Flame retardant for fiber containing phosphorus-containing polymer and flame-retardant fiber product

Abstract

To provide a phosphorus-based flame retardant exhibiting both superior initial flame retardance and superior durability against washing.SOLUTION: The present invention relates to a phosphorus-containing (meth)acrylic polymer comprising one or more specific phosphorus compounds as a (meth)acrylic monomer (A), and a flame retardant for fiber containing the same.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a flame retardant for textiles and flame retardant textile products containing a novel phosphorus-containing polymer. [Background technology]

[0002] While textile products are required to be flame retardant, they are also required to have the property of maintaining the desired flame retardant effect even after repeated washing (washing durability).

[0003] Currently, halogen compounds such as hexabromocyclododecane and tris(2,3-dibromopropyl)isocyanurate are known as flame retardants that can satisfy the requirements for flame retardancy and washing durability.Specific examples include a method of adding the flame retardant during melt spinning of raw yarn, and a method of contacting the flame retardant during processing after fiberization.In these methods, after adding the flame retardant, heat is applied to efficiently fix the flame retardant component, thereby carrying out flame retardant processing so as to maintain washing durability.

[0004] However, in light of recent global efforts to address environmental issues, there is a strong demand for a voluntary reduction in the use of halogenated compounds, which tend to generate toxic gases when burned. In light of this current situation, phosphorus-based flame retardants such as various phosphate ester compounds (Patent Documents 1-2), phosphonate ester compounds, and phosphinate ester compounds (Patent Documents 2-7) have been proposed as halogen-free flame retardant components that can be used both in the production stage of raw yarns and in post-processing in the form of woven or knitted fiber fabrics.

[0005] These low molecular weight phosphorus-containing compounds can impart flame retardancy to fibers by, for example, adding an appropriate amount during the production stage of raw yarn (e.g., during melt spinning) or by adding an appropriate amount to the dye solution of woven or knitted fiber fabrics and performing a same-bath exhaust process, but they have the following drawbacks.

[0006] First, phosphate ester compounds are often liquid, oily, or viscous fluids that have poor affinity for fibers, and therefore tend to exhibit plasticizer properties in the fibers, causing the dyes and flame retardants to bleed out.

[0007] Second, many of these phosphorus-containing compounds have very low fixation rates (exhaustion rates) when used on polyester fibers in a dye-and-exhaust bath. While high-temperature treatment of fibers is available to improve flame retardant fixation, few of these methods achieve sufficient fixation to improve wash durability. Another method for fixing flame retardants involves simultaneously attaching the flame retardant to the fibers and coating them with a synthetic resin such as a sizing agent to prevent removal. However, this method results in changes in appearance and hardening of the texture, significantly impairing the inherent characteristics of the textile product. Furthermore, heat treatment for fixation can lead to bleed-out problems, as well as problems with processing and the working environment, such as the generation of white smoke and mist due to the flame retardant's sublimation or thermal decomposition at high temperatures. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-328445 [Patent Document 2] International Publication No. WO2007-032277 [Patent Document 3] Special Publication No. 56-16798 [Patent Document 4] Special Publication No. 56-9178 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-275473 [Patent Document 6] Japanese Patent Application Laid-Open No. 2006-83491 [Patent Document 7] Japanese Patent Application Laid-Open No. 2005-9041 Summary of the Invention [Problem to be solved by the invention]

[0009] Thus, there is a strong demand for the development of a phosphorus-based flame retardant for textiles that can be uniformly attached to the fiber surface by post-processing of textile products, that has adhesion to the fiber itself, and that can melt, soften, penetrate and fix to the fiber, thereby providing initial flame retardancy as well as washing durability. However, at present, such a phosphorus-based flame retardant has not yet been developed.

[0010] Therefore, a main object of the present invention is to provide a phosphorus-based flame retardant which has excellent initial flame retardancy as well as excellent washing durability. [Means for solving the problem]

[0011] As a result of extensive research into achieving the above object, the present inventors have found that a phosphorus-containing polymer having a specific chemical structure can achieve the above object, and have thus completed the present invention.

[0012] That is, the present invention relates to a flame retardant for fibers and a flame-retardant fiber product containing the following phosphorus-containing polymer. 1. The following general formula (I): [ka] [In the formula, R1 represents a hydrogen atom or a methyl group; L1 and L2 are the same or different and represent an oxygen atom or an imino (NH) group; and R2 represents a hydrocarbon group which may be substituted with a substituent containing at least one of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom.] A phosphorus-containing (meth)acrylic polymer containing one or more phosphorus compounds represented by the following formula (A) as a (meth)acrylic monomer: 2. The phosphorus-containing (meth)acrylic polymer according to claim 1, having a weight average molecular weight Mw (where Mw indicates the relative weight average molecular weight based on standard polystyrene as measured with a differential refractometer by gel permeation chromatography) of 1,000 to 20,000. 3. A flame retardant for fibers, comprising the phosphorus-containing (meth)acrylic polymer according to item 1. 4. The flame retardant for fibers according to item 3, further comprising an aqueous medium and being liquid. 5. The flame retardant for textiles according to item 3, which is used for flame-retarding textile products by post-processing. 6. A flame-retardant fiber product comprising synthetic fibers and the flame retardant for fibers described in item 3 above. 7. The flame-retardant textile product according to item 6, wherein the synthetic fibers include polyester fibers. [Effects of the Invention]

[0013] According to the present invention, a phosphorus-based flame retardant having excellent initial flame retardancy and washing durability can be provided, that is, a flame retardant for fibers that can effectively suppress or prevent deterioration of flame retardancy caused by washing can be provided.

[0014] The flame retardant for fibers of the present invention can provide a high level of flame retardancy to textile products and at the same time, can also provide excellent washing durability (particularly washing durability in water), thereby enabling good flame retardancy to be maintained for a relatively long period of time.

[0015] The flame retardant of the present invention makes it possible to relatively easily flame-retard non-flame-retardant textile products through post-processing. Conventional techniques can temporarily impart flame retardancy to textile products by post-processing with a low-molecular-weight flame retardant, but the flame retardant falls off after washing, resulting in a decrease in flame retardancy. In contrast, the flame retardant for textiles of the present invention makes it possible to easily impart high flame retardancy to textile products, and because the polymer itself possesses flame retardancy, adhesion, and flexibility, it is possible to obtain flame-retardant textile products that combine high flame retardancy with washing durability. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 shows an IR chart of the phosphorus-containing polymer (Synthesis Example 12). [Figure 2] FIG. 2 shows an IR chart of the phosphorus-containing polymer (Comparative Example 5). DETAILED DESCRIPTION OF THE INVENTION

[0017] 1. Phosphorus-containing polymers The phosphorus-containing polymer of the present invention (polymer of the present invention) has the following general formula (I): [ka] [In the formula, R1 represents a hydrogen atom or a methyl group; L1 and L2 are the same or different and represent an oxygen atom or an imino (NH) group; and R2 represents a hydrocarbon group which may be substituted with a substituent containing at least one of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom.] The composition is characterized in that it contains one or more phosphorus-based compounds represented by the following formula (A):

[0018] In this specification, unless otherwise specified, the term "(meth)acrylic monomer" collectively refers to a monomer containing an acryloyl group and a monomer containing a methacryloyl group, and the term "(meth)acrylic compound" collectively refers to a compound containing an acryloyl group and a compound containing a methacryloyl group.

[0019] The polymer of the present invention contains the above-mentioned phosphorus-based compound as the (meth)acrylic monomer (A). That is, the polymer of the present invention includes not only a polymer of the (meth)acrylic monomer (A) but also a polymer of the (meth)acrylic monomer (A) with other monomers. The polymer of the (meth)acrylic monomer (A) further includes a) a polymer of one type of the (meth)acrylic monomer (A) and b) a polymer of two or more types of the (meth)acrylic monomer (A).

[0020] In general formula (I), R1 represents a hydrogen atom or a methyl group. L1 and L2 are the same or different and represent an oxygen atom or an imino (NH) group. Therefore, the following cases are included: when L1 and L2 are both oxygen atoms, when both are imino groups, when L1 is an oxygen atom and L2 is an imino group, and when L1 is an imino group and L2 is an oxygen atom. Furthermore, R2 represents a hydrocarbon group (alkylene group) which may be substituted with a substituent containing at least one of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. Therefore, R 2 may be an unsubstituted alkylene group. The substituent may be any one that can be used within a range that does not impair the effects of the present invention, and examples thereof include a phenoxy group (C6H5-O-). The number of carbon atoms in the hydrocarbon group is not limited, but is usually preferably 2 to 12 (including the number of carbon atoms in the substituent). The hydrocarbon group may be linear, branched, cyclic, or the like, with linear hydrocarbon groups being particularly preferred. The hydrocarbon group may be saturated or unsaturated.

[0021] The phosphorus-based compound to be the (meth)acrylic monomer (A) may be one kind of phosphorus-based compound among the phosphorus-based compounds represented by the general formula (I) above, or may be two or more kinds of phosphorus-based compounds among the phosphorus-based compounds represented by the general formula (I) above.

[0022] In the polymer of the present invention, the content of the (meth)acrylic monomer (A) is not particularly limited, but is usually about 50 to 100% by weight, and particularly preferably 70 to 100% by weight. Therefore, the polymer of the present invention may have a (meth)acrylic monomer (A) content of 100% by weight, in which case it may be either a homopolymer composed of one type of (meth)acrylic monomer (A) or a copolymer composed of two or more types of (meth)acrylic monomer (A). The copolymer may be any of an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer.

[0023] In the polymer of the present invention, when the content of the (meth)acrylic monomer (A) is less than 100% by weight, other monomers (A') may be contained within the range that does not impair the effects of the present invention. As the other monomers (A'), phosphorus-free (meth)acrylic compounds can be preferably used from the viewpoint of improving adhesion to substrates or dispersibility and compatibility in water or organic solvents.

[0024] Specific examples of phosphorus-free (meth)acrylic compounds include at least one of (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate; and polyethylene glycol (meth)acrylate having ethylene oxide as a repeating unit, but are not limited to these.

[0025] The proportion of the other monomer (A') in the polymer of the present invention may be the remainder of the content of the (meth)acrylic monomer (A) in the polymer of the present invention, and can be set to, for example, about 0 to 30% by weight, but is not limited thereto.

[0026] The weight-average molecular weight of the polymer of the present invention is usually 1,000 to 20,000, and preferably 1,000 to 10,000. In this case, the weight-average molecular weight refers to the polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight-average molecular weight is less than 1,000, the polymer is considered to be in almost the same state as a low-molecular-weight compound, and therefore sufficient washing durability may not be obtained. On the other hand, if the molecular weight exceeds 20,000, the dispersibility and compatibility in water or organic solvents may be significantly reduced, making handling difficult.

[0027] 2. Method for producing phosphorus-containing polymers, etc. (1) Method for producing phosphorus compounds The method for producing the phosphorus-based compound of the present invention is not particularly limited, but for example, the following method can be suitably adopted: That is, a method for producing the phosphorus-based compound represented by the above general formula (I), (a) reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with a trihalogenoisocyanurate to form a compound represented by the following general formula (II): [ka] [wherein X represents a halogen atom] (first step) obtaining a compound represented by the formula: (b) a step (second step) of reacting the compound represented by the general formula (II) with a (meth)acrylic compound having a hydroxy group and / or an amino group in the presence of an organic amine; The phosphorus-based compound of the present invention can be suitably obtained by a production method including the steps of:

[0028] 1st process In the first step, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is reacted with a trihalogenoisocyanurate to obtain the compound represented by the above general formula (II).

[0029] The trihalogeno isocyanurate used in step (a) is represented by the general formula (V): [ka] [In formula:X 1 , X 2 and X 3 and are the same or different and represent a halogen atom. The trihalogeno isocyanurate may be one type or two or more types.

[0030] X 1 , X 2 and X 3 The halogen atom represented by the formula (I) is not particularly limited, and examples thereof include a chlorine atom and a bromine atom.

[0031] From the viewpoints of ease of handling and economic efficiency, the trihalogeno isocyanurate is preferably a trihalogeno isocyanurate represented by the general formula (V) where X 1 , X 2 and X 3 A compound in which all of the groups are chlorine atoms (trichloroisocyanurate) is preferred. Trichloroisocyanurate is a compound known as a disinfectant and sterilant for pools, and commercially available products can also be used. Examples of commercially available products include "Star Trichloron PG (granular effective chlorine 90%)" from Nankai Chemical Co., Ltd. and "Neochlor 90W (granular effective chlorine 90%)" from Shikoku Chemical Co., Ltd.

[0032] The amount of trihalogenoisocyanurate used is not limited, but from the viewpoints of yield, ease of synthesis, etc., it is usually about 0.1 to 1 mol, particularly preferably 0.2 to 0.6 mol, and even more preferably 0.3 to 0.4 mol, per 1 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0033] The above reaction can be carried out in the presence of an organic solvent, if necessary. That is, a liquid phase reaction can be suitably employed. The organic solvent is not limited, and general aprotic organic solvents can be used, such as hydrocarbon solvents such as benzene, toluene, xylene, and n-hexane; ether solvents such as tetrahydrofuran and dioxane; and ester solvents such as ethyl acetate and butyl acetate. These can be used alone or in combination of two or more. Among these, hydrocarbon solvents are preferred in the present invention.

[0034] The reaction temperature in the first step is not particularly limited, but from the viewpoint of reaction yield, purity, etc., it is preferably 50°C or lower, and more preferably 0 to 40°C, and even more preferably 0 to 20°C (especially after all the trihalogenoisocyanurate has been added).

[0035] In a preferred embodiment of the present invention, for example, a step of intermittently adding a trihalogenoisocyanurate to a raw material liquid containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and an organic solvent can be suitably employed. In this way, by adjusting the amount of trihalogenoisocyanurate added each time, the liquid temperature can be easily controlled within the above range.

[0036] The reaction time for the above reaction is not particularly limited and can be, for example, about 10 minutes to 8 hours, and is particularly preferably 30 minutes to 4 hours.

[0037] Thus, in the first step, a compound of the general formula (II): [ka] [In the formula: X represents a halogen atom.] A compound represented by the formula:

[0038] The halogen atom represented by X is determined depending on the halogen atom in the trihalogenoisocyanurate used in Step 1. For example, when trichloroisocyanurate is used, X in the compound obtained in Step 1 will be a chlorine atom.

[0039] The progress of the reaction in the first step can be monitored by a conventional method such as chromatography. The structure of the reaction product can be determined by, for example, elemental analysis, MS (ESI-MS) analysis, IR analysis, 1 H-NMR, 13 It can be identified by C-NMR or the like.

[0040] After completion of the reaction in the first step, the solvent is distilled off, and the reaction product can be isolated and purified by a conventional method such as chromatography, recrystallization, etc. In the present invention, the reaction product in the first step can also be directly subjected to the second step without isolation and purification.

[0041] 2nd process In the second step, the compound represented by the general formula (II) is reacted with a (meth)acrylic compound having a hydroxyl group and / or an amino group in the presence of an organic amine. Through this reaction, the halogen group X in the general formula (II) is esterified to introduce an acryloyl group or a methacryloyl group.

[0042] The (meth)acrylic compound may be any compound having a hydroxy group and / or an amino group, and examples thereof include at least one of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)methacrylamide, N-(hydroxyethyl)acrylamide, N-(hydroxyethyl)methacrylamide, N-(4-hydroxyphenyl)acrylamide, and N-(4-hydroxyphenyl)methacrylamide, but are not limited to these.

[0043] The amount of the (meth)acrylic compound having a hydroxy group and / or an amino group used is not limited, but from the viewpoints of yield, ease of synthesis, etc., it is usually about 0.5 to 1.5 moles, particularly preferably 0.8 to 1.2 moles, and even more preferably 1.0 to 1.1 moles per mole of the compound represented by the general formula (II).

[0044] The above reaction can be carried out in the presence of an organic solvent, if necessary. That is, a liquid phase reaction can be suitably employed. The organic solvent is not limited, and general aprotic organic solvents can be used, such as hydrocarbon solvents such as benzene, toluene, xylene, and n-hexane; ether solvents such as tetrahydrofuran and dioxane; and ester solvents such as ethyl acetate and butyl acetate. These can be used alone or in combination of two or more.

[0045] The organic amine used in the second step is not particularly limited, and examples thereof include at least one tertiary amine such as trimethylamine (TMA), triethylamine (TEA), tripropylamine (TPA), tributylamine (TBA), pyridine, N,N-dimethylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, and 4-dimethylaminopyridine. Among these, trialkylamines such as TMA, TEA, TPA, and TBA are preferred, and triethylamine is more preferred from the viewpoints of ease of use, cost, and the like.

[0046] If necessary, various additives can be added in the second step, such as a polymerization inhibitor such as dibutylhydroxytoluene.

[0047] The reaction temperature in the second step is not particularly limited, but is preferably 50°C or lower, particularly preferably 0 to 40°C, from the viewpoint of reaction yield, purity, etc.

[0048] The reaction time for the above reaction can be, for example, about 10 minutes to 8 hours, but is not limited to this.

[0049] The progress of the reaction in the second step can be monitored by a conventional method such as chromatography. The structure of the reaction product can be analyzed by, for example, elemental analysis, MS (ESI-MS) analysis, IR analysis, 1 H-NMR, 13 It can be identified by C-NMR or the like.

[0050] After completion of the reaction in the second step, the solvent is distilled off, and the reaction product can be isolated and purified by a conventional method such as chromatography, recrystallization, etc. In this way, the desired phosphorus compound can be obtained.

[0051] (2) Method for producing phosphorus-containing polymer The phosphorus-containing polymer of the present invention can be suitably produced by a method including a step of subjecting raw materials containing one or more phosphorus-based compounds represented by the above general formula (I) to a polymerization reaction.

[0052] As described above, the raw material may be any of (a) a raw material containing one phosphorus-based compound as the phosphorus-based compound represented by the general formula (I), (b) a raw material containing two or more phosphorus-based compounds as the phosphorus-based compounds represented by the general formula (I), (c) a raw material containing one phosphorus-based compound as the phosphorus-based compound represented by the general formula (I) and a phosphorus-free (meth)acrylic compound, and (d) a raw material containing two or more phosphorus-based compounds as the phosphorus-based compounds represented by the general formula (I) and a phosphorus-free (meth)acrylic compound.

[0053] In the polymerization reaction, various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and precipitation polymerization can be used, but from the viewpoint of precise molecular weight control at a molecular weight of 20,000 or less, solution polymerization is preferred.

[0054] When solution polymerization is employed, polymerization can be carried out by a commonly known method. For example, a phosphorus-containing polymer can be obtained by using raw materials containing a phosphorus compound and, if necessary, a chain transfer agent, adding these to an organic solvent, and stirring the solution while heating in the presence of a polymerization initiator and replacing the atmosphere with an inert gas such as nitrogen or argon.

[0055] The reaction conditions can be appropriately set depending on, for example, the reaction solvent used, but the phosphorus-containing polymer can usually be obtained by continuing stirring at a temperature of about 40 to 120° C. for about 1 to 48 hours.

[0056] As the chain transfer agent, known or commercially available chain transfer agents can be used. Examples of the chain transfer agent include mercaptocarboxylic acids such as thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and thiomalic acid; mercaptocarboxylic acid esters such as methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and dipentaerythritol hexakis(3-mercaptopropionate). Examples of suitable chain transfer agents include, but are not limited to, esters; alkyl mercaptans such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, and 1,2-dimercaptoethane; mercaptoalcohols such as 2-mercaptoethanol, 4-mercapto-1-butanol, and α-thioglycerol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol, and 2-naphthalenethiol; disulfides such as 2-hydroxyethyl disulfide and tetraethyl thiuram disulfide; dithiocarbamates such as benzyl diethyl dithiocarbamate; and monomer dimers such as α-methylstyrene dimer. These may be used alone or in combination. In the present invention, it is particularly desirable to use mercaptocarboxylic acids as chain transfer agents.

[0057] The amount of chain transfer agent added during polymerization is not particularly limited, but is preferably about 0.01 to 0.5 equivalents, and more preferably 0.05 to 0.3 equivalents, per equivalent of the phosphorus-containing (meth)acrylic monomer (general formula I).

[0058] As the polymerization initiator, known or commercially available polymerization initiators can be used, including peroxide-based polymerization initiators, azo-based polymerization initiators, redox-based polymerization initiators, etc. More specific examples include at least one of 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionate)dimethyl, 4,4'-azobis(4-cyanovaleric acid), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, etc.

[0059] The amount of the polymerization initiator used is not limited, but it is usually suitable to use it in the range of 0.01 to 5 parts by weight per 100 parts by weight of the phosphorus-containing (meth)acrylic monomer.

[0060] When the above-mentioned monomer components are polymerized by solution polymerization, the solvent used for polymerization is not particularly limited as long as it is inert to the polymerization reaction. At least one of water and an organic solvent can be used as the solvent. Examples of the organic solvent include monoalcohols such as methanol, ethanol, isopropanol, and n-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran, dioxane, and 4-methyltetrahydropyran; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. glycol ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, and other glycol monoether esters;Examples of suitable solvents include alkyl esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, and ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane, and octane; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and phosphorus-containing solvents such as chloroform and dichloroethane. These may be used alone or in combination.

[0061] The amount of the organic solvent used is not particularly limited, but it can usually be used in the range of 100 to 5000 parts by weight per 100 parts by weight of the phosphorus-containing (meth)acrylic monomer.

[0062] 3.Flame retardants for textiles The present invention encompasses a flame retardant for fibers (the flame retardant of the present invention) containing the polymer of the present invention. The flame retardant of the present invention can be suitably used to impart flame retardancy to fibers (particularly synthetic fibers, preferably polyester fibers). More specifically, the flame retardant of the present invention can be suitably used to impart flame retardancy to textile products by post-processing.

[0063] The flame retardant of the present invention may contain a secondary component as needed, as long as the effect of the present invention is not impaired. For example, a halogen-free flame retardant component (hereinafter also referred to as a "second flame retardant component") can be suitably used as a component other than the polymer of the present invention.

[0064] The second flame-retardant component may be, for example, a phosphorus-containing compound, a nitrogen-containing compound, a sulfur-containing compound, a silicon-containing compound, or an inorganic metal compound, as long as the flame-retardant function of the polymer of the present invention is not impaired. In the present invention, these second flame-retardant components may be used alone or in combination of two or more. Furthermore, known or commercially available second flame-retardant components may also be used.

[0065] Examples of the phosphorus-containing compound include a) amine salts or metal salts of non-condensed or condensed phosphoric acids such as red phosphorus, phosphoric acid, and phosphorous acid; b) inorganic phosphorus-containing compounds such as boron phosphate; and c) phosphorus-containing ester compounds such as phosphoric orthophosphate esters or condensates thereof, phosphoric ester amides, phosphonic acid esters, and phosphinic acid esters.

[0066] Examples of the nitrogen-containing compound include a) triazine or triazole compounds or salts thereof [metal salts, (poly)phosphates, sulfates], b) urea compounds, (poly)phosphoric acid amides, hindered amines (HALS, particularly NOR-type HALS, etc.), etc.

[0067] Examples of the sulfur-containing compound include a) organic sulfonic acids (alkanesulfonic acids, arenesulfonic acids) or metal salts thereof, b) sulfonated polymers, and c) organic sulfonic acid amides or salts thereof (ammonium salts, metal salts).

[0068] Examples of the silicon-containing compound include a) resins containing (poly)organosiloxane, b) elastomers containing (poly)organosiloxane, c) silicone-based compounds such as oils containing (poly)organosiloxane, and d) zeolites.

[0069] Examples of the inorganic metal compound include compounds other than those mentioned above, such as a) metal salts of inorganic acids such as antimonates and borates, b) metal oxides such as antimony trioxide and antimony pentoxide, c) metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and d) metal sulfides.

[0070] The content of the second flame-retardant component is not particularly limited, but can be appropriately set within the range of, for example, the polymer of the present invention / second flame-retardant component (weight ratio) = 100 / 1 to 100 / 50, particularly within the range of 100 / 1 to 100 / 10.

[0071] The properties of the flame retardant of the present invention are not particularly limited and can be appropriately changed depending on the form, purpose, application, target of use, etc. Furthermore, the same form as that of known or commercially available flame retardants (or flame retardant processing agents) can also be adopted. Therefore, for example, forms such as a solution, dispersion, emulsion, aerosol, etc. can be suitably adopted. That is, the polymer of the present invention can be dissolved or dispersed in water, an organic solvent, etc., depending on the type, shape, etc. of the textile product. The concentration (solid content) of the polymer of the present invention when dissolved or dispersed is usually suitably adjusted to a range of about 1 to 50% by weight, but is not limited thereto.

[0072] In the case of a solution in which the polymer of the present invention is dissolved in an organic solvent, the polymer of the present invention may be dissolved by stirring in the organic solvent. In the case of a dispersion or emulsion in an aqueous medium, it is desirable to enhance the dispersibility and emulsification properties by adding a dispersant, an emulsifier, etc. as necessary. The dispersant or emulsifier is not particularly limited as long as it can enhance the dispersibility and emulsification properties, and various dispersants or emulsifiers can be used.

[0073] In this case, the aqueous medium may be 1) water alone or 2) a mixed solvent containing water and an organic solvent.

[0074] Examples of organic solvents include polar organic solvents that are extremely soluble in water, such as methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether, as well as petroleum-based solvents that are emulsifiable with water, such as toluene, xylene, and mineral turpentine. These may be used alone or in combination of two or more.

[0075] When a mixed solvent is used, the content of the organic solvent is not particularly limited and can be set appropriately taking into consideration the type of organic solvent, the degree of dispersion or emulsification, etc., but is usually 1 to 50% by weight, preferably 3 to 30% by weight.

[0076] The dispersant or emulsifier is not limited to any particular one, and may be any known or commercially available surfactant. In particular, at least one of an anionic surfactant and a nonionic surfactant is suitable for use in the present invention.

[0077] Examples of the anionic surfactant include at least one of higher alcohol sulfate salts, polyoxyethylene alkylphenyl sulfate salts, sulfated fatty acid ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, higher alcohol phosphate salts, and polyoxyethylene distyrenated phenol ether sulfate salts.

[0078] Examples of the nonionic surfactant include at least one of polyoxyalkylene natural fat alkyl ethers, polyoxyalkylene higher alcohol alkyl ethers, polyoxyalkylene alkylphenyl ethers, and polyhydric alcohol fatty acid esters.

[0079] The amount of surfactant added is not particularly limited and can be set appropriately taking into consideration, for example, the type of surfactant, the degree of dispersion or emulsification, etc., but when the dispersion medium (emulsification medium) is an aqueous medium, the amount is usually about 0.1 to 30% by weight, and preferably about 0.3 to 20% by weight.

[0080] Furthermore, a dispersion stabilizer or emulsion stabilizer can also be used as needed. Examples of dispersion stabilizers include at least one of polyvinyl alcohol, polyvinylpyrrolidone, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, xanthan gum, starch paste, etc. Examples of emulsion stabilizers include at least one of triglycerides such as castor oil (e.g., polyoxyethylene hydrogenated castor oil) and rapeseed oil; esters such as phosphate esters and phthalate esters; and higher alcohols.

[0081] The amount of these stabilizers to be added is not particularly limited and can be set appropriately taking into consideration, for example, the type of stabilizer, the degree of dispersion or emulsification, etc., but when the dispersion medium (emulsification medium) is an aqueous medium, the total amount of dispersion stabilizer or emulsion stabilizer is usually about 0.1 to 10% by weight, and preferably about 0.3 to 3% by weight.

[0082] Other additives that can be used include those used in known or commercially available flame retardants. Examples include sizing agents, colorants, softeners, light stabilizers, antioxidants, UV absorbers, penetrating agents, moisturizing agents, deodorizing agents, antistatic agents, and antifouling agents. The amounts of these additives can be appropriately determined depending on the type of flame retardant.

[0083] The flame retardant of the present invention preferably contains both the above-mentioned surfactant (at least one of anionic surfactants and nonionic surfactants) and a dispersion stabilizer or emulsion stabilizer. For example, a suitable composition of the flame retardant of the present invention, when the dispersion medium (emulsification medium) is an aqueous medium, includes about 1 to 50 wt %, preferably about 5 to 50 wt %, of the polymer of the present invention; about 0.1 to 30 wt %, preferably about 0.3 to 20 wt %, of the surfactant; and about 0.1 to 10 wt %, preferably about 0.3 to 3 wt %, of the dispersion stabilizer or emulsion stabilizer. Therefore, for example, a composition of about 20 to 54 wt % of the polymer of the present invention, about 5 to 20 wt % of the surfactant, about 1 to 3 wt % of the dispersion stabilizer or emulsion stabilizer, and about 40 to 60 wt % of the aqueous medium can be used.

[0084] The flame retardant of the present invention can be suitably prepared, for example, by mixing the predetermined components and then atomizing the mixture using an emulsifying device such as a homogenizer, a high-pressure homogenizer, or an ultrasonic homogenizer, or a dispersing device such as a ball mill or a bead mill.

[0085] The micronization conditions are not particularly limited, but it is sufficient that the average particle size of the dispersed fine particles (fine particles containing the polymer of the present invention, etc.) in the resulting dispersion or emulsion is 10 μm or less, and it is usually preferable to set it to about 0.05 to 5 μm, and it is more preferable to set it to 0.1 to 5 μm.

[0086] 4.Flame-retardant textile products The present invention includes a flame-retardant textile product comprising fibers and the flame retardant of the present invention, more specifically, a flame-retardant textile product in which the flame retardant of the present invention is spread on fibers.

[0087] The fibers are not particularly limited, and at least one of natural fibers, chemical fibers, inorganic fibers, and composite fibers thereof can be used. Specific examples of natural fibers include cotton, linen, silk, and wool. Examples of chemical fibers include rayon, acetate, polyester, nylon, acrylic, polyurethane, polypropylene, and cellulose. Examples of inorganic fibers include glass fiber, carbon fiber, and metal fiber. Mixtures of these fibers can also be used.

[0088] In the present invention, synthetic fibers are preferred, and polyester fibers are particularly preferred, from the viewpoint of the fixation of the flame-retardant component and processability. The polyester fibers are not limited, and examples thereof include at least one of polyethylene terephthalate fibers, polybutylene terephthalate fibers, polytrimethylene terephthalate fibers, and polylactic acid fibers.

[0089] The fibers may be in the form of monofilaments (short fibers or filaments) or woven or nonwoven fabrics. Therefore, the flame retardant of the present invention can be applied to ready-made woven or nonwoven fabrics or textile products (clothing, furniture, automobile parts, daily necessities, etc.) using these.

[0090] The method for flame-retarding fibers with the flame retardant of the present invention is not limited, and can be carried out by, for example, fixing the flame retardant of the present invention to fibers. Therefore, the method for producing a flame-retardant fiber product of the present invention includes a step of contacting fibers with the flame retardant of the present invention.

[0091] The method for producing the flame-retardant fiber product of the present invention (particularly the fixing method) may be any method as long as it can bring the flame retardant of the present invention into contact with fibers (particularly as long as it can coat the surfaces of the fibers that make up the fibers). For example, a dipping method, coating method, spraying method, brush coating method, etc. can be used to apply the flame retardant of the present invention to the entire surface of at least one side of the fabric in an amount equivalent to about 1 to 50% by weight in solid content of the average weight per unit area of ​​the fabric, and if necessary, a curing treatment can be performed by heat treatment to allow the flame retardant to penetrate into the interior.

[0092] More specifically, the method can be carried out by a process including the steps of: a) contacting fibers with the flame retardant of the present invention and then drying the fibers at a temperature of 120°C or less; and b) heat-treating the fibers containing the flame retardant of the present invention at about 140 to 180°C.

[0093] The method for bringing fibers into contact with the flame retardant of the present invention is not particularly limited, and examples thereof include, as described above, a method in which fibers are immersed in the flame retardant of the present invention, a method in which the flame retardant of the present invention is sprayed or applied to fibers, etc. The contact time is not particularly limited, and can be appropriately set depending on the type of fibers used, the degree of flame retardancy, etc.

[0094] The drying method is not particularly limited, and natural drying or heat drying can be used. In the case of heat drying, the drying temperature is preferably about 60 to 120° C. The drying time is preferably about 10 seconds to 30 minutes.

[0095] If necessary, the dried fibers may be subjected to a heat treatment (thermal curing treatment) typically at about 140 to 180°C (preferably 140 to 160°C). This treatment allows the polymer of the present invention to be more reliably fixed to the interior and surface of the fibers. The treatment method is not particularly limited, and can be carried out, for example, by heating a roll carrying the fibers (fabric) to the above temperature, or by passing the fibers through an atmospheric furnace set at the above temperature. The treatment time can be appropriately set depending on, for example, the heat treatment temperature and the degree of fixation of the flame retardant of the present invention, but is typically about 30 seconds to 5 minutes, preferably about 1 to 2 minutes.

[0096] When the polymer of the present invention (phosphorus-containing polymer microparticles or microparticles of the second flame-retardant component added simultaneously) contained in the flame retardant of the present invention has a sufficiently small average particle size of 0.01 to 10 μm, the polymer of the present invention is easily diffused and fixed throughout the entire surface structure of fibers by heat curing, making it possible to produce high-quality flame-retardant textile fibers. Therefore, the average particle size of the microparticles is preferably within the above range, and more preferably 0.05 to 5 μm.

[0097] The flame-retardant textile product of the present invention is characterized by the incorporation of a flame retardant containing, as a flame-retardant component, a polymer of the present invention, which has a phosphorus-containing compound represented by general formula (I) as a monomer. Since the polymer itself is highly flame-resistant, it can prevent the spread of fire through the textile. Furthermore, unlike low-molecular-weight compounds, the polymer of the present invention does not easily fall off during washing, and therefore has high washing durability, effectively preventing the loss of flame retardancy due to washing, such as washing with water or dry cleaning. In particular, it exhibits excellent effectiveness when washed using polar solvents such as water or alcohol.

[0098] Furthermore, unlike flame-retardant textile products made from fabrics or woven or knitted fabrics made from flame-retardant fibers, the flame-retardant textile products of the present invention can be made flame-retardant by post-processing any general-purpose non-flame-retardant textile product as needed, and therefore can be applied to both small-scale and mass-produced products without significantly impairing the inherent performance of the textile product. [Example]

[0099] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the examples, "%" indicates "% by weight."

[0100] <1. Compound Synthesis> In the following synthesis examples, phosphorus-containing (meth)acrylic polymers were synthesized by synthesizing phosphorus-containing (meth)acrylic monomers and then polymerizing them while controlling the molecular weight by adding a chain transfer agent. The synthesized compounds were identified and their molecular weights were measured by the following methods. (1) Tracking the reaction progress: GC The progress of the reaction was monitored by a gas chromatograph (GC-2010: manufactured by Shimadzu Corporation) equipped with a flame ionization detector (FID). (2) Molecular weight measurement: GPC The weight average molecular weight was measured using a gel permeation chromatography (GPC Alliance System, manufactured by Waters) equipped with a refractive index (RID) detector, and was calculated as a polystyrene equivalent value. In the GPC, a column named "Styragel (registered trademark) HR1 (column length: 4.6 × 300 mm, manufactured by Waters)" was used. (3) Identification of chemical structure: 1 H-NMR, 13 C-NMR and IR Hydrogen nuclear magnetic resonance (HNMR) was measured using a 600MHz superconducting nuclear magnetic resonance analyzer (JNM-ECA600: manufactured by JEOL Ltd.). 1 H-NMR) spectrum and carbon nuclear magnetic resonance ( 13 The structure of each synthetic product was determined by C-NMR spectroscopy and infrared absorption (IR) spectroscopy using a Fourier transform infrared spectrophotometer (IRaffinity-1S, manufactured by Shimadzu Corporation).

[0101] Synthesis Example 1 <Synthesis of (meth)acrylic monomer (1)> 500 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Co., Ltd.) and 2229 g of toluene (Ando Parachemie Co., Ltd.) were added to a four-neck flask equipped with a stirrer, a dropping funnel with a side tube, and a thermometer, and the mixture was stirred and cooled to below 20°C under a nitrogen atmosphere. 179 g of trichloroisocyanuric acid (Fujifilm Wako Pure Chemical Industries, Ltd.) was added in six portions to allow chlorination to proceed. Trichloroisocyanuric acid was added as needed to ensure the reaction temperature was always below 40°C. After addition, the mixture was stirred for an additional 2 hours at below 20°C. The reaction was terminated by adding 7.5 mL of anisole (Tokyo Chemical Industry Co., Ltd.). The nitrogen atmosphere was then replaced with a dehydrated air atmosphere, and 0.25 g of dibutylhydroxytoluene (Honshu Chemical Industry Co., Ltd.) (a polymerization inhibitor for acrylic groups) and 412 g of triethylamine (Kishida Chemical Co., Ltd.) were added. 274 g of 2-hydroxyethyl acrylate (Tokyo Chemical Industry Co., Ltd.) was then added dropwise via a dropping funnel equipped with a side tube at a rate such that the reaction temperature remained below 40°C, and the mixture was stirred for 6 hours. The reaction was terminated with water, and the mixture was washed with water, saturated aqueous sodium bicarbonate, saturated aqueous ammonium chloride, and saturated saline. The reaction mixture was concentrated under reduced pressure using an evaporator and recrystallized from a toluene-hexane mixed solvent to obtain 531 g of a white powder (70% yield). 1 H-NMR and 13 C-NMR measurement confirmed that the obtained compound was a phosphorus-containing acrylic monomer of the following formula (1). [ka] 1 H-NMR (600 MHz, CDCl 3 ;internal standard TMSδppm) 7.93-8.00(m,3H),7.73(br t,J=7.8Hz,1H),7.52(br td,J=4.8,7.8Hz,1H),7.38(br t,J=7.8Hz,1H),7,27(br t,J=8.4Hz,1H),7.22(brd,J=8.4Hz,1H),6.34(dd,J=1.2,17.4Hz,1H),6.01(dd,J=1 0.2,17.4Hz,1H),5.80(dd,J=1.2,10.2Hz,1H),4.38-4.41(m,2H),4.29-4.30(m,2H) 13 C-NMR (151 MHz, CDCl 3 ;internal standard TMSδppm) 165.8, 149.9, 137.2, 133.8, 131.6, 130.7, 130.3, 128.4, 127.9, 125.3, 124.9, 124.2, 122.6, 121.3, 120.3, 64.2, 63.2 <Synthesis of phosphorus-containing (meth)acrylic polymer (2)> A four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a Dimroth condenser was charged with 100 g of the phosphorus-containing acrylic monomer (1) synthesized in (1), 6.43 g of mercaptopropionic acid, 1.15 g of 2,2'-azobis(isobutyronitrile) [Fujifilm Wako Pure Chemical Industries, Ltd.], and 1.39 L of ethyl acetate [Hayashi Pure Chemical Industries, Ltd.]. The reaction temperature was then raised to 65°C under a nitrogen atmosphere and the mixture was aged for 16 hours. After confirming the disappearance of the phosphorus-containing acrylic monomer by GC, the solvent was evaporated under reduced pressure. The resulting polymer was dissolved in chloroform and reprecipitated with hexane / ethyl acetate = 1:1 (w / w) to obtain 105.4 g (98% yield) of a white solid polymer represented by the following formula (2). GPC analysis of the resulting phosphorus-containing polymer revealed a weight-average molecular weight (Mw) of 2200 (polystyrene equivalent). [ka]

[0102] Synthesis Example 2 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1, 161 mg of mercaptopropionic acid, 100 mg of 2,2'-azobis(isobutyronitrile), and 100 g of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 13 hours. The solvent was distilled off under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 9.44 g (yield 92%) of a white solid polymer represented by formula (2) was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 6,000 (polystyrene equivalent).

[0103] Synthesis Example 3 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1, 107 mg of mercaptopropionic acid, 100 mg of 2,2'-azobis(isobutyronitrile), and 100 g of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 13 hours. The solvent was distilled off under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 9.13 g (89% yield) of a white solid polymer represented by formula (2) was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 14,000 (polystyrene equivalent).

[0104] Synthesis Example 4 <Synthesis of (meth)acrylic monomer (3)> The reaction was carried out in the same manner as in Synthesis Example 1 for the phosphorus-containing acrylic monomer [compound (1)], except that 2-hydroxyethyl acrylate was changed to 301 g of 2-hydroxyethyl methacrylate [Light Ester HO-250(N): manufactured by Kyoeisha Chemical Co., Ltd.] and the recrystallization treatment was changed to flash column chromatography treatment, thereby obtaining 700 g of a colorless liquid compound (yield 88%). 1 H-NMR and 13 From the results of C-NMR measurement, it was confirmed that the obtained compound was a phosphorus-containing methacrylic monomer of the following formula (3). [ka] 1 H-NMR (600 MHz, CDCl 3 ;internal standard TMSδppm) 7.91-7.98(m,3H),7.71(t,J=7.8Hz,1H),7.50(td,J=4.8,7.8 Hz,1H),7.37(br t,J = 7.8 Hz,1H),7.26(br t,J = 6.6 Hz,1H),7.21(bra d,J = 8.4 Hz,1H),6.00(s,1H),5.51(br s,1H),4.37-4.41(m,2H),4.27-4.29(m,2H),1.84(br s,3H) 13 C-NMR (151 MHz, CDCl 3 ;internal standard TMSδppm) 149.8, 137.0, 135.6, 133.6, 130.6, 130.2, 128.3, 126.3, 125.2, 124.8, 124.1, 122.4, 121.3, 120.1, 64.1, 63.2, 18.2 <Synthesis of phosphorus-containing (meth)acrylic polymer (4)> 10.0 g of the phosphorus-containing methacrylic monomer [compound (3)] synthesized above, 617 mg of 3-mercaptopropionic acid, 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 14 hours. The solvent was removed by distillation under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 10.1 g (yield 94%) of a white solid, polymer (4), was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 2200 (polystyrene equivalent). [ka]

[0105] Synthesis Example 5 <Synthesis of phosphorus-containing (meth)acrylic polymer (5)> 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1, 1.23 g of n-dodecyl mercaptan [Tokyo Chemical Industry Co., Ltd.], 100 mg of 2,2'-azobis(isobutyronitrile), and 100 g of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 13 hours. The solvent was removed by distillation under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 8.61 g of a white solid, polymer (5), was obtained (yield 76%). GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 2300 (polystyrene equivalent). [ka]

[0106] Synthesis Example 6 <Synthesis of phosphorus-containing (meth)acrylic polymer (6)> 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1, 473 mg of 2-mercaptoethanol [Tokyo Chemical Industry Co., Ltd.], 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 17 hours. The solvent was distilled off under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 9.83 g (yield 93%) of a white solid, polymer (6), was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 1700 (polystyrene equivalent). [ka]

[0107] Synthesis Example 7 <Synthesis of phosphorus-containing (meth)acrylic polymer (7)> 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1, 655 mg of α-thioglycerol [Tokyo Chemical Industry Co., Ltd.], 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 14 hours. The solvent was removed by distillation under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 10.3 g (yield 96%) of a white solid, polymer (7), was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 1800 (polystyrene equivalent). [ka]

[0108] Synthesis Example 8 <Synthesis of (meth)acrylic monomer (8)> The reaction was carried out in the same manner as in Synthesis Example 1 for the phosphorus-containing acrylic monomer [compound (1)], except that 2-hydroxyethyl acrylate was replaced with 513 g of 2-hydroxy-3-phenoxypropyl acrylate (Tokyo Chemical Industry Co., Ltd.) and recrystallization was performed by flash column chromatography, thereby obtaining 645 g of a colorless liquid compound (yield 64%). 1 H-NMR and 13 From the results of C-NMR measurement, it was confirmed that the obtained compound was a phosphorus-containing acrylic monomer of the following formula (8). [ka] 1 H-NMR (600 MHz, CDCl 3 ;internal standard TMSδppm) 7.90-7.97(m,3H),7.69-7.73(m,1H),7.46-7.52(m,1H),7.16-7.37(m,5H),6.93-6.98(m,1H),6.82(dd,J=1.2,9.0 Hz,1.33H),6.77(d,J=8.4 Hz,0.67H),6.33-6.43(m,1H),5.99-6.08(m,1H),5.81-5.86(m,1H),5.18 -5.33(m,1H),4.43-4.50(m,1.33H),4.34-4.38(m,0.67H),4.15(t,J=4.8 Hz, 1.33H), 3.98-4.00(m, 0.67H) 13 C-NMR (151 MHz, CDCl 3 ;internal standard TMSδppm) 165.5, 165.2, 158.0, 149.8, 137.0, 133.6, 132.0, 131.7, 130.5, 130.3, 129.5, 128.3, 127.7, 125.2, 124.7, 124.0, 122.6, 122.3, 121.4, 120.2, 144.6, 73.3, 70.3, 67.0, 64.9, 64.1, 63.6 <Synthesis of phosphorus-containing (meth)acrylic polymer (9)> 10.0 g of the phosphorus-containing acrylic monomer compound [compound (8)] synthesized above, 471 mg of 3-mercaptopropionic acid, 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 15 hours. The solvent was removed by distillation under reduced pressure, and the polymer (9) was dissolved in ethyl acetate and reprecipitated with hexane to obtain 9.51 g (90% yield) of a white solid. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 2500 (polystyrene equivalent). [ka]

[0109] Synthesis Example 9 <Synthesis of (meth)acrylic monomer (10)> The reaction was carried out in the same manner as in Synthesis of Acrylic Monomer [Compound (1)] in Synthesis Example 1, except that 2-hydroxyethyl acrylate was changed to 333 g of 4-hydroxybutyl acrylate (Tokyo Chemical Industry Co., Ltd.) and the recrystallization treatment was changed to flash column chromatography treatment, thereby obtaining 620 g of a colorless liquid compound (yield 75%). 1 H-NMR and 13 From the results of C-NMR measurement, it was confirmed that the obtained compound was a phosphorus-containing acrylic monomer of the following formula (10). [ka] 1 H-NMR (600 MHz, CDCl 3 ;internal standard TMSδppm) 7.93-7.99(m,3H),7.73(t,J=8.4 Hz,1H),7.52(br td,J=4.8,7.8Hz,1H),7.39(br t,J=7.8 Hz,1H),7.27(br t,J=7.8 Hz,1H),7.24(dd,J=1.2,8.4 Hz,1H),6.36(dd,J=1.2,17.4 Hz,1H),6.07(dd,J=10.2,17.4 Hz,1H),5.80(br d,J=10.2 Hz,1H),4.19(dt,J=6.0,6.6 Hz,2H),4.06(t,J=6.6 Hz,2H),1.69-1.73(m,2H),1.58-1.63(m,2H) 13 C-NMR (151 MHz, CDCl 3 ;internal standard TMSδppm) 166.1, 149.9, 137.0, 133.5, 130.7, 130.5, 130.1, 128.4, 128.3, 125.3, 124.8, 124.1, 122.7, 121.6, 120.1, 66.1, 63.7, 27.0, 24.7 <Synthesis of phosphorus-containing (meth)acrylic polymer (11)> 10.0 g of the phosphorus-containing acrylic monomer compound [compound (10)] synthesized above, 592 mg of 3-mercaptopropionic acid, 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 14 hours. The solvent was removed by distillation under reduced pressure, and the polymer (11) was dissolved in chloroform and reprecipitated with hexane / ethyl acetate = 1:1 (w / w) to obtain 9.30 g (87% yield) of a pale yellow solid, polymer (11). GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 2000 (polystyrene equivalent). [ka]

[0110] Synthesis Example 10 <Synthesis of phosphorus-containing (meth)acrylic polymer (12)> 10.0 g of the phosphorus-containing acrylic monomer [compound (10)] synthesized in Synthesis Example 9, 816 mg of 2-ethyl-1-hexanethiol [Tokyo Chemical Industry Co., Ltd.], 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 14 hours. The solvent was removed by distillation under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 8.86 g (81% yield) of polymer (12) was obtained as a yellow viscous liquid. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 1900 (polystyrene equivalent). [ka]

[0111] Synthesis Example 11 <Synthesis of phosphorus-containing (meth)acrylic polymer (13)> 10.0 g of the phosphorus-containing acrylic monomer (compound (10)) synthesized in Synthesis Example 9, 1.14 g of 2-ethylhexyl thioglycolate (Tokyo Chemical Industry Co., Ltd.), 100 mg of 2,2'-azobis(isobutyronitrile), and 100 mL of ethyl acetate were mixed. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 14 hours. The solvent was removed by distillation under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 10.6 g (yield 95%) of a yellow viscous liquid, polymer (13), was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 2300 (polystyrene equivalent). [ka]

[0112] Synthesis Example 12 <Synthesis of phosphorus-containing (meth)acrylic polymer (14)> 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1 was mixed with 100 mg of 2,2'-azobis(isobutyronitrile) and 100 g of ethyl acetate without adding mercaptopropionic acid. The reaction temperature was raised to 65°C under a nitrogen atmosphere, and the mixture was aged for 13 hours. The solvent was removed by distillation under reduced pressure, and the polymer was dissolved in chloroform. After reprecipitation with hexane / ethyl acetate = 1:1 (w / w), 10.0 g of a white solid (yield 100%), polymer (14), was obtained. GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 16,000 (polystyrene equivalent). [ka]

[0113] Synthesis Example 13 10.0 g of the phosphorus-containing acrylic monomer [compound (1)] synthesized in Synthesis Example 1 was mixed with 100 mg of 2,2'-azobis(isobutyronitrile) and 180 g of chloroform without adding mercaptopropionic acid. The reaction temperature was raised to 60°C under a nitrogen atmosphere, and the mixture was aged for 13 hours. The reaction solution was concentrated and then reprecipitated with hexane / ethyl acetate = 1:1 (w / w) to obtain 7.0 g (70% yield) of a white solid polymer represented by formula (14). GPC analysis of the resulting phosphorus-containing polymer revealed that the weight-average molecular weight (Mw) was 18,000 (polystyrene equivalent).

[0114] <2. Preparation of flame retardants for fibers> Using the phosphorus-containing polymers obtained in the above synthesis examples, flame retardants were prepared as follows.

[0115] Example 1 35 parts by weight of the phosphorus-containing polymer (2) [Mw2200] obtained in Synthesis Example 1, 7 parts by weight of polyoxyethylene distyrenated phenol ether sulfate, and 3 parts by weight of polyoxyethylene hydrogenated castor oil were placed in a vessel equipped with a stirrer, heated to 80°C, and mixed. 55 parts by weight of water was then added little by little with stirring to emulsify the mixture, and the mixture was cooled to room temperature in a water bath while continuing to stir. Finally, the mixture was filtered through a gauze to obtain 100 parts by weight of a flame retardant as a uniform milky white liquid.

[0116] Example 2 Instead of Synthesis Example 1, the phosphorus-containing polymer (2) [Mw 6000] obtained in Synthesis Example 2 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant that was a uniform milky white liquid.

[0117] Example 3 Instead of Synthesis Example 1, the phosphorus-containing polymer (2) [Mw 14000] obtained in Synthesis Example 3 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant that was a uniform milky white liquid.

[0118] Example 4 Instead of Synthesis Example 1, the phosphorus-containing polymer (4) [Mw 2200] obtained in Synthesis Example 4 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0119] Example 5 Instead of Synthesis Example 1, the phosphorus-containing polymer (5) [Mw 2300] obtained in Synthesis Example 5 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0120] Example 6 Instead of Synthesis Example 1, the phosphorus-containing polymer (6) [Mw 1700] obtained in Synthesis Example 6 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0121] Example 7 Instead of Synthesis Example 1, the phosphorus-containing polymer (7) [Mw 1800] obtained in Synthesis Example 7 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0122] Example 8 Instead of Synthesis Example 1, the phosphorus-containing polymer (9) [Mw 2500] obtained in Synthesis Example 8 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant that was a uniform milky white liquid.

[0123] Example 9 Instead of Synthesis Example 1, the phosphorus-containing polymer (11) [Mw 2000] obtained in Synthesis Example 9 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0124] Example 10 Instead of Synthesis Example 1, the phosphorus-containing polymer (12) [Mw 1900] obtained in Synthesis Example 10 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0125] Example 11 Instead of Synthesis Example 1, the phosphorus-containing polymer (13) [Mw 2300] obtained in Synthesis Example 11 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0126] Example 12 Instead of Synthesis Example 1, the phosphorus-containing polymer (14) [Mw 16000] obtained in Synthesis Example 12 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0127] Example 13 Instead of Synthesis Example 1, the phosphorus-containing polymer (14) [Mw 18000] obtained in Synthesis Example 13 was used, and emulsified and dispersed in the same manner as in Example 1 to obtain a flame retardant as a uniform milky white liquid.

[0128] Comparative Example 1 Instead of the phosphorus-containing polymer obtained in the synthesis example, a phosphate-based flame retardant, 60% (w / w) aqueous solution of guanidine phosphate ("Non-nen 984" manufactured by Marubishi Yuka Kogyo Co., Ltd.), was used as the flame retardant.

[0129] Comparative Example 2 Instead of the phosphorus-containing polymer obtained in the synthesis example, a 55% (w / w) aqueous solution of condensed carbamate phosphate ("Non-Nen W2-50" manufactured by Marubishi Yuka Kogyo Co., Ltd.), which is a phosphate-based flame retardant, was used as a flame retardant.

[0130] Comparative Example 3 Instead of the phosphorus-containing polymer obtained in the synthesis example, a low molecular weight phosphorus-based flame retardant, a cyclic phosphonate ester, namely, an 80% (w / w) aqueous mixture of bis[(5-ethyl-2-methyl-2-oxo-1,3,2λ(5)-dioxaphosphinan-5-yl)methyl] methylphosphonate and (5-ethyl-2-methyl-2-oxo-1,3,2λ(5)-dioxaphosphinan-5-yl)methyl methyl methylphosphonate ("Non-Nen R031-5" manufactured by Marubishi Yuka Kogyo Co., Ltd.) was used to prepare a flame retardant.

[0131] Comparative Example 4 Instead of the phosphorus-containing polymer obtained in the synthesis example, an aromatic phosphonate ester, a low-molecular-weight phosphorus-based flame retardant, i.e., 9,10-dihydro-9-oxa-10-phenoxy-10-phosphaphenanthrene-10-oxide ("Non-Nen 73" manufactured by Marubishi Yuka Kogyo Co., Ltd.), was used, and wet-dispersed according to the method described below to obtain a uniform white dispersion of a flame retardant. A uniform mixture of 40 parts by weight of 9,10-dihydro-9-oxa-10-phenoxy-10-phosphaphenanthrene-10-oxide, 5 parts by weight of polyoxyethylene distyrenated phenol ether, 2 parts by weight of carboxymethyl cellulose (10% by weight aqueous solution), and 53 parts by weight of water was prepared, and this mixture was then placed in an agate pot (pulverized with zirconia beads of 2 mm diameter) and pulverized and dispersed in a planetary ball mill (manufactured by Fritsch GmbH) at an orbital rotation speed of 400 rpm for a rotation time of 2 hours to prepare a uniform white dispersion of a flame retardant.

[0132] Comparative Example 5 In Synthesis Examples 12 and 13, a phosphorus-containing acrylic monomer [compound (1)] was dissolved in ethyl acetate or chloroform, and a phosphorus-containing polymer (14) having a weight-average molecular weight of 16,000 to 18,000 was obtained by solution polymerization without using a chain transfer agent. In order to synthesize a polymer with an even higher molecular weight, emulsion polymerization was carried out. To 60.0 g of the phosphorus-containing acrylic monomer [compound (1)] obtained in Synthesis Example 1, 150 mg of sodium bicarbonate and 3.00 g of sodium dodecyl sulfate were added, and the mixture was dissolved in 550 g of water. The atmosphere was replaced with nitrogen over 15 minutes and the mixture was heated to 80°C. 50.0 g of a 1.20% (w / w) aqueous solution of ammonium persulfate was added dropwise over 30 minutes, and the mixture was aged at 80°C for 3 hours with stirring. After cooling to room temperature, the mixture was filtered through a mesh (#100) to obtain a polymer as a yellow-white emulsion (solid content 8.3%, particle size 60.2 nm). This polymer was insoluble in common organic solvents such as tetrahydrofuran and N,N-dimethylformaldehyde, and molecular weight measurement by GPC was not possible. Measurement of the residual monomer by GC revealed that the monomer conversion was nearly 100%. Furthermore, a comparison of the IR charts of the obtained polymer (Figure 1) and the polymer obtained in Synthesis Example 12 (Figure 2) revealed that they were nearly identical. This indicates that a polymer represented by chemical formula (14) with a weight-average molecular weight (Mw>approximately 20,000) higher than that of Synthesis Example 13 was obtained. Instead of Synthesis Example 1, a yellow-white emulsion of the phosphorus-containing polymer (14) [Mw>20,000] obtained as described above was used as a flame retardant.

[0133] <3. Production and evaluation of flame-retardant products> Test Example 1 Flame-retardant fabric samples were prepared by flame-retarding textiles with the flame-retardant agents obtained in each Example and Comparative Example as follows, and the samples were evaluated. The results of the flame-retardant performance tests for the flame-retardant fabric samples treated with each flame-retardant agent are shown in Table 1. Table 1 shows the amount of flame retardant applied at which the flame after-flame time, after-glow time, and char area of ​​each flame retardant are all marked "○" (the amount of flame retardant applied that meets the flame-retardant standard) in % owf (% owf: the percentage of the amount of flame retardant applied to the fabric weight). The same tests were also conducted on untreated polyester fabrics that had been flame-retarded.

[0134] (1) Flame retardant treatment for textile products (preparation of test samples) The flame retardant treatment was carried out on polyester fibers using the flame retardant treatment agents prepared in each of the Examples and Comparative Examples. The polyester fabric used had a basis weight of 164 g / m 2 The fabric used was a 100% polyester tropical (plain weave) fabric. Each flame retardant was diluted with water, a general-purpose organic solvent such as acetone, and the like to adjust the concentration of the flame retardant solution, and the polyester fabric was immersed in the solution, followed by padding (100% squeezing rate) and pre-drying for 10 minutes at 80° C. The padded fabric was then cured at 150° C. for 1 minute to obtain a flame-retardant fabric. The amount of flame retardant attached to polyester fabric was calculated from the increase in dry weight of the treated fabric relative to the dry weight of the untreated fabric. Furthermore, these flame-retardant treated fabrics were washed in water, and combustion tests were conducted on the treated fabrics in their initial state and after washing. Washing was performed five times in accordance with the Fire and Disaster Management Agency Notification No. 2 of June 28, 2019, "Standards for Washing Resistance Related to Flame Retardancy."

[0135] (2) Evaluation of flame retardant performance of flame-retardant processed textile products (Japanese Industrial Standards JIS L 1091 A-1 method) The flame-retardant fabric obtained above was subjected to a combustion test according to JIS L 1091 A-1 method (45° microburner method). The same combustion test was also carried out on a fabric that had been washed five times in water. (2-1) Afterflame time In evaluating the flame-retardant fabrics, the afterflame time specified in JIS L-1091 A-1 was measured four times in total by applying flame to the front or back of the fabric in both the vertical and horizontal directions. The evaluation criteria for afterflame time were as follows: ○: Afterflame duration 3 seconds after ignition was 3 seconds or less on all 4 occasions ×:Other (2-2) Afterglow time As with the afterflame time, the glow time was measured a total of four times. The glow time evaluation criteria were as follows: ○: The residual flame time after 3 seconds of ignition was 5 seconds or less on all four occasions ×:Other (2-3) Carbonization area As with the afterflame time, the charred area was measured a total of four times. The evaluation criteria for the unit area were as follows: ○: The carbonized area 3 seconds after ignition was 30cm for all four times. 2 The following ×:Other (2-4) Texture The texture of the flame-retardant fabric was checked by touch. The evaluation criteria for texture were as follows: ○: Has the same flexibility as unprocessed fabric △: Slightly harder to the touch compared to untreated fabric ×: Clearly stiffer than untreated fabric

[0136] [Table 1]

[0137] As is clear from the results in Table 1, when flame-retardant-treated polyester fibers, which have no flame retardancy at all when untreated, are flame-retarded, flame retardancy is imparted initially by flame-retardant treatment with a phosphorus-containing (meth)acrylic polymer having a weight-average molecular weight (Mw) of about 20,000 or less, and the resulting fabrics have acceptable flame retardancy for flame-retardant textiles in all of Examples 1 to 13 and Comparative Examples 1 to 4. In contrast, the phosphorus-containing (meth)acrylic polymer of Comparative Example 5, which has a weight-average molecular weight (Mw) of more than about 20,000, exhibited poor flame retardancy and failed to achieve a passing coating weight in the flame retardancy performance test (with a rating of ○ for afterflame time, afterglow time, and char area) using the A-1 method (45° microburner method) specified in JIS L 1091, suggesting that the flame retardancy of the phosphorus-containing (meth)acrylic polymer is strongly influenced by its molecular weight. The flame-retardant fibers treated with the flame-retardant agent comprising the phosphorus-containing (meth)acrylic polymer of the present invention did not show any noticeable decrease in flame-retardant performance even after washing in water, and it was found that the flame-retardant fiber products retained a relatively high level of flame retardancy (Examples 1 to 13).

[0138] Test Example 2 Flame retardant fabrics prepared in the same manner as in Test Example 1, "(1) Flame retardant treatment of textile products (preparation of test samples)," using the flame retardants of Examples 1, 2, 11, and Comparative Examples 1, 4, and 5, were subjected to a combustion test according to Japanese Industrial Standards JIS L 1091 A-4 (vertical method). The results are shown in Table 2. Table 2 shows the amount of flame retardant applied at which the char length, average char length, and flame drop ignition gauze ignition test scores for each flame retardant were all "○" at the beginning of the flame retardant treatment (the amount of flame retardant that passed the test) in % owf (on the weight of fiber: the percentage of the amount of flame retardant applied to the fabric weight). The same tests were also conducted on untreated flame-retardant fabric made of the same polyester fiber as that used in the flame retardant treatment.

[0139] (1) Carbonization length In evaluating the flame-retardant fabrics, the char length specified in JIS L-1091 A-4 was measured three times. The evaluation criteria for the char length were as follows: ○: Char length 3 seconds after ignition was 25.4 cm or less on all three occasions ×:Other (2) Flame ignition of flame droplet ignitable gauze As with the char length, the presence or absence of flame ignition of the flame drop ignitable gauze was measured three times. The evaluation criteria for the presence or absence of flame ignition of the flame drop ignitable gauze were as follows: ○: No gauze ignition occurred three times ×:Other (3) Average carbonization length The carbonization length was measured in the above (3) and the average of three measurements was calculated. The evaluation criteria for the average carbonization length were as follows: ○: Average carbonization length is 17.8cm or less ×:Other

[0140] [Table 2]

[0141] As is clear from the results in Table 2, the phosphorus-containing (meth)acrylic polymer of the present invention having a weight-average molecular weight (Mw) of approximately 20,000 or less has a very high level of flame retardancy, and shows the same tendency in the vertical method as in the 45° microburner method, and it can be seen that the high level of flame retardancy is maintained even after washing in water.

[0142] In contrast, when the low molecular weight phosphate-based flame retardant of the comparative example was used, the flame retardant component fell off during washing with water, resulting in a significant decrease in flame retardancy (Table 1, Comparative Example 1 in Table 2, and Comparative Example 2 in Table 1).

[0143] Furthermore, low molecular weight phosphonate ester flame retardants are fixed by spreading on the surface of the fiber structure of the polyester fabric and penetrating into the amorphous regions of the polyester, and therefore the amount of fixation tends to vary and vary depending on the fabric (Comparative Example 3 in Table 1, and Comparative Example 4 in Tables 1 and 2). However, with the phosphorus-containing (meth)acrylic polymer of the present invention, relatively strong penetration and adhesion occur on the surface of the fiber structure, so no difference is observed depending on the fabric and stable fixation can be maintained (Examples 1 to 13 in Table 1).

[0144] Regarding texture, for the same structure of a phosphorus-containing (meth)acrylic polymer, the texture tends to worsen as the molecular weight increases (Examples 12 and 13, Comparative Example 5 in Table 1), but it is clear that the texture improves when a chain aliphatic hydrocarbon is contained in the intramolecular structure (Examples 5, 9 to 11 in Table 1).

Claims

1. The following general formula (I): 【Chemistry 20】 [In the formula, R １ represents a hydrogen atom or a methyl group. １ and L ２ are the same or different and represent an oxygen atom or an imino (NH) group. ２ represents a hydrocarbon group which may be substituted with a substituent containing at least one of a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom. A phosphorus-containing (meth)acrylic polymer containing one or more phosphorus compounds represented by the following formula (A) as a (meth)acrylic monomer:

2. 2. The phosphorus-containing (meth)acrylic polymer according to claim 1, having a weight average molecular weight Mw (where Mw indicates the relative weight average molecular weight based on standard polystyrene as measured with a differential refractometer by gel permeation chromatography) of 1,000 to 20,000.

3. A flame retardant for fibers, comprising the phosphorus-containing (meth)acrylic polymer according to claim 1.

4. The flame retardant for fibers according to claim 3, further comprising an aqueous medium and being liquid in nature.

5. The flame retardant for fibers according to claim 3, which is used to impart flame retardancy to textile products by post-processing.

6. A flame-retardant fiber product comprising synthetic fibers and the flame retardant for fibers according to claim 3.

7. 7. The flame-retardant textile product according to claim 6, wherein the synthetic fibers include polyester fibers.

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