JP6271424B2 - Flame retardant processing chemical, flame retardant fiber production method and flame retardant fiber - Google Patents

Description

  The present invention relates to a flame retardant processing chemical, a method for producing a flame retardant fiber, and a flame retardant fiber.

  Conventionally, in order to impart flame retardancy to a fiber material, a flame-retardant processing agent in which a bromine-based or phosphorus-based flame retardant is dispersed or emulsified in water at the time of dyeing is placed in a bath, and heat treatment is performed while the fiber material is immersed. And a method of attaching a flame retardant is used (for example, Patent Documents 1 and 2). However, in the case of this method, since the adhesion efficiency of the flame retardant to the fiber material is low, it is necessary to treat in large quantities, and the flame retardant that does not adhere to the fiber material has a problem of being discharged into the environment. In addition, this method is problematic in that the flame retardant inhibits dyeing, so that the color changes or stains (spec stains) or kettle stains (can body contamination) occur on the fiber material.

  On the other hand, in the case of imparting flame retardancy by post-processing after dyeing, a flame retardant processing agent in which a phosphoric flame retardant such as guanidine phosphate or carbamate phosphate is dispersed, emulsified or dissolved in water is applied to the fiber material. Then, a heat treatment method is taken (for example, Patent Documents 3 and 4). In this post-processing method, since many flame retardants can be efficiently applied, the flame retardant property is higher than that in the dyeing method, and the phosphorus-based flame retardant is not easily discharged into the environment. However, in the post-processing method, since the flame retardant is not exhausted inside the fiber material, if water adheres to the fiber material, the fire retardant (ring-like spots) due to the flame retardant is generated after drying. In addition, when a phosphorus flame retardant is used in an automobile interior material, if a snow melting agent (calcium chloride) adheres to the interior material, the phosphorus flame retardant reacts with the snow melting agent (calcium chloride) and becomes a white calcium insoluble material. The problem of whitening of the fiber material occurs.

Japanese Unexamined Patent Publication No. 2007-9371 Japanese Unexamined Patent Publication No. 2011-195984 Japanese Unexamined Patent Publication No. 2008-163501 Japanese Unexamined Patent Publication No. 2009-256807

  An object of the present invention is to impart good flame retardancy to a fiber material, and to suppress the occurrence of wrinkles (ring-shaped spots) when water adheres to the fiber material and dries, and a snow melting agent is added to the fiber material. To provide a flame retardant processing agent capable of suppressing the occurrence of whitening when (calcium chloride) adheres, a method for producing a flame retardant fiber using the flame retardant processing agent, and a flame retardant fiber obtained by the production method It is.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved if the flame retardant processing agent essentially contains a specific acidic phosphate ester or a salt thereof. Reached.
That is, this invention is a flame retardant processing chemical | medical agent which essentially contains acidic phosphate ester or its salt, Comprising: The said acidic phosphate ester or its salt is a compound represented by following General formula (1).

（ただし、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換基を有してもよい炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又は炭素数６〜１２のアリール基であり、また、Ｒ^１とＲ^２が酸素原子又は窒素原子を介して相互に連結されて５〜７員環を形成してもよい。Ｍ^１は、水素原子、アルカリ性基、下記一般式（２）で表される官能基、置換基を有してもよい炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又は炭素数６〜１２のアリール基ある。Ｍ^２は、水素原子又はアルカリ性基である。ｍ及びｎは、それぞれ独立して、１〜３の整数である。）

(Wherein, ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent group, having 2 to 6 carbon atoms alkenyl or C6-12 It is an aryl group, and R ¹ and R ² may be connected to each other through an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring, where M ¹ is a hydrogen atom, an alkaline group, The functional group represented by the formula (2), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which may have a substituent, M ² is And m and n are each independently an integer of 1 to 3).

（ただし、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換基を有してもよい炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又は炭素数６〜１２のアリール基であり、また、Ｒ^１とＲ^２が酸素原子又は窒素原子を介して相互に連結されて５〜７員環を形成してもよい。ｍは１〜３の整数である。）

(Wherein, ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent group, having 2 to 6 carbon atoms alkenyl or C6-12 It is an aryl group, and R ¹ and R ² may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring, where m is an integer of 1 to 3.

In the general formula (1) and the general formula (2), it is preferable that R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. .
It in general formula (1), M ¹ is a hydrogen atom, an alkaline group, the general formula (2) represented by functional group or a substituent group which may having 1 to 6 carbon atoms alkyl group Is preferred.

In addition, as a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned problems can be solved if they are flame retardant processing agents that essentially contain the following specific acidic phosphate ester or salt thereof. The headline, the present invention has been reached.
That is, the present invention is a flame retardant processing agent that essentially contains an acidic phosphate ester or a salt thereof, wherein the acidic phosphate ester contains a hydroxyl group-containing compound containing a compound represented by the following general formula (3): It is formed by phosphoric esterification.

（ただし、Ｒ³及びＲ⁴は、それぞれ独立して、水素原子、置換基を有してもよい炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又は炭素数６〜１２のアリール基であり、また、Ｒ³とＲ⁴が酸素原子又は窒素原子を介して相互に連結されて５〜７員環を形成してもよい。ｌは、１〜３の整数である。）

(However, R < ³ > and R < ⁴ > are respectively independently a hydrogen atom, the C1-C6 alkyl group which may have a substituent, a C2-C6 alkenyl group, or C6-C12. It is an aryl group, and R ³ and R ⁴ may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring, where l is an integer of 1 to 3.

In General formula (3), it is preferable that R < ³ > and R < ⁴ > are respectively independently a C1-C6 alkyl group which may have a hydrogen atom or a substituent.

  It is preferable that the hydroxyl group-containing compound further includes a compound represented by the following general formula (4).

（Ｒ^５は、置換基を有してもよい炭素数１〜６のアルキル基、炭素数２〜６のアルケニル基又は炭素数６〜１２のアリール基である。）

(R ⁵ is an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

In the general formula (4), it is preferred that R ⁵ is an alkyl group having 1 to 6 carbon atoms which may have a substituent.

  The flame retardant processing agent of the present invention preferably further contains an alkyl acidic phosphate ester or a salt thereof.

The flame retardant processing chemical of the present invention is preferably used for vehicle interior materials.
The manufacturing method of the flame-retardant fiber of this invention includes the process of processing said flame-retardant processing chemical | medical agent into a fiber material.
The flame-retardant fiber of the present invention is a fiber material in which the above-mentioned flame-retardant processing chemical is adhered.

  The flame retardant processing agent of the present invention can impart good flame retardancy to the fiber material by containing a specific acidic phosphate ester or a salt thereof essentially. Moreover, generation | occurrence | production of the wrinkles (ring-shaped spot) when water adheres to a fiber material and dries can be suppressed. Furthermore, since a calcium insoluble matter does not generate | occur | produce by reaction with a snow melting agent (calcium chloride), generation | occurrence | production of whitening when a snow melting agent adheres to a fiber material can be suppressed.

  The flame retardant fiber obtained by the method for producing a flame retardant fiber of the present invention or the flame retardant fiber of the present invention is treated with the above flame retardant processing agent, and thus has good flame retardancy. When water adheres to the flame-retardant fiber and does not dry up when dried (ring-shaped spots), it does not whiten when a snow melting agent (calcium chloride) adheres to the flame-retardant fiber.

[Flame retardant chemicals]
The flame retardant processing chemical of the present invention essentially contains a specific acidic phosphate ester or salt thereof, and the acidic phosphate ester or salt thereof is a compound represented by the above general formula (1). By containing such specific acidic phosphate ester or a salt thereof essentially, the effects of the present application can be exhibited. 1 type may be sufficient as the compound represented by the said General formula (1), and it may contain 2 or more types. In addition, acidic phosphate ester means the phosphate ester or condensed phosphate ester which has at least 1 acidic hydroxyl group in a molecule | numerator.

In the general formula (1), R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number. 6 to 12 aryl groups, and R ¹ and R ² may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring. Among these, it is preferable that R ¹ and R ² are hydrogen atoms and alkyl groups having 1 to 6 carbon atoms which may have a substituent from the viewpoint of imparting excellent flame retardancy to the fiber material. It is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

In the general formula (1), M ¹ is a hydrogen atom, an alkaline group, functional group, an optionally substituted alkyl group having 1 to 6 carbon atoms represented by the general formula (2), 2 carbon atoms -6 alkenyl group or C6-C12 aryl group. Among these, M ¹ is a carbon atom which may have a hydrogen atom, an alkaline group, a functional group represented by the above general formula (2), or a substituent from the viewpoint that excellent flame retardancy can be imparted to the fiber material. It is preferably an alkyl group of 1 to 6, more preferably a hydrogen atom or an alkaline group, and further preferably a hydrogen atom or a guanidine salt.

In the general formula (1), M ² is a hydrogen atom or an alkaline group. Among these, M ² is preferably a hydrogen atom, an ammonium salt, an organic amine salt, a quaternary ammonium salt, a melamine salt, or a guanidine salt from the viewpoint that excellent flame retardancy can be imparted to the fiber material. More preferably, it is a guanidine salt.
In general formula (1), m and n are each independently an integer of 1 to 3. M is preferably 2 from the viewpoint that excellent flame retardancy can be imparted to the fiber material, and the volatility is small, and in the use of vehicle interior materials, the glass is clouded by volatilization of the flame retardant. From the viewpoint of excellent hydrolysis resistance, n is preferably 1.

In General Formula (2), R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or the number of carbon atoms. 6 to 12 aryl groups, and R ¹ and R ² may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring. m is an integer of 1-3. The preferred ranges of R ¹ , R ² and m are the same as those for R ¹ and R ^{2 in} the general formula (1).

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group and the like. As a C2-C6 alkenyl group, a propenyl group etc. are mentioned, for example. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group are preferable, a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable, and a methyl group, an ethyl group, More preferred are groups.

  Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, naphthyl group, biphenyl group, alkylaryl group (tolyl group, xylyl group, cumyl group, methylnaphthyl group, etc.). Among these, a phenyl group and an alkylaryl group are preferable, a phenyl group and a tolyl group are more preferable, and a phenyl group is more preferable.

  Examples of the substituent include a hydroxyl group and an amino group. As a C1-C6 alkyl group which has a substituent, a hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group etc. are mentioned, for example. Among these, a 2-hydroxyethyl group is preferable.

When R ¹ and R ² are connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring (hereinafter sometimes simply referred to as a cyclic group), the cyclic group includes, for example, a piperidino group Pyridine group, morpholino group, imidazole group and the like. Among these, a morpholino group is preferable.

  Examples of the alkaline group include alkali metal salts, alkaline earth metal salts, metal salts, ammonium salts, organic amine salts, quaternary ammonium salts, melamine salts, guanylurea salts, guanidine salts and the like. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include magnesium, calcium, and barium. Examples of the metal include zinc, aluminum, and zirconium. Organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, monoethylamine, diethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, Monomethylethanolamine, dimethylethanolamine, monoethylethanolamine, diethylethanolamine, tris (hydroxymethyl) aminomethane, etc.), polyamine (ethylenediamine, diethylenetriamine, polyethyleneimine, dicyandiamide condensate, dicyandiamide and polyalkylenepolyamine condensate, Condensation of dicyandiamide, polyalkylenepolyamine and urea Condensates of dicyandiamide with formaldehyde and the like) and the like. Examples of quaternary ammonium include tetramethylammonium, tetraethylammonium, tetramethanolammonium, and tetraethanolammonium. Among these, the alkaline group is preferably an ammonium salt, an organic amine salt, a quaternary ammonium salt, a melamine salt, a guanylurea salt, or a guanidine salt, more preferably an ammonium salt, an organic amine salt, or a guanidine salt, and further a guanidine salt. preferable.

  In addition, the flame retardant processing agent of the present invention essentially contains an acidic phosphate ester or a salt thereof, and the acidic phosphate ester contains a hydroxyl group-containing compound containing a compound represented by the above general formula (3). It is formed by acid esterification. Here, the hydroxyl group-containing compound refers to a component having a hydroxyl group in the molecule and capable of constituting phosphoric acid and an ester. The compound represented by the general formula (1) is formed by phosphorylating a hydroxyl group-containing compound including the compound represented by the general formula (3) (or neutralizing the acidic phosphate ester). ).

The hydroxyl group-containing compound essentially contains the compound represented by the general formula (3). In General Formula (3), R ³ and R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a carbon number. 6 to 12 aryl groups, and R ³ and R ⁴ may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring.
Examples and preferred ranges of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the cyclic group which may have a substituent are represented by the general formula (1). The thing similar to what was described by R < ¹ >, R < ² > can be mentioned. Among these, R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent from the viewpoint of imparting excellent flame retardancy to the fiber material. A hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.
l is an integer of 1 to 3, and 1 is preferably 2 from the viewpoint that excellent flame retardancy can be imparted to the fiber material and the volatility is small, and in terms of the problem of fogging in vehicle interior material applications.

  Examples of the compound represented by the general formula (3) include monoethanolamine, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, butylaminoethanol, dibutylaminoethanol, diethylaminoethanol, monoisopropanolamine, dimethylaminopropanol, diethylaminopropanol , Diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine and the like. Among these, monoethanolamine, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, monoisopropanolamine, diethanolamine, and triethanolamine are preferable, and monoethanolamine, methylaminoethanol, dimethylaminoethanol, ethylaminoethanol, and diethanolamine are preferable. More preferred is monoethanolamine.

  30-100 mol% is preferable, as for the ratio of the compound represented by General formula (3) to the said whole hydroxyl group containing compound, 50-100 mol% is more preferable, and 65-100 mol% is further more preferable.

The hydroxyl group-containing compound is represented by the above general formula (4) because the pH of the flame retardant processing agent can be adjusted and the occurrence of whitening when the snow melting agent (calcium chloride) adheres to the fiber material can be suppressed. It is preferable that a compound is further included.
In General Formula (4), R ⁵ is an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples and preferred ranges of the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, and the aryl group having 6 to 12 carbon atoms which may have a substituent are R ¹ in the general formula (1), it can be exemplified similar to that described in R ^2. Among these, R ⁵ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, because it can impart excellent flame retardancy to the fiber material and has excellent resistance to wrinkles. A methyl group is more preferable.

  Examples of the compound represented by the general formula (4) include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1- Examples include hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol propanol, ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, and neopentyl glycol. Among these, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, ethylene glycol, propylene glycol are preferable, and methanol, ethanol, ethylene glycol , Propylene glycol is more preferable, and methanol and ethanol are more preferable.

  When the said hydroxyl group containing compound contains the compound represented by General formula (4), the ratio of the compound represented by General formula (3) to the said whole hydroxyl group containing compound has preferable 30-99 mol%. 50 to 99 mol% is more preferable, and 65 to 95 mol% is more preferable. 1-70 mol% is preferable, as for the ratio of the compound represented by General formula (4) to the said whole hydroxyl group containing compound, 1-50 mol% is more preferable, and 5-35 mol% is more preferable.

  The total ratio of the compound represented by the general formula (3) and the compound represented by the general formula (4) in the hydroxyl group-containing compound is preferably 35 to 100 mol%, more preferably 50 to 100 mol%, 65 More preferred is ˜100 mol%.

The hydroxyl group-containing compound is a trihydric or higher polyhydric alcohol (except for the compound represented by the general formula (3) and the compound represented by the general formula (4)) as long as the effects of the present invention are not impaired. It may contain. Examples of the trihydric or higher polyhydric alcohol include sorbitol, sorbitol, sorbide, sorbitan, pentaerythritol, trimethylolpropane, glycerin, xylitol, erythritol, saccharides and the like.
The proportion of the polyhydric alcohol in the entire hydroxyl group-containing compound is preferably from 0.1 to 20 mol%, more preferably from 0.1 to 10 mol%, still more preferably from 0.1 to 5 mol%.

  An acidic phosphate ester obtained by converting a hydroxyl group-containing compound into a phosphate ester reacts with a hydroxyl group-containing compound and phosphoric anhydride, phosphoric acid, condensed phosphoric acid (eg, pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid)), etc. It means an acidic phosphate ester obtained. There is no limitation in particular about the method of phosphoric acid esterification, A well-known method is employable. In addition, the reaction composition may vary depending on the reaction conditions such as the charging method, charging order, reaction temperature, reaction time, reaction pressure, etc. of each component, but the reaction conditions are not limited, and multiple reactants can be mixed. Also good. The reaction temperature is usually 0 to 200 ° C., and the reaction time is usually 0.1 to 20 hours. The reaction product is a mixed ester mainly composed of the monoester, diester, and condensed phosphate ester represented by the general formula (1). Depending on the reaction conditions, phosphoric acid, condensed phosphoric acid (pyrophosphoric acid, polyphosphoric acid ( Metaphosphoric acid) etc.) may remain as unreacted substances or may be by-produced. These ratios are various and are not particularly limited. By-product phosphoric acid and condensed phosphoric acid are by-produced because a calcium insoluble matter may be generated by reaction with a snow melting agent (calcium chloride). Less phosphoric acid and condensed phosphoric acid are preferred. Specifically, the ratio of phosphoric acid and condensed phosphoric acid to the compound represented by the general formula (1) is preferably 0 to 30% by weight, and more preferably 0 to 10% by weight.

In the phosphoric esterification, the reaction molar ratio of the hydroxyl group-containing compound and the phosphorus element (hydroxyl group-containing compound / phosphorus element) is not particularly limited, but is usually 1.5 / 1 to 1/1. If it is larger than 1.5 / 1, the hydroxyl group-containing compound is likely to remain unreacted, which may adversely affect fogging and bleeding properties. On the other hand, if the ratio is less than 1/1, the amount of condensed phosphate increases, but phosphoric acid, condensed phosphoric acid (such as pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid), etc.) remain as unreacted substances, or are by-produced. It becomes easy.
In the phosphoric acid esterification, when phosphoric anhydride is used, the reaction molar ratio of the hydroxyl group-containing compound and phosphorus element is usually 1.5 / 1, and the molar ratio of the monoester to diester to be formed is about 1/1. It is. When the phosphorous element source includes phosphoric acid, condensed phosphoric acid (eg, pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid)), the reaction molar ratio between the hydroxyl group-containing compound and the phosphorous element is usually smaller than 1.5 / 1, Usually 1.5 / 1 to 1/1. The molar ratio of the monoester and diester produced at this time is usually 1/1 to 1/0.

  The obtained acidic phosphate ester can be neutralized by adding an alkali or the like, if necessary, to obtain a salt of the acidic phosphate ester. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium phosphate, sodium tripolyphosphate, sodium carbonate, ammonia, alkylamine (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamine (monoethanolamine, diethanolamine, triethanolamine). Ethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethylethanolamine, tris (hydroxymethyl) aminomethane, etc., polyamine (ethylenediamine, diethylenetriamine, polyethyleneimine, dicyandiamide condensate, dicyandiamide and poly Condensates of alkylene polyamines, dicyandiamide and polyalkylene polyamines And condensates of urea, dicyandiamide condensation products of formaldehyde and the like), guanyl urea, guanidine, guanidine carbonate, melamine, and the like. Among these, ammonia, alkylamine, alkanolamine, guanidine, guanidine carbonate, and melamine are preferable, ammonia, alkylamine, alkanolamine, guanidine, and guanidine carbonate are more preferable, and guanidine and guanidine carbonate are more preferable. The neutralization is preferably performed so that the pH of the flame retardant processing chemical is 3-7.

  When the hydroxyl group-containing compound is converted to a phosphoric acid ester, a diluent, a solvent, or the like can be used. Examples of the diluent and solvent include water, hydrocarbon (hexane, cyclohexane, etc.), ketone (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon (toluene, xylene, etc.), acid (phosphoric acid, sulfuric acid, etc.), ether ( Diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, etc.), esters (ethyl acetate, dimethyl sulfate, trimethyl phosphate, diethyl phosphate, etc.) and the like.

  In addition, when the hydroxyl group-containing compound is converted to a phosphoric ester, other components other than those described above can be used. For example, a catalyst, an antioxidant, a light stabilizer, a coloring inhibitor, an antifoaming agent, a flame retardant and the like can be mentioned.

  The flame retardant processing chemical of the present invention is not particularly limited as long as it contains the above acidic phosphate ester or a salt thereof. The proportion of the acidic phosphate ester or salt thereof in the flame retardant processing chemical is preferably 0.01 to 100% by weight, more preferably 0.1 to 70% by weight.

  The flame retardant processing agent of the present invention preferably contains water in order to impart flame retardancy to the fiber material. The water may be pure water, distilled water, purified water, soft water, ion exchange water, industrial water, well water, tap water, or the like. The ratio of water in the total flame retardant processing chemical is preferably 0.01 to 99.9% by weight, and more preferably 30 to 99.9% by weight.

In the flame retardant processing agent of the present invention, a component comprising an acidic phosphate ester or a salt thereof other than the above acidic phosphate ester or a salt thereof (hereinafter sometimes referred to as the component (A)), because of its excellent resistance to kicking. It is preferable that (B) is included. Here, the component (A) is an acidic phosphate ester formed by phosphorylating a hydroxyl group-containing compound including the compound represented by the general formula (1) and the compound represented by the general formula (3). It means at least one selected from the salts.
As the component (B), for example, an acidic phosphate ester obtained by converting the compound represented by the general formula (4) into a phosphoric ester or a salt thereof can be exemplified, and is represented by the general formula (4). It can be obtained by reacting a compound with phosphoric anhydride, phosphoric acid, condensed phosphoric acid (such as pyrophosphoric acid or polyphosphoric acid (metaphosphoric acid)) and the like. There is no limitation in particular about the method of phosphoric acid esterification, A well-known method is employable similarly to the above-mentioned.
Examples of the acidic phosphate ester of component (B) include alkyl acidic phosphate esters (methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, etc. ), Acidic phosphate esters such as 2-hydroxyethyl phosphate, and salts thereof.

The salt may be an alkali metal salt, alkaline earth metal salt, ammonium salt, organic amine salt, quaternary ammonium salt, metal salt, melamine salt, guanidine salt, or the like. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include magnesium, calcium, and barium. Organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethyl) Ethanolamine, etc.), polyamines (ethylenediamine, diethylenetriamine, polyethyleneimine, dicyandiamide condensate, dicyandiamide and polyalkylenepolyamine condensate, dicyandiamide, polyalkylenepolyamine and urea condensate, dicyandiamide and formaldehyde condensate, etc.) It is done. Examples of quaternary ammonium include tetramethylammonium, tetraethylammonium, tetramethanolammonium, and tetraethanolammonium.
Examples of the acidic phosphate ester salt of component (B) include methyl guanidine phosphate, dimethyl guanidine phosphate, and methyl monoethanolamine phosphate.

Among these components (B), alkyl acid phosphates or salts thereof are preferred from the viewpoint of excellent flame retardancy and excellent resistance to wrinkles. Methyl phosphate, dimethyl phosphate, ethyl phosphate, diethyl phosphate, phosphorus Isopropyl acid, diisopropyl phosphate or a salt thereof is more preferable, and methyl phosphate, dimethyl phosphate or a salt thereof is more preferable.
The weight ratio of component (A) to component (B) (component (A) / component (B)) is preferably 99/1 to 1/99, more preferably 99/1 to 40/60, and 95/5. ~ 60/40 is more preferred.

  1 to 100 weight% is preferable, as for the weight ratio of the component (A) to the non volatile matter of the flame-retardant processing chemical | medical agent of this invention, 30 to 100 weight% is more preferable, and 60 to 95 weight% is further more preferable. Here, the non-volatile content is measured when a certain amount of sample is spread flat on an aluminum sheet and dried at 110 ° C. under irradiation with an infrared lamp, and the fluctuation range of volatile content for 150 seconds becomes 0.15% by weight. It is the remainder when it is set as the end point of.

  The flame retardant processing agent of the present invention is phosphoric acid, condensed phosphoric acid (pyrophosphoric acid, polyphosphoric acid (metaphosphoric acid)) in order to further suppress the occurrence of whitening when a snow melting agent (calcium chloride) adheres to the fiber material. Etc.) and at least one component (C) selected from these salts is preferably substantially not contained. Specifically, the weight ratio of the component (C) in the nonvolatile content of the flame retardant processing chemical is preferably 30% by weight or less, more preferably 10% by weight or less, and further preferably 1% by weight or less. Examples of the component (C) include phosphate carbamate, polyphosphate carbamate, ammonium polyphosphate salt, guanidine phosphate salt, and guanylurea phosphate salt.

  The flame retardant processing chemical of the present invention may contain components other than those described above as long as the effects of the present invention are not impaired. Other components include, for example, solvents (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pen Tanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2 -Methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, benzyl alcohol, solfit, polyalkylene glycol, acetone, methyl ethyl ketone, -Pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, pentyl lactate, diisopropyl ether, dioxane, tetrahydrofuran, pyridine, N, N- Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), pH adjusting agent, chelating agent, potential adjusting agent, flame retardant, surfactant (anionic surfactant, nonionic surfactant, cationic surfactant) , Amphoteric surfactants, etc.), antiseptics, antifoaming agents, anti-discoloring agents and the like.

  By blending a small amount of the solvent, the work efficiency and stability at low temperature are improved due to the decrease in viscosity. However, when the content increases, problems may occur with respect to production and storage. Therefore, the ratio of the solvent in the whole flame retardant processing chemical is preferably 20% by weight or less. There is no limitation in particular about the content rate of said other component other than that.

  The pH of the flame retardant processing chemical of the present invention is not particularly limited, but 1 to 9 is preferable and 3 to 7 is more preferable from the viewpoint of the stability of the flame retardant processing chemical.

  It is preferable that the flame-retardant processing chemical | medical agent of this invention is comprised with the component which melt | dissolves in water and water. If an insoluble component is contained in water, problems such as poor product stability and uneven adhesion during processing may occur. In addition, if a surfactant or the like is used to dissolve, emulsify, or disperse components insoluble in water, the bleed property may be poor.

  There is no limitation in particular as a manufacturing method of the flame-retardant processing chemical | medical agent of this invention, A well-known method is employable. For example, it can be produced by adding water to the above acidic phosphate ester or a salt thereof and dissolving it, and adding other components as necessary.

  The flame retardant processing chemical of the present invention is not limited to a target material as long as the effects of the present invention can be exhibited, but it is preferably used for imparting flame retardancy to a fiber material. That is, the flame retardant processing agent of the present invention is preferably for fibers. Although there is no limitation in particular about the usage form of the flame retardant processing chemical | medical agent of this invention, Usually, it dilutes and uses for water etc. The fiber material will be described later.

[Method for producing flame-retardant fiber]
The manufacturing method of the flame-retardant fiber of this invention includes the process (processing process) which processes the said flame-retardant processing chemical | medical agent to a fiber material.

  Textile materials include natural fibers such as cotton, hemp, wool, silk, polyester, nylon, polyamide, polyacryl, polyvinyl chloride, polyvinyl alcohol, polyurethane, polyimide, rayon, diacetate, triacetate, polyarylate, polylactic acid, Examples thereof include synthetic fibers such as polyethylene and polypropylene. Preferably, it is a fiber material containing synthetic fibers such as polyester, nylon, polyamide, polyacryl, polyvinyl chloride, polyvinyl alcohol, polyurethane, polyimide, rayon, diacetate, triacetate, polyarylate, polylactic acid, polyethylene, polypropylene, More preferably, it is a fiber material containing polyester.

  Examples of the polyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sodiosulfoisophthalate polyethylene / polyoxybenzoyl terephthalate, polybutylene. Examples include terephthalate / isophthalate.

  The fiber material may be composed of only one type or may be composed of a plurality of types. It may be either blended or woven. The form of the fiber material is not limited, and examples thereof include yarn, woven fabric, knitted fabric, nonwoven fabric, rope, and string.

  Components such as dyes, pigments, other flame retardants, ultraviolet absorbers and matting agents may be attached to the fiber material in advance. Examples of the dye include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, and the like, preferably disperse dyes and cationic dyes. A disperse dye is more preferable. The disperse dye is not particularly limited, and known dyes can be used. For example, Sumikaron dye, Kayalon Polyester dye, Miketon Polyester dye, Palanil dye, Dianix dye, TD dye, Kiwalon Polyester dye, Terasil dye, Foron dye, Serilene dye and the like can be mentioned.

Other flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, cresyl Dixylenyl phosphate, dicresyl xylenyl phosphate, triisopropylphenyl phosphate, diphenylxenyl phosphate, phenyldixenyl phosphate, diphenylorxenyl phosphate, phenyldiorxenyl phosphate, triorxenyl phosphate, trimetaxenyl Phosphate, triparaxenyl phosphate, trixenyl phosphate, α Naphthyl diphenyl phosphate, di-α-naphthylphenyl phosphate, β-naphthyl diphenyl phosphate, di-β-naphthylphenyl phosphate, 2-phenoxyethyl diphenyl phosphate, 5,5-dimethyl-2- (4′-phenylphenoxy) -1 , 3,2-dioxaphosphorinane-2-oxide, 1,3,2-dioxaphosphorinane- {2- (1,1′-biphenyl-2-yloxy)}-5,5-dimethyl-2- Oxide, 5,5-dimethyl-2- (
Phosphate esters such as 2'-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide; resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixylenyl phosphate) , Hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), hydroquinone bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), bisphenol A bis (dixylenyl phosphate) ) Condensed phosphate esters such as: dimethyl methylphosphonate, diethyl ethylphosphonate, dipropyl methylphosphonate, tributyl methylphosphonate, dibutyl phosphonate Butyl, diphenyl phenylphosphonate, dicresyl phenylphosphonate, dixylyl phenylphosphonate, phenyl cresyl phenylphosphonate, bis [(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) Phosphorous esters such as methyl] methylphosphonate-P, P′-dioxide, (5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyldimethylphosphonate-P-oxide Phosphorous acid or salts thereof such as methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, phenylphosphonic acid; dimethyl phosphinic acid dimethyl, diethyl diethylphosphinic acid ethyl, dimethylphosphinic acid propyl, dibutylphosphinic acid butyl, diphenylphosphinic acid phenyl, diphenyl Cresyl phosphinate , Hypophosphorous acid esters such as xylyl diphenylphosphinate and metal salts of diethylphosphinic acid; hypophosphorous acid such as dimethylphosphinic acid, diethylphosphinic acid, dibutylphosphinic acid and diphenylphosphinic acid or salts thereof; trimethylphosphine oxide, triethylphosphine Oxide, tri-n-propylphosphine oxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, tricyclohexylphosphine oxide, tolylphosphine oxide, tris-3-hydroxypropyl Phosphine oxide, tris (2-methylphenyl) phosphine oxide, tris (4-methylphenyl) phosphine oxide, tris (2,6-dimethyl) Phosphine oxides such as phenyl) phosphine oxide, tris (2,6-dimethoxyphenyl) phosphine oxide, tribenzylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone; 10-benzyl-9,10-dihydro-9-oxo- Phosphaphenanthrene derivatives such as 10λ (5) -phosphaphenanthrene = 10-oxide, 10-phenoxy-9,10-dihydro-9-oxo-10λ (5) -phosphaphenanthrene = 10-oxide; diphenyl = (phenyl Amido) phosphate, Phosphate ester amide such as phenyl bis (phenylamido) phosphate; Chlorine-containing phosphate ester; Chlorine-containing condensed phosphate ester; Phosphorus-containing polyester resin; Hexaphenoxycyclotriphosphazene, Hex Phosphazenes such as methoxycyclotriphosphazene and hexapropoxycyclotriphosphazene; decabromodiphenyl ether, ethylenebis (pentabromodiphenyl), tetrabisphenol A, bromoethylenebis (tetrabromophthalimide), tris (tribromophenoxy) triazine, tris (2 , 3-dibromopropyl) isocyanurate, brominated flame retardants such as brominated polystyrene; antimony trioxide and the like.

  Examples of ultraviolet absorbers include 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole 2- {2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl} benzotriazole, 2- [2'-hydroxy, 4'- (2 "-hydroxy) butoxyphenyl] -5-chlorobenzotriazole, 2- (2 ', 4'-dihydroxy-5'-benzoylphenyl) -5-chlorobenzotriazole, 2- (2', 4'-dihydroxy -3'-benzoylphenyl) -5-chlorobenzotriazole, 2- (3'-benzoyl-2'-hydroxy-5'-methylphenyl) benzotria Benzotriazole UV absorbers such as 2-hydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. Benzophenone ultraviolet absorber; 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) -phenol, 2,4-bis (2,4-dimethylphenyl) Triazines such as -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2'-hydroxy-4'-propoxyphenyl) -4,6-diphenyl-s-triazine UV absorbers; benzoxazinone UV absorbers such as 2,2 '-(p-phenylene) di-3,1-benzoxazin-4-one; Cyanoacrylate ultraviolet absorbers such as ru-2-cyano-3,3-diphenyl acrylate and (2-ethylhexyl) -2-cyano-3,3-diphenyl acrylate; salicylate ultraviolet rays such as pt-butylphenyl salicylate An absorbent etc. are mentioned.

  The treatment step is a step of bringing the acid phosphate ester or the salt thereof of the present invention into contact with the fiber material by bringing the flame retardant processing chemical into contact with the fiber material.

  As the treatment step, for example, the fiber material is immersed in a flame-retardant processing agent or a bath obtained by diluting the flame-retardant processing agent with water (treatment bath), and the acidic phosphate ester or salt thereof of the present invention is adhered to the fiber. The material is heat treated and dried. 20-230 degreeC is preferable and the temperature of heat processing has more preferable 90 to 200 degreeC. The heat treatment time is preferably 0.1 to 120 minutes. The adhesion can be performed by a padding method, a spray method, a coating method, or the like. The heat treatment may be either dry heat treatment or wet heat treatment. Examples of the adhesion heat treatment method include pad-dry, spray-dry, spray-dry-cure, pad-dry-steam, pad-steam, pad-dry-cure, and the like.

In addition, as the treatment step, for example, by immersing the fiber material in a bath obtained by diluting a flame retardant processing agent with water, the acid phosphate ester or a salt thereof of the present invention is imparted to the fiber material, and the fiber material is used. Durability can also be imparted by performing heat treatment at 30 ° C. or higher for 2 to 120 minutes in the immersed state. This processing step can be performed using, for example, a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.
The pH of the treatment bath is preferably 1-9, and more preferably 3-7.

  In the method for producing a flame-retardant fiber of the present invention, the treatment bath in the treatment step may contain other components other than the above within a range not impairing the effects of the present invention. For example, the other flame retardants, surfactants, solvents, scouring agents, dispersants, bath softeners, chelating agents (polycarboxylic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), hydroxyethanedi Phosphonic acid, nitrilotrismethylene phosphonic acid, phosphonic acid, glutamic acid diacetic acid and their salts, etc.), dyes, carrier agents, pH adjusters (formic acid, acetic acid, lactic acid, phosphoric acid, citric acid, malic acid, carbonic acid and these Salt), pH slide agent, potential regulator, defoaming agent (mineral oil, silicone, etc.), deodorant, antibacterial agent (silver compound, quaternary ammonium salt, etc.), softener, antistatic agent, repellent Water / oil repellent (fluorine resin, paraffin wax, etc.), antifouling agent, SR agent (water-soluble polyester resin, polyester-polyalkylene glycol polycondensate, fluorine resin, etc.), Finishing agent, synthetic resin (polyester resin, acrylic resin, polyurethane resin, melamine resin, phenol resin, etc.), UV absorber, hydrophilizing agent, smoothing agent, sewing agent (liquid paraffin, mineral oil, paraffin wax, silicone) ), A crosslinking agent (carbodiimide, epoxy, isocyanate, oxazoline, melamine resin, phenol resin, etc.). These may be used alone or in combination of two or more.

  It is preferable that the method for producing a flame-retardant fiber of the present invention includes a step of scouring a fiber material (scouring step) before the processing step of the flame-retardant processing chemical. By carrying out the scouring treatment, impurities such as spinning oil, spinning oil, knitting oil, weaving oil, glue and the like can be removed, and flame retardancy is improved. The scouring treatment method is not particularly limited, but heat treatment is performed at 50 ° C. or more for 1 to 120 minutes in a state where the fiber material is immersed in a bath diluted with water, and scouring, washing, rinsing, dehydration, drying, and the like are performed. For example, it can be performed using a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.

In addition, the method for producing a flame-retardant fiber of the present invention includes a processing step of processing a dye, the above-mentioned other flame retardant, an ultraviolet absorber, or the like on the fiber material before the processing step of the flame-retardant processing agent. It is preferable. In the case of a processing step accompanied by adhesion of other components, usually, flame retardancy, wrinkles, bleeding properties, etc. are reduced, but the method for producing flame retardant fibers of the present invention suppresses these performance degradations. Therefore, it is preferable to have other processing steps. In addition, the flame-retardant processing chemical treatment process is performed after these processing steps, thereby inhibiting dyeing and changing the color, as well as stains on fabric materials (spec stains) and kettle stains (can body contamination). Can solve the problem.
There is no particular limitation on the processing method, but the fiber material is immersed in a water-diluted bath to give them, and heat treatment is performed at 80 ° C. or higher for 2 to 120 minutes in the state where the fiber material is immersed. Impart durability. For example, it can be performed using a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like. The processing step may be performed in the same bath as the above-described scouring step.

  In the method for producing a flame-retardant fiber of the present invention, a synthetic resin emulsion such as an acrylic resin or a urethane resin or a synthetic resin solution may be processed after the processing step of the flame-retardant processing chemical. There is no restriction | limiting in particular in a processing method, A coating, a pad, spray processing etc. can be mentioned. As the coating treatment, an air knife coater, a roll coater, a blade coater, a bar coater, a brush coater, a gravure coater or the like can be used. The synthetic resin emulsion or the synthetic resin solution may contain other components such as other flame retardants.

[Flame-retardant fiber]
The flame-retardant fiber of the present invention is obtained by the method for producing a flame-retardant fiber of the present invention. In the flame-retardant fiber of the present invention, the amount of the acid phosphate ester or salt thereof of the present invention attached to the fiber material is the type and structure of the fiber material, the type and amount of other fiber processing agents attached to the fiber material. However, it is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight with respect to the flame-retardant fiber (whole fiber including deposits). 5 to 10% by weight is more preferable. When the adhesion amount is less than 0.01% by weight, sufficient flame retardancy may not be imparted to the fiber material. On the other hand, if the amount of adhesion exceeds 30% by weight, the resulting flame-retardant fiber may have a poor texture and may not be economical.

  The flame retardant fiber of the present invention preferably contains a dye. Examples of the dye include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, and the like, preferably disperse dyes and cationic dyes. A disperse dye is more preferable. 0.001 to 50 weight% is preferable with respect to a flame-retardant fiber, 0.01 to 20 weight% is more preferable, and 0.1 to 10 weight% is further more preferable.

  The flame retardant fiber of the present invention preferably contains an ultraviolet absorber. The content of the ultraviolet absorber is preferably 0.01 to 10% by weight, more preferably 0.01 to 3% by weight, and still more preferably 0.05 to 1% by weight with respect to the flame retardant fiber.

  Moreover, the flame-retardant fiber of this invention may contain other flame retardants other than the acidic phosphate ester of this invention, or its salt in the range which does not impair the effect of this invention.

  The flame retardant fiber of the present invention preferably contains an acidic phosphate ester or a salt thereof other than the acidic phosphate ester or a salt thereof of the present invention. Salts such as methyl phosphate and dimethyl phosphate are preferred, and examples thereof include methyl guanidine phosphate and dimethyl guanidine phosphate. The content of the acidic phosphate ester or salt thereof other than the acidic phosphate ester or salt thereof of the present invention is preferably 0.01 to 10% by weight, and 0.01 to 5% by weight, based on the flame-retardant fiber. More preferred is 0.05 to 3% by weight.

  The flame-retardant fiber of the present invention is excellent in flame retardancy, and is a vehicle interior material for automobiles, airplanes, railways, ships, etc .; bedding such as futons, mattresses, sheets, pillows, covers, blankets, towels; Clothing such as fire clothes; Curtains, blinds, sofas, chairs, paper bags, carpets, carpets, table cloths, cushions, shoji screens, bran, etc .; display plywood, fiberboards, books, black curtains, construction sheets, It can be used for many applications such as industrial materials such as tents and filters.

  Since the flame-retardant fiber of the present invention does not react with a snow melting agent, it is suitably used for vehicle interior materials such as automobiles that are required not to react with the snow melting agent as well as flame retardancy and resistance to flaking. be able to. Examples of the automobile interior material include a seat back, a door panel, a head lining, a seat cushion, an armrest, a curtain, a mattress, a sun visor, a seat belt, a front panel, a floor cover, and a side panel.

  The flame-retardant fiber of the present invention includes UL-94 vertical combustion test, UL-94 thin material vertical combustion test, JIS-L-1091 method A (microburner method, Meckel burner method, horizontal method, vertical method), B Method (surface combustion test), C method (burning rate test), D method (flame contact test), E method (oxygen index method test), JIS-D-1201, FMVSS-302 method (combustion test of automotive interior materials) It is preferably used for applications that are applied to combustion tests such as

The present invention will be described in detail in the following examples and comparative examples, but the present invention is not limited thereto. Examples 1, 4, 5, 6, 8, 11, 16, 19, 21, and 22 are used as reference examples.

[Manufacture of flame retardant processing chemicals]
(Production Example 1)
In a 2000 mL four-necked flask, 183 g of monoethanolamine was added under a nitrogen atmosphere, stirred and cooled, and 142 g of phosphoric anhydride was gradually added over 1 hour while maintaining 60 to 80 ° C. After the addition, the mixture was stirred at 100 ° C. for 3 hours, 325 g of water was added and cooled, and water was added to adjust the non-volatile content to 50% by weight. Here, the non-volatile content is measured when a certain amount of sample is spread flat on an aluminum sheet and dried at 110 ° C. under irradiation with an infrared lamp, and the fluctuation range of volatile content for 150 seconds becomes 0.15% by weight. It is the remainder when it is set as the end point of.

(Production Example 2)
In a 2000 mL four-necked flask, 122 g of monoethanolamine and 32 g of methanol were placed in a nitrogen atmosphere, stirred and cooled, and 142 g of phosphoric anhydride was gradually added over 1 hour while maintaining 60 to 80 ° C. After the addition, the mixture was stirred at 100 ° C. for 3 hours, 296 g of water was added and cooled, and water was added to adjust the non-volatile content to 50% by weight.

(Production Example 3)
In a 2000 mL four-necked flask, 48 g of methanol was placed in a nitrogen atmosphere, stirred and cooled, 71 g of phosphoric anhydride was gradually added over 1 hour while maintaining 60 to 80 ° C., and stirred at 70 ° C. for 3 hours. Next, 61 g of monoethanolamine and 9 g of water were added, and 71 g of phosphoric anhydride was gradually added over 1 hour. The mixture was stirred at 100 ° C. for 3 hours, 90 g of guanidine carbonate and 300 g of water were added and cooled, and water was added to adjust the non-volatile content to 50% by weight.

(Production Example 4)
In a 2000 mL four-necked flask, under a nitrogen atmosphere, 122 g of monoethanolamine and 46 g of phosphoric acid (85% by weight) were added, stirred and cooled, and 114 g of phosphoric anhydride was gradually added over 1 hour while maintaining 60-80 ° C. The mixture was added and stirred at 100 ° C. for 3 hours. 250 g of water was added and cooled, and water was added to adjust the non-volatile content to 50% by weight.

(Production Example 5)
Under a nitrogen atmosphere, 122 g of monoethanolamine and 230 g of phosphoric acid (85% by weight) were placed in a 2000 mL four-necked flask and stirred at 180 ° C. for 10 hours while distilling off water. Next, 18 g of guanidine carbonate and 270 g of water were added and cooled, and water was added to adjust the non-volatile content to 50% by weight.

(Production Example 6)
Except for using 225 g of methylaminoethanol instead of 183 g of monoethanolamine, a flame-retardant processing agent 6 having a nonvolatile content of 50% by weight was obtained in the same manner as in Production Example 1.

(Production Example 7)
Except for using 150 g of methylaminoethanol instead of 122 g of monoethanolamine, a flame retardant processing chemical 7 having a nonvolatile content of 50% by weight was obtained in the same manner as in Production Example 2.

(Production Example 8)
Except for using 267 g of dimethylaminoethanol instead of 183 g of monoethanolamine, a flame retardant processing chemical 8 having a nonvolatile content of 50% by weight was obtained in the same manner as in Production Example 1.

(Production Example 9)
Except for using 125 g of 13.6 wt% aqueous ammonia instead of 90 g of guanidine carbonate, flame retardant processing chemical 9 having a nonvolatile content of 50 wt% was obtained in the same manner as in Production Example 3.

(Production Example 10)
Except for using 40 g of caustic soda instead of 90 g of guanidine carbonate, a flame-retardant processing chemical 10 having a nonvolatile content of 50% by weight was obtained in the same manner as in Production Example 3.

(Production Example 11)
In a 2000 mL four-necked flask, under a nitrogen atmosphere, 115 g of phosphoric acid (85 wt%) and 61 g of monoethanolamine were added, stirred and cooled, and 142 g of anhydrous phosphoric acid was gradually added over 1 hour while maintaining 60-80 ° C. I put it in. After the addition, the mixture was stirred at 100 ° C. for 3 hours, 42 g of dicyandiamide and 52 g of diethylenetriamine were added, stirred at 150 ° C. for 3 hours, 420 g of water was cooled, and water was added so that the non-volatile content was 50% by weight. A flame retardant processing agent 11 was obtained.

(Production Example 12)
Into a 2000 mL four-necked flask, add 720 g of flame retardant processing chemical 2, 240 g of Phoslex A-1 (manufactured by SC Organic Chemical Co., Ltd.), and 180 g of guanidine carbonate. Stir and add water so that the non-volatile content is 50% by weight. The flame retardant processing chemical 12 was obtained by adjusting.

(Production Example 13)
In a 2000 mL four-necked flask, 1000 g of flame retardant processing chemical 2, 280 g of Phoslex A-2 (SC Organic Chemical Co., Ltd.), and 252 g of dicyandiamide were added, stirred at 100 ° C. for 3 hours, cooled, and the non-volatile content was 50% by weight Then, water was added to adjust to obtain a flame retardant processing chemical 13.

(Production Example 14)
In a 2000 mL four-necked flask, put 880 g of flame retardant processing chemical 2, 320 g of Phoslex A-3 (manufactured by SC Organic Chemical Co., Ltd.) and 180 g of guanidine carbonate, stir and cool, and add water so that the nonvolatile content is 50% by weight. In addition, the flame retardant processing chemical 14 was obtained by adjusting.

(Production Example 15)
In a 2000 mL four-necked flask, add 720 g of flame retardant processing chemical 2, 60 g of Phoslex A-1 (SC Organic Chemical Co., Ltd.) and 45 g of guanidine carbonate, stir and cool, and add water so that the nonvolatile content is 50% by weight. In addition, the flame retardant processing chemical 15 was obtained by adjusting.

(Production Example 16)
In a 2000 mL four-necked flask, under a nitrogen atmosphere, Phoslex A-1 (manufactured by SC Organic Chemical Co., Ltd.) 120 g, monoethanolamine 122 g, phosphoric acid (85 wt%) 115 g, stirred, cooled, and maintained at 60-80 ° C. Then, 71 g of phosphoric anhydride was gradually added over 1 hour. After the addition, the mixture was stirred at 100 ° C. for 3 hours, cooled by adding 480 g of water and 90 g of guanidine carbonate, and adjusted by adding water so that the non-volatile content was 50% by weight.

(Production Example 17)
Into a 2000 mL four-necked flask, add 720 g of flame retardant processing chemical 2, 500 g of diphenyl phosphoric acid, and 180 g of guanidine carbonate, stir, cool, and add water to adjust the non-volatile content to 50% by weight. 17 was obtained.

(Production Example 18)
In a 2000 mL four-necked flask, add 720 g of flame retardant processing chemical 2, 160 g of ethylphosphonic acid 70% by weight aqueous solution, and 168 g of dicyandiamide, stir at 100 ° C. for 3 hours, cool, and add water so that the nonvolatile content is 50% by weight. In addition, the flame retardant processing chemical 18 was obtained by adjusting.

(Production Example 19)
In a 2000 mL four-necked flask, 1000 g of flame retardant processing agent 11 and 20 g of becamine M-3 (melamine resin) (manufactured by DIC) were added and stirred to obtain flame retardant processing agent 19.

(Production Example 20)
In a 2000 mL four-necked flask, 1000 g of flame retardant processing agent 15 and 20 g of becamine M-3 (melamine resin) (manufactured by DIC) were added and stirred to obtain flame retardant processing agent 20.

(Production Example 21)
In a 2000 mL four-necked flask, 1000 g of flame retardant processing agent 11 and 20 g of Aquanate 210 (isocyanate) (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added and stirred to obtain flame retardant processing agent 21.

(Production Example 22)
In a 2000 mL four-necked flask, 1000 g of flame retardant processing agent 11 and 20 g of Epocross WS-300 (manufactured by Nippon Shokubai Co., Ltd.) were added and stirred to obtain flame retardant processing agent 22.

[Flame retardancy evaluation method]
About the sample obtained by the flame-retarding process, according to the automobile interior material combustion test shown by FMVSS-302 method (JIS-D-1201), the average value of 20 measurements was calculated, and the burning rate was measured. An average burning rate of 80 mm / min or less was accepted.

[Kiwatsuki resistance evaluation method]
In a room at 20 ° C. and 65%, 2 cc of 90 ° C. hot water is dropped on the flame retardant cloth, and then air-dried indoors. About the circumference | surroundings of the location where the hot water was dripped, the generation | occurrence | production state of the mark (Kiwatsuki) which the hot water spread was evaluated.
<Judgment>
○: No wrinkles are recognized.
Δ: Slight wrinkles are observed.
X: A clear wrinkle is recognized.

[Bleedability evaluation method]
The flame-resistant fabric was subjected to a friction fastness test (dry test and wet test) with a friction tester type II in JIS L 0849 in a room at 20 ° C. and 65%, and evaluated by a series. The larger the series, the better the bleeding.

[Reactivity with snow melting agent]
100 g of flame retardant processing chemical and 100 g of calcium chloride 10 wt% aqueous solution were mixed, and the appearance after standing for 1 day was evaluated.
○: No white precipitate is observed.
X: A white precipitate is recognized.

<Scouring dyeing processing>
In a mini color dyeing pot of a mini color dyeing machine (manufactured by Teksam Giken Co., Ltd.), water, scouring agent Marpon ISD-1 (1 g / L, Matsumoto Yushi Seiyaku Co., Ltd.), Kayalon Polyster Black RV-SF300 (3 Weight% owf (manufactured by Nippon Kayaku Co., Ltd.) was added while being dissolved in water at 30 to 35 ° C., and then adjusted to pH 4.5 with an acetic acid / sodium acetate buffer to prepare a dyeing bath.
Next, the polyester tropical living machine was put into the prepared dyeing bath and treated with a mini color. The bath ratio at that time was 1:20. As treatment conditions, the temperature was raised to 135 ° C. at a rate of 2 ° C. per minute and maintained at 135 ° C. for 40 minutes. Then, when it cooled and became 70 degreeC, the dyeing bath was discarded and it washed with water for 5 minutes.
Next, a bath containing 1 g / L of Marpomarvelin S-1520 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), hydrosulfite 2 g / L, and caustic soda 2 g / L as a soaping agent, with a bath ratio of 1:20 and a temperature of 80 ° C. Then, a soaping treatment was performed for 15 minutes, washed with water, and dried at 160 ° C. for 1 minute to obtain a polyester fiber for flame retardant processing.

<Flame retardant processing>
Immerse the polyester fiber for flame-retardant processing in a treatment solution containing 5% by weight of the flame-retardant processing agent and 3% by weight of Matsumoto Silicone Softener N-20 (silicone softener, Matsumoto Yushi Seiyaku Co., Ltd.) The drawing rate was 90%), drying was performed at 110 ° C. for 3 minutes, and curing was performed at 160 ° C. for 1 minute to obtain a flame-retardant processed cloth.

[Example 1]
About the said flame-retardant processing polyester fiber which carried out the scouring dyeing process, the flame-retardant processing was performed using the flame-retardant processing chemical | medical agent 1 obtained by manufacture example 1, and the flame-retardant processed cloth was obtained. The obtained sample was evaluated for flame retardancy, fluff resistance, and bleeding.
Moreover, the reactivity with a snow melting agent was evaluated using the flame retardant processing chemical 1 obtained in Production Example 1. These results are shown in Table 1.

[Examples 2 to 22]
Evaluation was performed in the same manner as in Example 1 except that the flame retardant processing chemical 1 was changed to the flame retardant processing chemicals 2 to 22 shown in Production Examples 2 to 22, respectively. The results are shown in Table 1.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 except that the flame retardant processing chemical 1 was changed to Apinon 307 (manufactured by Sanwa Chemical Co., Ltd.), which is a 50% by weight aqueous solution of guanidine phosphate. The results are shown in Table 1.

[Comparative Example 2]
Evaluation was performed in the same manner as in Example 1 except that the flame retardant processing chemical 1 was changed to Apinon 145 (manufactured by Sanwa Chemical Co., Ltd.), which is a 45% by weight aqueous solution of guanidine sulfamate. The results are shown in Table 1.

[Comparative Example 3]
Using a sand grinder, water 45g, O, O, O ', O'-tetrakis (2,6-dimethylphenyl) -O, O'-p-phenylene-bisphosphate 40g, Haitenol NE-053 (Daiichi Kogyo) A 15 g mixture (manufactured by Pharmaceutical Co., Ltd.) was wet pulverized for 10 hours and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
Using a sand grinder, a mixture of 45 g of water, 40 g of tris (2,3-dibromopropyl) isocyanurate, and 5 g of Labelin FP (Daiichi Kogyo Seiyaku Co., Ltd.) was wet-ground for 10 hours. And evaluated. The results are shown in Table 1.

[Comparative Example 5]
In a 2000 mL four-necked flask, 222 g of t-butanol was placed in a nitrogen atmosphere, stirred and cooled, 142 g of phosphoric anhydride was gradually added over 3 hours while maintaining 60 to 80 ° C., and stirred at 70 ° C. for 3 hours. did. 180 g of guanidine carbonate and 480 g of water were added and cooled, and water was added to adjust the non-volatile content to 50% by weight to obtain a flame retardant processing chemical. Evaluation was performed in the same manner as in Example 1 using this flame retardant processing chemical. The results are shown in Table 1.

  Examples 1-22 used as the flame retardant processing chemicals of the present invention are excellent in all of flame retardancy, resistance to flaking, bleeding, and reactivity with snow melting agents. On the other hand, Comparative Examples 1-5 are inferior in any one of a flame retardance, a fluff resistance, a bleeding property, and the reactivity with a snow melting agent.

  The flame-retardant processing agent for fibers of the present invention can be suitably used when imparting flame retardancy to a fiber material. The flame-retardant fiber of the present invention can be used in many applications such as vehicle interior materials, bedding, clothing, interiors, and industrial materials.

Claims (9)

A flame retardant processing agent that essentially contains an acidic phosphate ester or a salt thereof,
The flame-retardant processing chemical | medical agent whose said acidic phosphate ester or its salt is a compound represented by following General formula (1).

(Wherein, ^{R 1} and ^{R 2} are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent group, having 2 to 6 carbon atoms alkenyl or C6-12 an aryl group, also, R ¹ and R ² are good .M ¹ also form a 5- to 7-membered ring are connected to each other through an oxygen atom or a nitrogen atom may have a substituent An alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, M ² is a hydrogen atom or an alkaline group, and m and n are each independently, It is an integer from 1 to 3.) Oite the general formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon hydrogen atom or a carbon atoms which may have a substituent, a flame according to claim 1 Fuel processing chemicals. A flame retardant processing agent that essentially contains an acidic phosphate ester or a salt thereof,
The flame retardant processing chemical agent in which the acidic phosphate ester is obtained by phosphorylating a hydroxyl group-containing compound containing a compound represented by the following general formula (3) and a compound represented by the following general formula (4) .

(However, R < ³ > and R < ⁴ > are respectively independently a hydrogen atom, the C1-C6 alkyl group which may have a substituent, a C2-C6 alkenyl group, or C6-C12. It is an aryl group, and R ³ and R ⁴ may be connected to each other via an oxygen atom or a nitrogen atom to form a 5- to 7-membered ring, where l is an integer of 1 to 3.

(R ⁵ is an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.) In general formula (3), the flame retardant processing of Claim 3 whose R < ³ > and R < ⁴ > is a C1-C6 alkyl group which may have a hydrogen atom or a substituent each independently. Drugs. The flame retardant processing agent according to claim 6, wherein in General Formula (4), R ⁵ is an alkyl group having 1 to 4 carbon atoms which may have a substituent. The flame retardant processing agent according to any one of claims 1 to 5 , further comprising an alkyl acidic phosphate ester or a salt thereof. The flame-retardant processing chemical according to any one of claims 1 to 6 , which is used for vehicle interior materials. Comprising the step of treating the flame retarding agent according to any one of claims 1 to 7 the fiber material, The method of producing a flame-resistant fiber. A flame retardant fiber, wherein the flame retardant processing agent according to any one of claims 1 to 7 is attached to a fiber material.