanate. It is preferably at least one selected from the group consisting of trimers, and the content of the phosphoric ester compound (B) is the content of phosphorus derived from the compound as an aqueous polyurethane resin composition The amount is preferably 0.1 to 3% by mass.

  Since the water-based polyurethane resin composition of the present invention contains a suitable amount of a phosphoric ester mixture having good storage stability, it is a flame retardant water-based polyurethane resin composition excellent in storage stability and environmental suitability. By applying, a fiber material excellent in flame retardancy and environmental suitability can be easily obtained.

  Hereinafter, the flame retardant water-based polyurethane resin composition of the present invention and the flame retardant polyester fiber obtained by coating the same will be described in detail, but the present invention is not limited thereto, and Inventions that can be easily modified by those skilled in the art based on the description are also included in the present invention.

但し、上記式（１）におけるｎは１〜５の整数、Ｒ^１及びＲ^２は、それぞれ独立して水素原子又はメチル基を表し、Ｒ^３は、単結合、酸素原子、硫黄原子、−Ｃ（ＣＨ_３）_２−、又は−ＳＯ_２−を表す。 The flame retardant aqueous polyurethane resin composition of the present invention is a urethane prepolymer (A) prepared by reacting a polyol (a), a polyisocyanate (b), and an anionic group introducing agent (c) by a known method. And the urethane prepolymer composition containing the phosphoric acid ester compound (B) represented by the following general formula (1) so that the component (A) and the component (B) are contained in 10 to 70% by mass in water. And further, the urethane prepolymer of component (A) thus dispersed is crosslinked by a chain extender (C).

However, n in the above formula (1) is an integer of 1 to 5, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ is a single bond, an oxygen atom, a sulfur atom, -C (CH ₃ ) ₂ — or —SO ₂ — is represented.

Although the manufacturing method of the water-based polyurethane resin composition of this invention is not specifically limited, About the preparation of the dispersion liquid containing the said (A) component and (B) component, the following method is mentioned, for example.
(1) A urethane prepolymer is produced by reacting a polyol, polyisocyanate and an anionic group introducing agent, and then a urethane prepolymer composition is prepared by adding a phosphate ester compound, and then further anionic as necessary. A method in which a composition obtained by adding a base neutralizing agent is added and dispersed in an aqueous solution containing an emulsifier as necessary (prepolymer mixing method).
(2) A polyol, polyisocyanate, and an anionic group introducing agent are reacted to produce a urethane prepolymer, and then a phosphoric acid ester compound is added to prepare a urethane prepolymer composition. Then, an aqueous solution to which an anionic group neutralizing agent and / or an emulsifier is added is further added to the prepolymer composition and dispersed (phase inversion method).
In the present invention, a chain extender such as polyamine is added to the urethane prepolymer composition dispersed in water by the above method (1) or (2) to chain extend the urethane prepolymer in water.

When the phosphoric acid ester compound (B) is added, the phosphoric acid ester compound (B) is added after dispersing the urethane prepolymer in water, or after adding the phosphoric acid ester compound in water in advance, When the method of dispersing in water is employed, the phosphoric acid ester compound (B) is separated and settled after the production of the flame retardant aqueous polyurethane resin composition, which is not preferable.
Therefore, in the present invention, as described in the above (1) and (2), it is necessary to mix the phosphate ester compound (B) with the urethane prepolymer (A) and then disperse it in water.

Next, each component of the aqueous polyurethane resin composition of the present invention will be described.
First, the polyol (a) for preparing the urethane prepolymer (A) is not particularly limited and can be appropriately selected from known ones. For example, polyester polyol, polycarbonate diol, polyether polyol and the like can be mentioned. These may be used alone or in combination of two or more.

  Examples of the polyester polyol include ring-opening polymerization of aliphatic polyester polyols obtained by esterifying low molecular weight polyols and polycarboxylic acids, and cyclic ester compounds such as ε-caprolactone and γ-valerolactone. Polyester obtained, these copolyesters, etc. can be used.

Examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, and 1,2-butane. Diol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3 -Propanediol, neopentyl glycol, 2-buty 2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane Aliphatic polyols such as ditrimethylolpropane, tritrimethylolpropane and pentaerythritol; alicyclic structure-containing polyols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; and alkylene oxide adducts of bisphenol A and bisphenol A, Bisphenol-type polyols such as bisphenol S and alkylene oxide adducts of bisphenol S can be used.
Among these, in the present invention, it is preferable to use an aliphatic polyol or an alicyclic structure-containing polyol, and it is more preferable to use an aliphatic diol.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and dimer acid; 1,4-cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid. Alicyclic polycarboxylic acid; orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimellitic acid, pyromellitic Aromatic polycarboxylic acids such as acids; and anhydrides or ester derivatives thereof can be used alone or in combination of two or more. Among these, in the present invention, it is preferable to use an aliphatic polycarboxylic acid, and it is more preferable to use an aliphatic dicarboxylic acid.

  As said polyester polyol, it is preferable to use the polyester polyol which has an aromatic structure from viewpoints, such as the intensity | strength when it is used as a coating film, and chemical resistance, Among these, the low molecular weight which has 2-6 carbon atoms is preferable. What is obtained by reacting a polyol and an aromatic polycarboxylic acid is more preferable.

  As polycarbonate diol which can be used for the said polyol (a), what is obtained by making carbonate and / or phosgene react with the polyol mentioned later can be used, for example.

  Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, diphenyl carbonate, dinaphthyl carbonate, and phenyl naphthyl carbonate.

  Examples of the polyol for producing the polycarbonate diol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5 -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl- 1,3-propanediol, neo Nthyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octane Low molecular weight dihydroxy compounds such as diol, 1,4-cyclohexanedimethanol, hydroquinone, resorcin, bisphenol A, bisphenol F, 4,4′-biphenol, and polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol Alternatively, polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate and polycaprolactone can be used. Among these, in the present invention, it is preferable to use an aliphatic diol, and it is more preferable to use 1,6-hexanediol.

  In addition, as the polyether polyol that can be used for the polyol (a), for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogens as an initiator is used. Can do.

  Examples of the initiator include water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexane Diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, 2-butyl-2-ethyl -1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, diglycerin, trimethylolpropane, Ditrimethylolpropane, tritrimethylolpropane, 1,2,6-hexanetriol, triethanolamine, triisopropanolamine, pentaerythritol, dipentaerythritol, sorbitol, saccharose, ethylenediamine, N-ethyldiethylenetriamine, 1,2-diamino Propane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, diethylenetriamine, phosphoric acid, acidic phosphate ester and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Among the polyester polyols, polycarbonate diols, and polyether polyols described above, polyester polyols or polycarbonate diols are used from the viewpoint of physical properties such as water resistance and strength when the prepared aqueous urethane resin composition is used as a coating film. Is preferable, and polycarbonate diol using 1,6-hexanediol is more preferable.

  The number average molecular weight of the polyol (a) used in the present invention is not particularly limited, but is preferably 300 to 5000, and more preferably 500 to 3000.

  The polyisocyanate (b) for producing the urethane prepolymer (A) in the present invention is not particularly limited and can be appropriately selected from known ones. For example, aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylisocyanate Aliphatic diisocyanates such as diisocyanates, and dimers and trimers of these polyisocyanates, and modified products such as burette isocyanates can be used alone or in combination of two or more. .

  Among the above polyisocyanates, from the viewpoint of light resistance when the produced flame-retardant aqueous urethane resin composition is used as a coating film, aliphatic diisocyanate, aliphatic isocyanate dimer, or aliphatic isocyanate trimer Are preferred, and isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate are particularly preferred.

Examples of the anionic group introducing agent (c) for preparing the urethane prepolymer (A) used in the present invention include carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, and dimethylolvaleric acid. And polyols containing a sulfonic acid group such as 1,4-butanediol-2-sulfonic acid.
Among the anionic group introducing agents, from the viewpoint of easy availability, it is preferable to use a polyol containing a carboxyl group, and it is more preferable to use dimethylolpropionic acid.

Next, the ratio of the polyol (a), the polyisocyanate (b), and the anionic group introducing agent (c), which are components constituting the urethane prepolymer (A), will be described.
In the production of the urethane prepolymer (A) in the present invention, the ratio of the total isocyanate group equivalent of the polyisocyanate (b) and the total hydroxyl group equivalent contained in the polyol (a) and the anionic group introducing agent (c) (NCO When / OH) is less than 1.0, a urethane prepolymer having a hydroxyl group at the terminal is formed. However, the terminal isocyanate prepolymer is generally preferred from the viewpoint of water dispersibility and higher molecular weight due to chain extension, etc., than the urethane prepolymer having a hydroxyl group at the terminal.

Accordingly, in the present invention, the ratio (NCO / OH) is preferably 1.0 or more, but if it is less than 1.1, the urethane prepolymer has a relatively high molecular weight and tends to have poor water dispersibility. The storage stability of the water-based polyurethane resin composition that is the final product may deteriorate.
On the other hand, when the ratio (NCO / OH) exceeds 2.5, production problems such as a rapid foaming caused by carbon dioxide, which is generated in accordance with the reaction between the isocyanate group and water when the prepolymer is dispersed in water, are produced. Moreover, the problem that the adhesiveness with respect to the base material of a coating film is inferior may be produced.

Therefore, in the urethane prepolymer (A) of the present invention, the polyol (a), the polyisocyanate (b), and the anionic group introducing agent so that the ratio (NCO / OH) ratio is 1.1 to 2.5. It is preferable to mix | blend (c), It is more preferable to mix | blend so that it may become 1.2-2.0, It is especially preferable to mix | blend so that it may become 1.3-1.8.
The amount of the anionic group introducing agent (c) is preferably such that the acid value of the urethane prepolymer is 20 to 80 from the viewpoint of easier dispersion in water. Is more preferably 25-50.

  In the production of the urethane prepolymer (A), a solvent which is inert to the reaction and has a high affinity with water may be used as necessary. Suitable examples of such a solvent include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and the like. It is preferable that the usage-amount of these solvents is 3-200 mass parts with respect to 100 mass parts of urethane prepolymers. When using a solvent having a boiling point of 100 ° C. or lower as these solvents, it is preferable to synthesize the aqueous polyurethane resin and then remove the solvent by distillation under reduced pressure or the like.

但し、上記式（１）におけるｎは１〜５の整数であり、Ｒ^１及びＲ^２は、それぞれ独立して水素原子又はメチル基を表し、Ｒ^３は、単結合、酸素原子、硫黄原子、−Ｃ（ＣＨ_３）_２−、又は−ＳＯ_２−を表す。 Next, the phosphate ester compound (B) represented by the following general formula (1) will be described.

Here, n in the formula (1) is an integer from 1 to 5, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or a methyl group, ^{R 3} represents a single bond, an oxygen atom, a sulfur atom, —C (CH ₃ ) ₂ — or —SO ₂ — is represented.

In the present invention, among the phosphate ester compounds (B) represented by the above formula (1), those in which R ³ is a single bond or —C (CH ₃ ) ₂ — are easily available. And preferably a single bond.

  The phosphate ester compound (B) used in the present invention is a mixture of phosphate esters where n is an integer of 1 to 5, but the content of the component where n = 1 is the phosphate ester compound (B). It is necessary that it is 75-85 mass% in the total amount of, and it is preferable that it is 78-82 mass%. When the content of the component where n = 1 is the above-mentioned ratio, the storage stability when the produced flame-retardant aqueous polyurethane resin composition is stored for a long period is good, and the fiber coated with the composition is used. The material can have high flame retardancy. On the other hand, when the content of the component where n = 1 is less than 75% by mass, a fiber material having high flame retardancy is obtained although the storage stability of the aqueous polyurethane resin composition is good. I can't. Moreover, when there is more content of the component which is n = 1 than 85 mass%, although the fiber material which has high flame retardance is obtained, the storage stability of a water-based polyurethane resin composition falls remarkably.

  The proportion of the phosphate ester compound (B) contained in the urethane prepolymer composition before being dispersed in water is the phosphorus content derived from the phosphate ester compound (B) with respect to the total amount of the aqueous polyurethane resin composition. It is preferable to mix | blend so that it may become 0.1-3 mass%, and it is more preferable to mix | blend so that it may become 0.5-2 mass%. When the phosphorus content is less than 0.1% by mass, the flame retardancy tends to be insufficient. When the phosphorus content is more than 3% by mass, the viscosity of the urethane prepolymer composition is increased and water is added. Tends to be difficult to disperse.

  The method for synthesizing the phosphate ester compound (B) is not particularly limited. For example, 4,4′-dihydroxybiphenyl is reacted with phenol and phosphorus oxychloride in the presence of a catalyst such as magnesium chloride to remove the phosphoric acid ester compound (B). It can be synthesized by hydrochloric acid. In this case, the content ratio of the phosphoric acid ester compound of n = 1 can be adjusted to 75-85 mass% by adjusting the usage-amount of phosphorus oxychloride with respect to 4,4'-dihydroxybiphenyl. The preferred amount of phosphorus oxychloride to be used is 3.0 to 5.5 moles, more preferably 3.5 to 4.5 moles per mole of 4,4'-dihydroxybiphenyl.

In order to disperse the urethane prepolymer composition in water, in the present invention, an anionic group neutralizing agent and / or an emulsifier is used as necessary.
Examples of the anionic group neutralizing agent include trialkylamines such as trimethylamine, triethylamine, and tributylamine; N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, 1- N, N-dialkylalkanolamines such as dimethylamino-2-methyl-2-propanol; tertiary amine compounds of trialkanolamines such as N-alkyl-N, N-dialkanolamines and triethanolamine; ammonia And basic compounds such as trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

  In the present invention, among these anionic group neutralizing agents, from the viewpoint of improving the weather resistance and water resistance after drying, it is preferable to use a highly volatile one that is easily dissociated by heat. Preference is given to using trimethylamine or triethylamine. These neutralizing agents may be used alone or in combination of two or more.

  The amount of the anionic group neutralizing agent used in the present invention is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents per 1 equivalent of anionic group. preferable. If the amount of the anionic group neutralizing agent used is too large or insufficient, it is difficult to disperse the urethane prepolymer composition in water, the storage stability of the aqueous urethane resin composition is reduced, and There is a possibility that problems such as deterioration of mechanical properties such as strength of the water-based urethane resin film and various physical properties such as water resistance may occur.

  Examples of the emulsifier used in the present invention include ordinary anionic surfactants and nonionic surfactants, primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, and the like. There may be mentioned known surfactants such as cationic surfactants such as pyridinium salts and amphoteric surfactants such as betaine type, sulfate type and sulfonic acid type.

  Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate; polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; sodium Alkyl sulfonates such as sulforicinoleate, alkali metal salts of sulfonated paraffins, ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine abiates; sodium benzenesulfonate, alkali phenol Alkyl aryl sulfonates such as alkali metal sulfates of hydroxyethylene High alkyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, dialkyl sulfosuccinate, polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl aryl sulfate salt, polyoxyethylene ether phosphate, polyoxyethylene alkyl ether acetic acid Salts, N-acylamino acid salts, N-acylmethyltaurine salts and the like.

  Examples of the nonionic surfactant include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; and alcohols having 1 to 18 carbon atoms. Examples include ethylene oxide and / or propylene oxide adduct, ethylene oxide and / or propylene oxide adduct of alkylphenol, ethylene glycol and / or propylene oxide adduct of alkylene glycol and / or alkylene diamine, and the like.

  Examples of the alcohol having 1 to 18 carbon atoms constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, tertiary amyl alcohol, Examples include hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, and stearyl alcohol.

  Examples of the alkylphenol include phenol, methylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 3,5-di-tert-butylphenol, 4- (1,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, and Bisphenol F etc. are mentioned.

  Examples of the alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1 , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. Can be mentioned. Moreover, as alkylenediamine, what substituted the alcoholic hydroxyl group of these alkylene glycol by the amino group etc. are mentioned. Further, the ethylene oxide and propylene oxide adducts may be random adducts or block adducts.

  Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazolinium. Examples thereof include laurate.

  Examples of the amphoteric surfactant include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethyl Examples include betaine types such as metal salts of carboxymethyl betaine and hydroxypropyl phosphate; amino acid types such as metal salts of β-laurylaminopropionic acid, sulfate ester types, and sulfonic acid types.

  In the present invention, among the above-mentioned emulsifiers, it is preferable to use a nonionic surfactant that is easily available and can be used at low cost, and fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; It is more preferable to use an ethylene oxide and / or propylene oxide adduct of an alcohol having 1 to 18 carbon atoms.

  The amount of the emulsifier used is 100 parts by mass of the total amount of the components (A) to (C) in the polyurethane resin from the viewpoint of the water resistance of the coating film obtained by applying the flame retardant aqueous urethane resin composition. It is preferable that it is 0-30 mass parts with respect to it, It is more preferable that it is 0-20 mass parts, It is most preferable not to use an emulsifier component.

  Examples of the chain extender (C) for extending the water-dispersed urethane prepolymer composition in water include ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1. , 3-propanediol, diethylene glycol, triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2 , 4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2 Aliphatic diols such as methyl-1,8-octanediol and 1,9-nonanediol; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, piperazine, 2 -Low molecular diamines such as methylpiperazine; polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; mensen diamine, isophorone diamine, norbornene diamine, aminoethylaminoethanol, bis (4-amino-3-methyldicyclohexyl) ) Methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) unde Cycloaliphatic diamines such as m-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine Polyamines such as aromatic diamines such as diethyltoluenediamine and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene; succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, 1, Hydrazines such as 6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide; Hydra Emissions, and water, and the like.

  In the present invention, among these, diamines, hydrazides and hydrated hydrazine or water are preferably used from the viewpoints of availability and reaction, and ethylenediamine, adipic acid dihydrazide, hydrazine hydrate or water is preferably used. It is particularly preferred to use it.

  The amount of the chain extender used is such that the equivalent ratio of the chain extender to the isocyanate reactive group is 1 equivalent to the isocyanate group in the urethane prepolymer before the chain extension reaction, from the viewpoint of the film properties of the aqueous polyurethane resin. The amount is preferably in the range of 0.1 to 1.0.

In the water-based polyurethane resin composition of the present invention, various commonly used additives can be added as necessary within a range not inhibiting the effects of the present invention.
Specific examples of these additives include, for example, cross-linking agents, various weathering agents (hindered amine light stabilizers, ultraviolet absorbers and antioxidants), silane coupling agents that particularly enhance adhesion to substrates, and colloidal Inorganic colloidal sol such as silica or colloidal alumina, tetraalkoxysilane and its condensation polymer, chelating agent, epoxy compound, pigment, dye, film-forming aid, curing agent, external cross-linking agent, viscosity modifier, leveling agent, antifoaming agent , Anticoagulant, radical scavenger, heat resistance imparting agent, inorganic or organic filler, plasticizer, lubricant, fluorine or siloxane antistatic agent, reinforcing agent, catalyst, thixotropic agent, wax Examples thereof include a clouding agent, an antibacterial agent, an antifungal agent, an antiseptic and an antirust agent.

  Examples of the crosslinking agent include adducts of urea, melamine, benzoguanamine and the like with formaldehyde; amino resins such as alkyl ether compounds composed of these adducts and alcohols having 1 to 6 carbon atoms; polyfunctional epoxy compounds; A functional isocyanate compound; a blocked isocyanate compound; a polyfunctional aziridine compound; Specific examples of these include oxazoline compounds, epoxy compounds, carbodiimide compounds, aziridine compounds, melamine compounds, and zinc complexes.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Triazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- hydroxy -4- _(3-C 12 ~C ₁₃ mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylpheny ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 1,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5 Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5 -Di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-di-tert Benzoates such as 3 butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyl Substituted oxanilides such as oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; and various Examples include metal salts or metal chelates, particularly nickel or chromium salts or chelates.

Examples of the antioxidant include phosphorus-based, phenol-based, and sulfur-based antioxidants. Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, and tris (nonylphenyl). Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octyl phosphite, Diphenyl decyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, di Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra _{(C 12} alkyl _{-C 15} mixed alkyl alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis ( 4,6-diamy Phenyl)]-isopropylidene diphenyl phosphite, tetratridecyl-4,4′-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl) -5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis) 3-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine N-6-yl) oxy] ethylamine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-tetrakis (1,1-dimethylethyl) Dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] propyl] phenol, and 2-butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol Monophosphite etc. are mentioned.

  Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditertiarybutyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditertiarybutyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy) -3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propyl Lopionate], tocopherol and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic esters of polyols.

  The amount of the weathering agent (hindered amine light stabilizer, ultraviolet absorber and antioxidant) used is 0.001 based on 100 parts by mass of the total amount of the components (A) to (C) in the aqueous polyurethane resin composition. It is preferably 10 to 10 parts by mass, more preferably 0.01 to 5 parts by mass. If the amount is less than 0.001 part by mass, a sufficient addition effect may not be obtained. If the amount is more than 10 parts by mass, water dispersion stability and physical properties of the coating film may be adversely affected.

  As a method of adding these weathering agents, a method of adding to a urethane raw material polyol, a method of adding to a urethane prepolymer, a method of adding to a water phase during water dispersion of the urethane prepolymer, a method of adding after water dispersion Any method may be used, but from the viewpoint of easy operation, a method of adding to the raw material polyol and a method of adding to the urethane prepolymer are preferable.

The flame-retardant polyester fiber of the present invention is a product obtained by treating a polyester fiber with a treatment liquid containing the aqueous polyurethane resin composition of the present invention.
As the treatment liquid, the water-based polyurethane resin composition of the present invention may be used as it is, but it is preferable to use a solution obtained by appropriately diluting the water-based polyurethane resin composition.

  The concentration of the polyurethane resin in the treatment liquid is not particularly limited, but is preferably 1 to 20% by mass in the treatment liquid. In addition, components other than the water-based polyurethane resin composition can be further appropriately added to the treatment liquid.

  The polyester fiber treated using the water-based polyurethane resin composition of the present invention and the treatment method are not particularly limited. For example, for various polyester fiber materials such as knitted fabrics and non-woven fabrics, the water-based polyurethane resin composition is directly or diluted, and is applied by an arbitrary method such as a padding method, a coating method, or a spray method, and dried. It is possible to obtain a flame-retardant polyester-based fiber. This makes it possible to improve the strength against pulling, tearing, abrasion, and the like without reducing the flame retardancy of the fabric to be treated. Thus, the polyester fiber in the present specification is a concept including not only a single fiber but also a fiber processed product.

  Moreover, the drying temperature after performing the (application | coating) process by the water-based polyurethane resin composition of this invention to a polyester-type fiber raw material is not restrict | limited in particular, You may air dry at room temperature or heat-dry. Also good. Usually, from a viewpoint of processing efficiency, drying is performed at 80 to 200 ° C. for about 1 minute to 5 hours. In addition, when treating polyester fiber materials, any flame retardant may be used in combination as a flame retardant aid, even if a water-based polyisocyanate, carbodiimide, oxazoline, or epoxy crosslinking agent is used in combination. Also good.

The amount of the water-based polyurethane resin composition imparted to the flame retardant polyester fiber of the present invention is the amount of the phosphorus compound of the component (B) when no phosphorus-containing compound is used in addition to the component (B) in the present invention. It is preferable that the derived phosphorus content is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyester fiber.
Hereinafter, the present invention will be described more specifically using examples and comparative examples. In the following examples and the like,% is based on mass unless otherwise specified.

<Synthesis Example 1: Synthesis of phosphate ester compound (P-1)>
To 186.2 g (1 mol) of 4,4′-dihydroxybiphenyl, 0.95 g (0.01 mol) of magnesium chloride was added as a catalyst, and 844.9 g (3.8 mol) of phosphorus oxychloride was added. For 3 hours. Excess phosphorus oxychloride was distilled off under reduced pressure, and then 376.4 g (4.0 mol) of phenol was added and reacted at 120 to 140 ° C. for 7 hours. The obtained crude product was dissolved in xylene, washed with an aqueous solution containing an acid, dehydrated and desolvated to obtain a phosphate ester (P-1).

  Moreover, the content of the compound corresponding to n = 1 is calculated | required with respect to the total amount of each compound corresponding to n = 1-5 in General formula (1) in P-1 by the liquid chromatograph measurement by the following conditions. As a result, it was 80.1 mass%. The content of the remaining phosphate ester is 16.8% by mass for the compound corresponding to n = 2 in the formula (1), 2.8% by mass for the compound corresponding to n = 3, and the compound corresponding to n = 4. Was 0.3 mass%, and the compound corresponding to n = 5 was 0 mass%.

<Synthesis Example 2: Synthesis of phosphate ester compound (P-2)>
To 186.2 g (1 mol) of 4,4′-dihydroxybiphenyl, 0.95 g (0.01 mol) of magnesium chloride was added as a catalyst, and 667.0 g (3.5 mol) of phosphorus oxychloride was added. For 3 hours. Excess phosphorus oxychloride was distilled off under reduced pressure, and then 376.4 g (4.0 mol) of phenol was added and reacted at 120 to 140 ° C. for 7 hours. The obtained crude product was dissolved in xylene, washed with an aqueous solution containing an acid, dehydrated and desolvated to obtain a phosphate ester compound (P-2).
Moreover, the content of the compound corresponding to n = 1 is calculated | required with respect to the total amount of each compound corresponding to n = 1-5 in General formula (1) in P-2 by the liquid chromatograph measurement by the following conditions. As a result, it was 76.0 mass%. The content of the remaining phosphate ester is 19.2% by mass for the compound corresponding to n = 2 in the formula (1), 4.1% by mass for the compound corresponding to n = 3, and the compound corresponding to n = 4. Was 0.7% by mass, and the compound corresponding to n = 5 was 0% by mass.

<Synthesis Example 3: Synthesis of Phosphate Ester Compound (P-3)>
To 186.2 g (1 mol) of 4,4′-dihydroxybiphenyl, 0.95 g (0.01 mol) of magnesium chloride was added as a catalyst, and 889.3 g (4 mol) of phosphorus oxychloride was added. Reacted for hours. After excess phosphorus oxychloride was distilled off under reduced pressure, 423.5 g (4.5 mol) of phenol was added and reacted at 120 to 140 ° C. for 7 hours. The obtained crude product was dissolved in xylene, washed with an aqueous solution containing an acid, dehydrated and desolvated to obtain a phosphate ester compound (P-3).
Moreover, the content of the compound corresponding to n = 1 with respect to the total amount of each compound corresponding to n = 1 to 5 in the general formula (1) in P-3 by liquid chromatographic measurement under the following measurement conditions. As a result, it was 84.9% by mass. The content of the remaining phosphate ester is 9.4 mass% for the compound corresponding to n = 2 in the formula (1), 5.1 mass% for the compound corresponding to n = 3, n The content of the compound corresponding to = 4 was 0.6% by mass, and the content of the compound corresponding to n = 5 was 0% by mass.

Synthesis Example 4 Synthesis of Phosphate Ester Compound (P-4) 0.95 g (0.01 mol) of magnesium chloride as a catalyst was added to 186.2 g (1 mol) of 4,4′-dihydroxybiphenyl, and phosphorus oxychloride was added to 600 .3 g (2.7 mol) was added and reacted at 80-100 ° C. for 3 hours. Excess phosphorus oxychloride was distilled off under reduced pressure, and then 376.4 g (4.0 mol) of phenol was added and reacted at 120 to 140 ° C. for 7 hours. The obtained crude product was dissolved in xylene, washed with an aqueous solution containing an acid, dehydrated and desolvated to obtain a phosphate ester compound (P-4).
Moreover, the content of the compound corresponding to n = 1 is calculated | required with respect to the total amount of each compound corresponding to n = 1-5 in General formula (1) in P-4 by the liquid chromatograph measurement by the following conditions. As a result, it was 70.5 mass%. The content of the remaining phosphate ester is 22.2% by mass for the compound corresponding to n = 2 in the formula (1), 5.6% by mass for the compound corresponding to n = 3, n The content of the compound corresponding to = 4 was 1.6% by mass, and the content of the compound corresponding to n = 5 was 0.1% by mass.

<Synthesis Example 5: Synthesis of Phosphate Ester Compound (P-5)>
To 186.2 g (1 mol) of 4,4′-dihydroxybiphenyl, 0.95 g (0.01 mol) of magnesium chloride was added as a catalyst, and 1500.8 g (6.3 mol) of phosphorus oxychloride was added. For 3 hours. After excess phosphorus oxychloride was distilled off under reduced pressure, 423.5 g (4.5 mol) of phenol was added and reacted at 120 to 140 ° C. for 7 hours. The obtained crude product was dissolved in xylene, washed with an aqueous solution containing an acid, dehydrated and desolvated to obtain a phosphate ester compound (P-5).
Moreover, the content of the compound corresponding to n = 1 is calculated | required with respect to the total amount of each compound corresponding to n = 1-5 in General formula (1) in P-5 by the liquid chromatograph measurement on the following conditions. As a result, it was 89.8 mass%. The content of the remaining phosphate ester is 7.0% by mass for the compound corresponding to n = 2 in the formula (1), 3.2% by mass for the compound corresponding to n = 3, and the compound corresponding to n = 4. Was 0% by mass, and the compound corresponding to n = 5 was 0% by mass.

<Measurement conditions of liquid chromatograph>
Apparatus: JASCO Corporation, Pump (PU-2089 PLUS),
Detector (MD-2018 PLUS)
Column: manufactured by Senshu Scientific Co., Ltd. (PEGASIL ODS φ4.6 mm × L250 mm)
Column temperature: 40 ° C
Detection wavelength: 261 nm
Developing solvent: MeOH / 0.3% phosphoric acid aqueous solution

<Manufacture of urethane prepolymer composition>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 365 g (0.19 mol) of Duranol S-6002 (polycarbonate diol having a number average molecular weight of 2000, manufactured by Asahi Kasei Chemicals Corporation) as a polyol. In addition, 248 g (1.1 mol) of isophorone diisocyanate was added as a polyisocyanate, 71.5 g (1.07 mol) of dimethylolpropionic acid was added as an anionic group introducing agent, and 238.3 g of N-ethyl-pyrrolidone was further added. After mixing uniformly, it was made to react at 110-120 degreeC for 3 hours. It was confirmed that the isocyanate content (NCO%) was 1.72%, and further, 51.3 g (0.51 mol) of triethylamine and 1025 g of P-1 were added and mixed uniformly to obtain a urethane prepolymer composition. (UP-1) was obtained. The NCO% is an amount defined by JIS K 1603-1, and means the mass% of NCO groups in the urethane prepolymer containing a solvent.

<Water dispersion / high molecular weight process>
To a 1 L plastic container equipped with a disper, add 574.7 g of water and 0.02 g of Adecanate B-1016 (antifoaming agent, manufactured by ADEKA Corporation) and mix uniformly, and then add UP-1 at 30 to 35 ° C. 399.2g was added and it stirred at 30 degreeC for 15 minutes. Next, 9.74 g (ethylene diamine 0.082 mol) of a mixture having a mass ratio of (ethylene diamine / water) of 1/3 was added dropwise as a chain extender and stirred at 30 ° C. for 1 hour. After confirming disappearance of the NCO group, an aqueous polyurethane resin PUD-1 was obtained.
The solution of PUD-1 was evaluated by carrying out a storage stability test, a UL94 standard VTM test, and a flame retardance test by a 45-degree coil method by the method described below.

<Storage stability test>
The obtained PUD-1 solution was put in a glass bottle, allowed to stand for 1 month in an atmosphere at 25 ° C., and the appearance was visually evaluated as follows.
A: No separation of the resin was observed at all B: Slight separation of the resin or precipitation of the resin was observed C: Many separation of the resin or precipitation of the resin was observed

<UL94 standard VTM test>
The obtained PUD-1 solution was applied onto a PET film having a length of 21 cm, a width of 30 cm, and a thickness of 0.1 mm using a bar coater so that the thickness of the urethane resin was 1 μm. After leaving still at 24 degreeC, it was made to heat-dry at 120 degreeC for 1 hour, and the PET film by which the polyurethane resin was apply | coated was produced.
The obtained PET film coated with polyurethane resin was cut into a size of 20 cm × 5 cm and wound around an aluminum metal rod having a diameter of 12.7 mm to prepare a test piece for UL94 standard VTM test.
About this test piece, the flame retardance test was performed and determined according to UL (Underwriters Laboratories) "Test for Flammability of Plastic Materials UL 94". As a judgment method, the above-mentioned test piece was kept vertical, the flame of the burner was removed after indirect flame was burned for 3 seconds at the lower end, and the time when the fire that ignited the test piece disappeared was measured. Next, at the same time that the fire was extinguished, a second flame contact was performed for 3 seconds, and the time for the ignited fire to extinguish was measured as in the first time. Moreover, it was also evaluated at the same time whether or not the cotton under the test piece was ignited by the falling fire type.
The combustion rank was given according to UL-94 standard from the 1st and 2nd combustion time, the presence or absence of cotton ignition, etc. The combustion rank of VTM-0 is the highest, and the flame retardancy decreases as VTM-1 and VTM-2. However, those not corresponding to any of the ranks of VTM-0 to VTM-2 were defined as NR.

<Flame retardance test by 45 degree coil method>
A padding treatment in which the obtained PUD-1 solution was immersed in a commercially available polyester felt having a length of 10 cm, a width of 10 cm, and a thickness of 1 mm was performed and dried at 150 ° C. for 3 hours. Then, the felt made from polyester containing PUD-1 was cut | disconnected so that one side might be 10 cm and mass might be 1 g, and the resin processed cloth was obtained.
A coil with an inner diameter of 10 mm and a length of 150 mm is prepared from a hard stainless steel wire having a diameter of 0.5 mm as defined in JIS G 4309 so that the distance between each other is 2 mm. A test piece of a resin processed cloth provided with a wire was prepared.
The above test piece is wound around an aluminum metal rod having a diameter of 12.7 mm, and the test piece is brought into contact with the flame of the burner oriented in the vertical direction so that the angle is 45 degrees. Judgment was made as follows.
When the test piece ignites, remove the test piece from the burner, confirm that the fire of the test piece has extinguished, repeat the above test with the test piece in contact again, and the test piece burns out and ignites. The number of flame contact until it stopped was measured. The greater the number of times of contact and ignition, the higher the flame retardancy, and the lower the number of ignition times, the lower the flame retardance.

  A water-based polyurethane resin PUD-2 was obtained in the same manner as in Example 1 except that P-2 was used instead of P-1. The obtained PUD-2 was evaluated in the same manner as in Example 1 by carrying out a storage stability test, a UL94 standard VTM test, and a 45 degree coil method flame retardancy test.

  A water-based polyurethane resin PUD-3 was obtained in the same manner as in Example 1 except that P-3 was used instead of P-1. The obtained PUD-3 was evaluated in the same manner as in Example 1 by carrying out a storage stability test, a UL94 standard VTM test, and a 45 degree coil method flame retardancy test.

Comparative Example 1
A water-based polyurethane resin PUD-4 was obtained in the same manner as in Example 1 except that P-4 was used instead of P-1. The obtained PUD-4 was evaluated in the same manner as in Example 1 by conducting a storage stability test, a UL94 standard VTM test, and a flame retardance test by a 45-degree coil method.

Comparative Example 2
A water-based polyurethane resin PUD-5 was obtained in the same manner as in Example 1 except that P-5 was used instead of P-1. The obtained PUD-5 was evaluated in the same manner as in Example 1 by conducting a storage stability test, a UL94 standard VTM test, and a flame retardance test by a 45-degree coil method.

Comparative Example 3
<Manufacture of urethane prepolymer composition>
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 365 g (0.19 mol) of Duranol S-6002 as a polyol, 248 g (1.1 mol) of isophorone diisocyanate as a polyisocyanate, As an anionic group-introducing agent, 71.5 g (1.07 mol) of dimethylolpropionic acid was added, and 238.3 g of N-ethyl-pyrrolidone was added and mixed uniformly, followed by reaction at 110 to 120 ° C. for 3 hours. It was. It was confirmed that the isocyanate content (NCO%) was 1.72%, and further 51.3 g (0.51 mol) of triethylamine was added and mixed uniformly to obtain a urethane prepolymer composition (UP-2). Got.

<Water dispersion / high molecular weight process>
To a 1 L plastic container equipped with a disper, add 574.7 g of water and 0.02 g of Adecanate B-1016 and mix uniformly, then add 204.7 g of UP-2 at 30 to 35 ° C., and stir at 30 ° C. for 15 minutes. did. Next, 9.74 g (ethylene diamine 0.082 mol) of (ethylenediamine / water) mixture having a mass ratio of 1/3 was added dropwise as a chain extender and stirred at 30 ° C. for 1 hour to confirm that the NCO group disappeared. did. Then, 194.5g of P-1 was added, and it was made to stir at 30 degreeC for 1 hour, and water-based polyurethane resin PUD-6 was obtained. From the obtained PUD-6, as soon as the stirring was stopped, a component considered to be phosphorus-containing compound P-1 was separated. For this reason, about PUD-6, the storage stability test similar to Example 1, the UL94 standard VTM test, and the flame retardance test by a 45 degree | times coil method were not able to be performed.

表１の結果から、本発明の水系ポリウレタン樹脂組成物は、貯蔵安定性が良好である上、ポリエステルフィルム、及びポリエステル繊維に対して良好な難燃性を付与できることが確認された。 Table 1 shows the evaluation results of Examples 1 to 3, Comparative Example 1, and Comparative Example 2.

From the results of Table 1, it was confirmed that the water-based polyurethane resin composition of the present invention has good storage stability and can impart good flame retardancy to the polyester film and polyester fiber.

  Since the water-based polyurethane resin composition of the present invention is excellent in storage stability, it can be used not only for various resin products and paints, but also for the polyester fiber material of the present invention to which this resin composition is applied. Since it has high flame retardancy, it is suitable for vehicle interior sheet materials such as automobiles and railways, and interior sheet materials such as curtains and carpets, and is extremely useful industrially.

Claims (5)

A urethane prepolymer (A) obtained by reacting at least a polyol (a), a polyisocyanate (b), and an anionic group introducing agent (c), and a phosphate ester compound represented by the following general formula (1) ( A chain extender (C) is further added to the dispersion obtained by dispersing B) so that the total amount of the component (A) and the component (B) is 10 to 70% by mass in water. A flame retardant aqueous polyurethane resin composition, wherein the content of the phosphate ester represented by n = 1 in the phosphate ester compound (B) is the phosphate ester compound (B) It is 75-85 mass% with respect to the total amount.

Here, n in the formula (1) is an integer from 1 to 5, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or a methyl group, ^{R 3} represents a single bond, an oxygen atom, a sulfur atom, —C (CH ₃ ) ₂ — or —SO ₂ — is represented. The flame-retardant water-based polyurethane resin composition according to claim 1, wherein the polyol (a) is a polyester polyol and / or a polycarbonate diol. 3. The polyisocyanate (b) is at least one selected from the group consisting of aliphatic diisocyanates, aliphatic isocyanate dimers, and aliphatic isocyanate trimers. Flame retardant aqueous polyurethane resin composition. The content of the phosphoric acid ester compound (B) is an amount of 0.1 to 3% by mass in the aqueous polyurethane resin composition as the content of phosphorus derived from the compound. The flame-retardant water-based polyurethane resin composition described in any one. A flame retardant polyester fiber obtained by applying the flame retardant water-based polyurethane resin composition according to any one of claims 1 to 4.