JP4619432B2 - Method for producing phosphonate ester - Google Patents

Description

  The present invention relates to a flame retardant processing agent containing a phosphonic ester, a method for producing a flame retardant fiber using the processing agent, and a flame retardant fiber produced by the production method.

  In general, fiber products, except for flame retardant fibers such as glass fibers, are burned with poor self-extinguishing properties, and therefore flame retardant or flame proofing is required.

  Conventionally, as a method for flame-retarding a textile product, for example, a method in which the fiber product is brought into contact with a flame-retardant processing agent in a raw yarn manufacturing stage or a fiber post-processing stage is known. As flame retardant processing agents, for example, compounds containing halogen, phosphorus and the like are widely used for organic materials, and compounds such as aluminum hydroxide, magnesium hydroxide and ammonium polyphosphate are widely used for inorganic materials.

  In addition to demands for flame retardancy, textile products are also required to have durability against water washing, dry cleaning, and the like. Currently, there is a halogen compound hexabromocyclododecane as a flame retardant that can satisfy the conditions of flame retardancy and washing durability. Specifically, a method of bringing a flame retardant processing agent containing hexabromocyclododecane into contact with the raw yarn melt spinning, a method of bringing the processing agent into contact with at the time of post-processing of the fiber, and applying heat to efficiently add the flame retardant component By fixing, flame retardant treatment is performed while maintaining washing durability.

  However, in view of recent efforts to deal with global environmental problems, it is strongly desired to use a halogen compound (for example, hexabromocyclododecane) that easily generates harmful gases during combustion.

  In view of such a current situation, various phosphoric acid ester compounds (patents) are used as flame retardant components that are halogen-free compounds and can be applied to both the production stage of raw yarns and post-processing in the form of fiber knitted fabrics. Literature 1); phosphonic acid ester compounds and phosphinic acid ester compounds (Patent Literatures 2 to 4); phosphazene compounds (Patent Literatures 5 to 6) and the like have been proposed.

  These phosphorus-containing compounds, for example, by adding an appropriate amount to the raw yarn production stage (for example, at the time of melt spinning), adding an appropriate amount to the dyeing solution of the fiber knitted fabric, and exhausting the same bath, etc. Although flame retardancy can be imparted to the fiber, it has the following drawbacks.

  That is, the phosphoric acid ester compound is often a liquid, oily or viscous fluid, and often has a poor affinity for the fiber. Tend to induce bleed-out.

  Further, the phosphorus-containing compounds described in these patent documents generally have a strong tendency to impair dyeing fastness such as friction fastness of fibers.

  Further, many of these phosphorus-containing compounds have a very low fixation rate (exhaust rate) to the fiber when the polyester fiber is subjected to exhaust dye bath treatment. On the other hand, when applied to the fiber at high temperature to improve the fixing rate of the flame retardant, the problem of bleed out occurs, and white smoke, mist, etc. occur due to sublimation or thermal decomposition of the flame retardant component at high temperature. I have a processing problem.

In the phosphonic acid ester compound described in Patent Document 4, since the dyeing property and weather resistance (light) property of the fiber are remarkably lowered, there is a problem that the performance inherent to the fiber product is greatly impaired.
JP 2000-328445 A Japanese Patent Publication No. 56-16798 Japanese Patent Publication No.56-9178 JP 2002-275473 A JP-A-8-291467 Japanese Patent Laid-Open No. 10-298188

  The present invention is a flame retardant processing agent containing no halogen, and can be suitably applied to both the production stage of the raw yarn and the post-processing in the form of a fiber woven or knitted fabric, and is excellent while ensuring the washing durability of the fiber. The main object is to provide a flame retardant processing agent comprising a phosphorus-containing compound capable of imparting flame retardancy.

  As a result of intensive studies to achieve the above object, the present inventor has found that a flame retardant processing agent containing a specific phosphonic acid ester can achieve the above object, and has completed the present invention.

That is, this invention relates to the flame-retardant processing agent containing the following phosphonic acid ester, the manufacturing method of a flame-retardant fiber using this processing agent, and the flame-retardant fiber manufactured by this manufacturing method.
1. The following general formula (I)

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
The flame retardant processing agent characterized by including the phosphonic acid ester represented by these.
2. Item 2. The flame retardant processing agent according to Item 1, wherein solid phosphonate fine particles are dispersed in a dispersion medium, and the average particle size of the fine particles is 0.1 to 5 µm.
3. Item 2. The flame retardant processing agent according to Item 1, which is an emulsion in which dispersed fine particles containing a liquid phosphonic acid ester are dispersed in a dispersion medium, and the average particle size of the fine particles is 0.1 to 5 µm.
4). The manufacturing method of a flame-retardant fiber including the process which the flame-retardant processing agent in any one of said claim | item 1-3 is made to contact fiber.
5. The method for producing a flame-retardant fiber according to item 4, wherein the flame-retardant finish is brought into contact with the fiber, the fiber is dried at less than 150 ° C, and then the fiber is heat-treated at 150 to 200 ° C.
6). Item 5. The method for producing flame-retardant fibers according to Item 4, wherein the temperature of the flame-retardant processing agent at the time of contact is 100 to 150 ° C.
7). The following general formula (I)

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A flame retardant fiber obtained by fixing a phosphonic acid ester represented by
8). The flame-retardant fiber manufactured by the manufacturing method in any one of said item 4-6.
9. Item 9. The flame retardant polyester fiber according to item 7 or 8, wherein the fiber is a polyester fiber.
10. The following general formula (I)

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A phosphonic acid ester represented by the following chemical formula (II)

A compound represented by the following general formula (III) is reacted with a halogen compound in the presence of an amine:

[Wherein X represents a halogen atom. ]
A phosphonic acid derivative represented by the formula:

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A process for producing a phosphonic acid ester, comprising dehydrohalogenating a phenol derivative represented by the formula:

Hereinafter, the flame retardant processing agent containing the phosphonic acid ester of the present invention, the method for producing the flame retardant fiber using the processing agent, and the flame retardant fiber produced by the production method will be described in detail.

Flame retardant processing agent containing phosphonic acid ester The flame retardant processing agent of the present invention has the following general formula (I)

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
It contains the phosphonic acid ester represented by these.

  R in the general formula (I) represents a hydrogen atom or a hydrocarbon group which may have a substituent. R is preferably a hydrogen atom rather than a hydrocarbon group. The hydrocarbon group may be any of a chain (which may be either a straight chain or a branched chain) and a ring (which may be any of a monocyclic ring, a condensed polycyclic ring, a bridged ring and a spiro ring). An example is a cyclic hydrocarbon group having a side chain. Further, the hydrocarbon group may be either saturated or unsaturated.

  Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group, and an arylalkyl group. As carbon number of these hydrocarbon groups, 1-18 are preferable and about 1-4 are more preferable.

  Specific examples of the phosphonic acid ester represented by the general formula (I) include compounds represented by the following formulas (1) to (5).

  The flame retardant processing agent of the present invention is preferably in the state of a dispersion or an emulsion (emulsion). That is, a dispersion is preferred when the phosphonate is solid, and an emulsion is preferred when the phosphonate is liquid. For example, the phosphonic acid ester represented by the above formulas (1), (3) and (4) is a solid, and the phosphonic acid ester represented by the formulas (2) and (5) is a viscous liquid. As the dispersion medium (emulsion medium), water is preferable in consideration of environmental aspects.

  When the solid phosphonate fine particles are dispersed in the dispersion medium, the average particle size of the fine particles is not particularly limited, but the fixing rate (exhaust rate) to the fiber when the fiber is flame-retardant processed is In consideration, 10 μm or less, particularly 0.1 to 5 μm is preferable. The average particle size of the fine particles in the case of an emulsion in which dispersed fine particles containing a phosphonic acid ester are dispersed in a dispersion medium is not particularly limited, but is preferably 10 μm or less, particularly preferably 0.1 to 5 μm. With such an average particle diameter, the phosphonic acid ester is easily fixed uniformly on the fiber surface and inside during flame-retardant processing.

  The flame retardant processing agent of the present invention may contain an additive as necessary in order to enhance the dispersibility or emulsification of the phosphonate fine particles.

  The additive is not particularly limited as long as it can improve dispersibility or emulsification, and various dispersants or emulsifiers can be used. Specifically, at least one of an anionic surfactant and a nonionic surfactant is suitable.

  Examples of the anionic surfactant include higher alcohol sulfate, polyoxyethylene alkylphenyl sulfate, sulfated fatty acid ester, alkylbenzene sulfonate, alkyl naphthalene sulfonate, and higher alcohol phosphate. It is done.

  Examples of nonionic surfactants include polyoxyalkylene natural oil alkyl ethers, polyoxyalkylene higher alcohol alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyhydric alcohol fatty acid esters, and the like.

  The addition amount of the surfactant is not particularly limited and can be appropriately set in consideration of the type of the surfactant, the degree of dispersion or emulsification, etc., but when the dispersion medium (emulsion medium) is water, usually 1 to It is about 30% by weight, preferably about 3 to 20% by weight.

  A dispersion stabilizer or an emulsion stabilizer can also be used. Examples of the dispersion stabilizer include polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, xanthan gum, starch paste and the like. Examples of the emulsion stabilizer include triglycerides such as castor oil and rapeseed oil; esters such as phosphate ester and phthalate ester; higher alcohols and the like.

  The amount of these stabilizers to be added is not particularly limited, and can be appropriately set in consideration of the type of stabilizer, the degree of dispersion or emulsification, etc. When the dispersion medium (emulsion medium) is water, It is about 0.1 to 10% by weight, preferably about 1 to 3% by weight.

  As other additives, a processing agent generally used for fiber processing can be used, and examples thereof include a softening agent, a deodorizing agent, and an antistatic agent. The addition amount of these processing agents can be appropriately set according to the type of flame retardant processing.

  The flame retardant processing agent of the present invention preferably contains both the above-described surfactant (at least one of an anionic surfactant and a nonionic surfactant) and a dispersion or emulsion stabilizer. For example, as a suitable composition of the flame retardant processing agent, when the dispersion medium (emulsion medium) is water, the phosphonate fine particles are 10 to 50% by weight, preferably about 25 to 35% by weight; The composition is 30% by weight, preferably about 3 to 20% by weight; 0.1 to 10% by weight, preferably about 1 to 3% by weight of the dispersion or emulsion stabilizer.

  The flame retardant processing agent of the present invention can be prepared, for example, by mixing predetermined raw materials and then stirring with a disperser such as a homogenizer, a ball mill, or a bead mill. The stirring conditions are not particularly limited, but in the dispersion or emulsion obtained by stirring, the average particle size of the dispersed fine particles (phosphonic acid ester solid fine particles or liquid phosphonic acid ester-containing fine particles) is 10 μm or less, particularly preferably 0.8. It is preferable to set so that it may become 1-5 micrometers.

Production method of phosphonate ester The production method of the phosphonate ester represented by the above general formula (I) is not particularly limited, but it is preferably produced by the following production method.

  That is, the following chemical formula (II)

A compound represented by the following general formula (III) is reacted with a halogen compound in the presence of an amine:

[Wherein X represents a halogen atom. ]
A phosphonic acid derivative represented by the formula:

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A production method of dehydrohalogenating a phenol derivative represented by the formula is preferred.

  As the compound represented by the chemical formula (II), a known one or a commercially available product may be used.

As a method for synthesizing the phosphonic acid derivative represented by the general formula (III) from the compound represented by the chemical formula (II), conventionally, as described in J. Chem. Research (S), 1998, 355-
From 6-Oxo-4-phenyl (6H) dibenz [c, e] [1,2] oxaphophorin
A method using a route for synthesizing 6-Oxo-6-phenoxy-4-phenyl (6H) dibenz [c, e] [1,2] oxaphophorin is known.

  When the synthetic route disclosed in the above publication is applied, the following chemical formula (II)

The desired phosphonic acid derivative can be synthesized by refluxing the compound represented by formula (5) with phosphorus pentachloride in excess carbon tetrachloride. However, this method is not suitable for mass synthesis. This is because it is necessary to use carbon tetrachloride in excess, and it is difficult to react solid phosphorus pentachloride having high toxicity and high reactivity at a high temperature in terms of reaction control. Furthermore, since a large amount of hydrogen chloride gas is generated and impurities are easily generated, the yield is low, and it takes time for purification and is not an economically advantageous method.

  In view of this point, the present inventor has developed the following synthesis route. That is, this is a synthetic route for obtaining a phosphonic acid derivative represented by the general formula (III) by reacting a compound represented by the chemical formula (II) with a halogen compound in the presence of an amine.

In this synthetic route, the amine desorbs hydrogen (H ⁺ ) bonded to phosphorus from the compound represented by the chemical formula (II). Then, the phosphonic acid derivative represented by the general formula (III) is obtained by substituting the halogen atom in the halogen compound for the leaving part. Note that the amine that has received the proton (H ⁺ ) loses one halogen atom, and returns to the original amine state by donating a proton to the halogen compound having a negative charge. Thus, in the reaction pathway, the amine acts catalytically on the halogen substitution reaction.

  Although the kind of amine is not particularly limited, for example, triethylamine (TEA), pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. 3.0] -5-nonene, 4-dimethylaminopyridine and the like. Among these, TEA is economically preferable.

No particular limitation is imposed on the halogen compound, for example, carbon tetrachloride (CCl _4), be mentioned as carbon tetrabromide (CBr ₄₎ is preferable.

  Although the preparation ratio of the compound represented by the chemical formula (II) and the halogen compound is not particularly limited, the halogen compound is used in an amount of 1 to 2 mol, preferably 1 to 1. mol per mol of the compound represented by the chemical formula (II). About 2 moles. The amine can be set in accordance with the type of amine, as long as the amount of the catalyst used in the above reaction is allowed to coexist.

  The above reaction may be performed in a solvent as necessary. Examples of the solvent include hydrocarbon solvents such as benzene, toluene and n-hexane; ether solvents such as tetrahydrofuran and dioxane, aprotic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform, and the like. .

In the case of phosphonic acid chloride in which X = Cl (chlorine atom) in the general formula (III), for example, carbon tetrachloride (CCl) is contained in a solvent containing the compound represented by the chemical formula (II) and triethylamine (TEA). ₄ ) can be suitably synthesized by dropwise mixing. Since this synthesis reaction proceeds rapidly from 0 ° C. to room temperature (20 ° C.), it is advantageous compared to the conventional route. When a halogen other than Cl (for example, Br) is introduced into X, the reaction may be performed using a desired halogen compound (for example, carbon tetrabromide (CBr ₄ )). However, from the viewpoint of cost, it is most preferable to introduce Cl into X using carbon tetrachloride as described above.

  In order to dehydrohalogenate the phosphonic acid derivative represented by the general formula (III) and the phenol derivative represented by the general formula (IV), both are simply mixed at 0 ° C. to room temperature (20 ° C.). It's okay. The mixing ratio is not particularly limited, but the phenol derivative may be mixed in an amount of 1 to 2 mol, preferably about 1 to 1.2 mol, with respect to 1 mol of the phosphonic acid derivative. Also in this reaction, a solvent can be used as necessary. The type of the solvent is the same as described above. In addition, since the said amine acts also as a catalyst which accelerates | stimulates a dehydrohalogenation reaction, it is preferable to make an amine coexist.

  In order to efficiently proceed with the above series of reactions, in the synthesis of the derivative of the general formula (III), the derivatives of the chemical formula (II) and the general formula (IV) may be present in the same reaction system from the beginning of the reaction. . In this case, the produced derivative of the general formula (III) quickly undergoes a dehydrohalogenation reaction with the derivative of the general formula (IV), so that the phosphonic acid ester represented by the general formula (I) can be obtained very easily. Because it is. In addition, the amine used for the synthesis of the derivative of the general formula (III) functions as a catalyst for the subsequent dehydrohalogenation reaction and does not need to be removed. When the phosphonic acid ester represented by the general formula (I) is synthesized by the production method of the present invention, the desired product is obtained in a yield of 90% or more under favorable conditions.

Method for Producing Flame Retardant Fiber The flame retardant finish of the present invention can be suitably applied to the production of flame retardant fiber.

  The kind of fiber which performs a flame-retardant process is not specifically limited, A natural fiber, a synthetic fiber, and these composite fibers are included. Specifically, examples of natural fibers include cotton, hemp, silk, and wool. Synthetic fibers include fibers such as rayon, acetate, polyester, nylon, acrylic, and polyurethane. Among these, polyester fibers are preferable, and specific examples thereof include regular polyester fibers, cationic dyeable polyester fibers, and polyester original fibers. In addition, a composite fiber of nylon fiber, acrylic fiber, urethane fiber, cotton or the like and polyester fiber is also preferable.

  The flame retardant processing can be performed by fixing the phosphonic acid ester (flame retardant component) represented by the general formula (I) to the fiber. Therefore, the method for producing a flame retardant fiber of the present invention includes a step of bringing a flame retardant finish into contact with the fiber.

Although the manufacturing method of the flame retardant fiber of this invention is not specifically limited if the process of making a flame retardant processing agent contact is included, For example, the following manufacturing methods are suitable.
(1) A manufacturing method in which a fiber is dried after contacting the fiber with a flame retardant and then heat-treated at 150 to 200 ° C, and (2) a flame retardant heated to 100 to 150 ° C. The manufacturing method including the process of making a fiber contact.

Hereinafter, the production methods (1) and (2) will be described.
(1) Manufacturing method In this manufacturing method, after making a flame-retardant processing agent contact a fiber, a fiber is dried at less than 150 degreeC, and the fiber is then heat-processed at 150-200 degreeC.

  The method of bringing the flame retardant agent into contact with the fiber is not particularly limited, and examples thereof include a method of immersing the fiber in the flame retardant agent and a method of spraying or applying the flame retardant agent to the fiber. The contact time is not particularly limited and can be appropriately set according to the type of fiber, the degree of flame retardancy, and the like.

The drying method is not particularly limited, and natural drying or heat drying can be employed. The drying temperature in the case of heat drying is less than 150 ° C., preferably about 60 to 100 ° C., and the drying time is preferably about 5 to 30 minutes.

After drying, the fiber is heat treated at 150-200 ° C, preferably 160-190 ° C. By the heat treatment, the phosphonic acid ester is fixed inside and on the surface of the fiber. The heat treatment can be performed, for example, by a method of heating a roll carrying the fiber (fabric) to the above temperature, a method of passing through an atmosphere furnace set at the above temperature, or the like. The heat treatment time can be appropriately set according to the heat treatment temperature, the fixing degree of the processing agent, and the like, but is usually 30 seconds to 5 minutes, preferably about 1 to 2 minutes.
(2) Manufacturing Method This manufacturing method includes a step of bringing a flame retardant agent at a temperature of 100 to 150 ° C., particularly 110 to 130 ° C., into contact with the fiber. By bringing the flame retardant finishing agent heated to 100 to 150 ° C. into contact with the fiber, the phosphonic acid ester is fixed inside and on the surface of the fiber. In particular, this production method is effective when the fibers are polyester fibers.

  The contact method of both is not specifically limited, The above-mentioned immersion, spraying, application | coating, etc. can be utilized. For example, in the case of immersion, the phosphonic acid ester can be fixed to the fiber by immersion for about 1 to 60 minutes. After the contact, a drying process may be performed under the same conditions as described above.

  In any of the above production methods, when the average particle diameter of the phosphonic acid ester (phosphonic acid ester solid fine particles or liquid phosphonic acid ester fine particles) contained in the flame retardant processing agent is as small as 0.1 to 10 μm, heat treatment is performed. Thus, the phosphonic acid ester is easily diffused and fixed in an amorphous region inside the fiber (especially polyester fiber), and a flame-retardant fiber (flame-retardant polyester fiber) can be easily produced.

  The flame-retardant fiber of the present invention is formed by fixing the phosphonic acid ester represented by the general formula (I), and has a property that it itself is difficult to burn. Can be easily separated from the non-flammable part (for example, when the bottom of the curtain is ignited, only the fiber of the flammable part is easily separated from the non-flammable part and falls off), thus preventing the spread of the fiber. it can. In addition, the durability to washing is high, and a reduction in flame retardancy due to washing with water, dry cleaning, or the like is suppressed. Furthermore, since the phosphonic acid ester represented by the general formula (I) has high weather resistance (light), the performance inherent in the fiber is not greatly impaired and is suitable for mass production.

  Since the flame retardant processing agent of the present invention does not contain halogen, generation of harmful gas is suppressed even when the flame retardant fiber is burned.

  The flame retardant processing agent of the present invention can be suitably applied to both the raw yarn production stage and the post-processing in the form of fiber knitted fabric, and imparts excellent flame retardancy to the fiber while ensuring the washing durability of the fiber. it can.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.
<Synthesis of Phosphonate Esters Represented by Formulas (1) to (5)>
In the following synthesis examples 1 to 5, the purity of the produced compound was confirmed by high performance liquid chromatography with a photodiode array (PDA) three-dimensional UV detector (Alliance HPLC system: Waters). In addition, high-performance liquid chromatography (LC / MS, integrity system) with a hydrogen nuclear magnetic resonance ( ¹ H-NMR) spectrum and a mass spectrometer using a 300 MHz nuclear magnetic resonance absorption analyzer (JNM-AL300: manufactured by JEOL Ltd.): The structure of each product compound was identified from the mass spectrum by Waters).

Synthesis example 1
In a four-necked flask equipped with a stirrer equipped with a dropping funnel with a side tube and a thermometer, 32.4 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 14.1 g of phenol, 17.2 g of triethylamine and 150 ml of dichloromethane were added, and 30.8 g of carbon tetrachloride was added to the dropping funnel with a side tube. A calcium chloride tube was attached to the upper end of the dropping funnel to prevent moisture in the air from entering the reaction system, and stirring was started. The flask was immersed in ice water and cooled to 10 ° C. Carbon tetrachloride was added dropwise so that the reaction solution temperature did not exceed 15 ° C., and stirring was continued for 1 hour after the addition. The reaction solution was washed with a 2% aqueous sodium hydroxide solution, further washed with tap water and a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The dried reaction liquid was concentrated under reduced pressure to obtain a pale yellow liquid crude product, and recrystallized with methanol-water to obtain 43.5 g of a compound represented by the formula (1) in the form of a white powder. The purity of the obtained compound was 99.1%.

¹ H-NMR (CDCl ₃ ): δ / ppm 7.02-7.12 (m, 3H), 7.18-7.29 (m, 4H), 7.33-7.37 (m, 1H ), 7.46-7.51 (m, 1H), 7.67-7.73 (m, 1H), 7.91-8.03 (m, 3H)
LC / MS (EI, 70 eV): M ⁺ ; m / z = 308 (calculated value C ₁₈ H ₁₃ O ₃ P = 308.27)
Synthesis example 2
Into a four-necked flask equipped with a stirrer equipped with a dropping funnel with a side tube and a thermometer, 43.2 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3-cresol 21. 6 g, 22.3 g of triethylamine, and 200 ml of toluene were added, and 40.0 g of carbon tetrachloride was added to the dropping funnel with a side tube. A calcium chloride tube was attached to the upper end of the dropping funnel to prevent moisture in the air from entering the reaction system, and stirring was started. The flask was immersed in ice water and cooled to 10 ° C. Carbon tetrachloride was added dropwise so that the reaction solution temperature did not exceed 15 ° C., and stirring was continued for 1 hour after the addition. The reaction solution was washed with a 2% aqueous sodium hydroxide solution, further washed with tap water and a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The dried reaction solution was concentrated under reduced pressure to obtain a pale yellow liquid crude product, and treated with activated carbon to obtain 58.0 g of a compound represented by the formula (2) as a slightly yellow transparent liquid. The purity of the obtained compound was 96.8%.

¹ H-NMR (CDCl ₃ ): δ / ppm 2.26 (s, 3H), 6.78-6.81 (d, 1H), 6.89-6.99 (m, 2H), 7. 08-7.13 (t, 1H), 7.21-7.31 (m, 2H), 7.36-7.42 (m, 1H), 7.47-7.54 (m, 1H), 7.70-7.76 (m, 1H), 7.90-8.05 (m, 3H)
LC / MS (EI, 70 eV): M ⁺ ; m / z = 322 (calculated value C ₁₉ H ₁₅ O ₃ P = 322.29)
Synthesis example 3
To a four-necked flask equipped with a stirring device equipped with a dropping funnel with a side tube and a thermometer, 21.6 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4-t-butylphenol 15.0 g, 11.1 g of triethylamine, and 150 ml of dichloromethane were added, and 20.0 g of carbon tetrachloride was added to the dropping funnel with a side tube. A calcium chloride tube was attached to the upper end of the dropping funnel to prevent moisture in the air from entering the reaction system, and stirring was started. The flask was immersed in ice water and cooled to 10 ° C. Carbon tetrachloride was added dropwise so that the reaction solution temperature did not exceed 15 ° C., and stirring was continued for 1 hour after the addition. The reaction solution was washed with a 2% aqueous sodium hydroxide solution, further washed with tap water and a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The dried reaction liquid was concentrated under reduced pressure to obtain a pale yellow liquid crude product, and recrystallized with methanol-water to obtain 31.0 g of a compound represented by the formula (3) in the form of a white powder. The purity of the obtained compound was 98.8%.

¹ H-NMR (CDCl ₃ ): δ / ppm 1.24 (s, 9H), 6.94-6.99 (m, 2H), 7.22-7.43 (m, 5H), 7. 50-7.56 (m, 1H), 7.72-7.79 (m, 1H), 7.94-8.07 (m, 3H)
LC / MS (EI, 70 eV): M ⁺ ; m / z = 364 (calculated value C ₂₂ H ₂₁ O ₃ P = 364.37)
Synthesis example 4
Into a four-necked flask equipped with a stirrer equipped with a dropping funnel with a side tube and a thermometer, 4,3.2 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-phenylphenol 34 0.0 g, 22.3 g of triethylamine, and 200 ml of toluene were added, and 40.0 g of carbon tetrachloride was added to the dropping funnel with a side tube. A calcium chloride tube was attached to the upper end of the dropping funnel to prevent moisture in the air from entering the reaction system, and stirring was started. The flask was immersed in ice water and cooled to 10 ° C. Carbon tetrachloride was added dropwise so that the reaction solution temperature did not exceed 15 ° C., and stirring was continued for 1 hour after the addition. The reaction solution was washed with a 2% aqueous sodium hydroxide solution, further washed with tap water and a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The dried reaction liquid was concentrated under reduced pressure to obtain a pale yellow liquid crude product, and recrystallized with methanol-water to obtain 71.2 g of a compound represented by the formula (4) in the form of a white powder. The purity of the obtained compound was 99.8%.

¹ H-NMR (CDCl ₃ ): δ / ppm 6.96-7.05 (m, 4H), 7.08-7.36 (m, 8H), 7.56-7.79 (m, 5H) )
LC / MS (EI, 70 eV): M ⁺ ; m / z = 384 (calculated value C ₂₄ H ₁₇ O ₃ P = 364.37)
Synthesis example 5
Into a four-necked flask equipped with a stirrer equipped with a dropping funnel with a side tube and a thermometer, 5.2 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 4-octylphenol; 0 g, 2.7 g of triethylamine, and 50 ml of MTBE (t-butyl methyl ether) were added, and 4.9 g of carbon tetrachloride was added to the dropping funnel with a side tube. A calcium chloride tube was attached to the upper end of the dropping funnel to prevent moisture in the air from entering the reaction system, and stirring was started. The flask was immersed in ice water and cooled to 10 ° C. Carbon tetrachloride was added dropwise so that the reaction solution temperature did not exceed 15 ° C., and stirring was continued for 1 hour after the addition. The reaction solution was washed with a 2% aqueous sodium hydroxide solution, further washed with tap water and a saturated aqueous sodium chloride solution, and then dried over anhydrous magnesium sulfate. The dried reaction solution was concentrated under reduced pressure to obtain a pale yellow liquid crude product. The crude product was separated and purified by flash chromatography using a silica gel column (eluent: n-hexane / ethyl acetate = 5/1) to give a compound 8 represented by the formula (5) as a colorless and transparent liquid. 0.1 g was obtained. The purity of the obtained compound was 96.1%.

¹ H-NMR (CDCl ₃ ): δ / ppm 0.85-0.89 (t, 3H), 1.26 (s, 10H), 1.53 (s, 2H), 2.48-1. 53 (t, 2H), 6.91-7.04 (m, 4H), 7.20-7.52 (m, 4H), 7.68-7.73 (m, 1H), 7.91- 8.04 (m, 3H)
LC / MS (EI, 70 eV): M ⁺ ; m / z = 420 (calculated value C ₂₆ H ₂₉ O ₃ P = 420.48)
<Preparation of flame retardant finishing agent>
Example 1
A phosphonic acid ester compound 40 represented by the formula (1) is added to a uniform mixed solution of 5 parts by weight of polyoxyethylene distyrenated phenol ether sulfate, 2 parts by weight of carboxymethyl cellulose (10% by weight aqueous solution) and 53 parts by weight of water. Part by weight was added, and the mixture was put into an agate pot (pulverized with 2 mmΦ zirconia beads) and ground and dispersed with a planetary ball mill (manufactured by Fritsch) at a revolution speed of 400 rpm and a rotation time of 2 hours. A uniform white dispersion liquid flame retardant was obtained.

  As a result of measuring the average particle size of the obtained flame retardant processing agent with a particle size distribution measuring device (laser diffraction / scattering type particle size distribution size LA-910, manufactured by Horiba, Ltd.), the median size was 0.824 μm. .

Example 2
Instead of the phosphonic acid ester compound represented by the formula (1), the phosphonic acid ester compound represented by the formula (2) was pulverized and dispersed in the same manner as in Example 1 to obtain a uniform white dispersion liquid. A flame retardant was obtained.

  As a result of measuring the average particle size as described above, the median size was 1.946 μm.

Example 3
Instead of the phosphonic acid ester compound represented by the formula (1), the phosphonic acid ester compound represented by the formula (3) was pulverized and dispersed in the same manner as in Example 1 to obtain a uniform white dispersion liquid. A flame retardant was obtained.

  As a result of measuring the average particle diameter as described above, the median diameter was 1.910 μm.

Example 4
Instead of the phosphonic acid ester compound represented by the formula (1), the phosphonic acid ester compound represented by the formula (4) was ground and dispersed in the same manner as in Example 1, and it was difficult to form a uniform white dispersion liquid. A flame retardant was obtained.

  As a result of measuring the average particle diameter as described above, the median diameter was 1.116 μm.

Example 5
Instead of the phosphonic acid ester compound represented by the formula (1), the phosphonic acid ester compound represented by the formula (5) was pulverized and dispersed in the same manner as in Example 1 to obtain a uniform white dispersion liquid. A flame retardant was obtained.

  As a result of measuring the average particle diameter as described above, the median diameter was 1.012 μm.

Comparative Example 1
Instead of the phosphonic acid ester compound represented by the formula (1), hexabromocyclododecane (manufactured by Nichiho Chemical Co., Ltd.) was used and pulverized and dispersed in the same manner as in Example 1 to obtain a uniform white dispersion liquid. A flame retardant finish was obtained.

  As a result of measuring the average particle size as described above, the median size was 1.108 μm.

Comparative Example 2
In place of the phosphonic acid ester compound represented by the formula (1), resorcinol bis (diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd.) was used and pulverized and dispersed in the same manner as in Example 1 to obtain a uniform white dispersion. A liquid flame retardant was obtained.

As a result of measuring the average particle diameter in the same manner as described above, the median diameter was 0.215 μm.

<Flame-retardant processing of polyester fiber fabric>
Using each flame retardant processing agent prepared in Examples 1 to 5 and Comparative Examples 1 and 2, the polyester fiber was flame retardant processed. As the polyester fiber, a regular polyester / cationic dyeable polyester woven fabric (90/10) having a basis weight of 233 g / m ^2, which is composed of a regular polyester and a cationic dyeable polyester, which are extremely difficult to flame-retardant. ) Was used.

  As the flame retardant processing method, the following two types of processing examples 1 and 2 were adopted.

Processing example 1
The polyester fabric was padded (squeezing rate 70%) with 7 types of treatment liquids prepared to contain 20% by weight of each flame retardant, and then dried at 80 ° C. for 5 minutes. Next, heat setting was performed at 180 ° C. for 1 minute. Then, it wash | cleaned with the washing | cleaning liquid of the following composition, and it dried for 5 minutes at 80 degreeC, and performed the flame-retardant process.
<Cleaning liquid>
・ Soda ash 1.0 g / L
Processing example 2
Using a mini-color dyeing machine (manufactured by Teksam Giken Co., Ltd.), the polyester fabric undyed cloth is subjected to an exhaust treatment solution having the following composition (treatment solution capable of imparting flame retardancy simultaneously with dyeing) and a bath ratio of 1: 10. After treatment at a temperature of 45 ° C. for 5 minutes, the temperature was raised to 120 ° C. at 2 ° C./minute, and the treatment was performed in a bath under the condition of dyeing at 120 ° C. for 60 minutes. Next, after cooling to 80 ° C., reduction cleaning was performed with a reduction cleaning treatment solution having the following composition, followed by rinsing, followed by drying, followed by drying at 180 ° C. for 1 minute to give flame retardant processing.
<Exhaust treatment liquid>
owf: indicates the weight of fiber.
-Kiwalon P Blue E-SP (disperse dye, manufactured by Kiwa Chemical Industry Co., Ltd.) 0.1% owf
-Kiwalon P Red E-SP (disperse dye, manufactured by Kiwa Chemical Industry Co., Ltd.) 0.1% owf
-Kiwalon P Yellow E-SP (disperse dye, manufactured by Kiwa Chemical Industry Co., Ltd.) 0.1% owf
・ Kayacrill Blue GSL-ED (cationic dye, manufactured by Nippon Kayaku Co., Ltd.) 0.1% owf ・ Kayacrill Red GL-ED (cationic dye, manufactured by Nippon Kayaku Co., Ltd.) 0.1% owf
-Kayacrill Yellow 3RL-ED (cationic dye, manufactured by Nippon Kayaku Co., Ltd.) 0.1% owf
・ KP leveler AL (dispersion leveling agent, manufactured by Nippon Kayaku Co., Ltd.) 0.5 g / L
Acetic acid (pH adjuster) 0.1 mL / L
・ Flame retardant (flame retardant obtained in Examples 1 to 9 and Comparative Example 1) 20% owf
<Reduction cleaning solution>
・ Hydrosulfite 1.0 g / L
・ Soda ash 1.0 g / L
<Flame retardance confirmation test: Combustion test>
About the flame-retardant polyester fiber obtained by the above, the flame-retardant evaluation test by JIS L-1091 A-1 (micro burner method) and JIS L-1091 D (coil method) was done. In addition, the flame retardancy evaluation test was also performed on water washing and dry cleaning performed five times in accordance with the Fire and Disaster Management Agency Notification No. 1 on February 21, 1986. In the evaluation, the afterflame time and the number of times of flame contact specified in JIS L-1091 were measured three times. The results of flame retardancy evaluation of flame retardant processed fiber samples treated with each flame retardant working fluid are shown in the table. In addition, the test was done similarly about the flame-retardant unprocessed fiber of the polyester-type fiber used for the flame-retardant processing. The results are shown in Table 1 below.

Claims (1)

The following general formula (I)

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A phosphonic acid ester represented by the following chemical formula (II)

A compound represented by the following general formula (III) is reacted with a halogen compound in the presence of an amine:

[Wherein X represents a halogen atom. ]
A phosphonic acid derivative represented by the formula:

[Wherein, R represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A process for producing a phosphonic acid ester, comprising dehydrohalogenating a phenol derivative represented by the formula: