JP2002256269A - Liquid flame-retardant processing agent and processing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid flame-retardant processing agent containing neither heavy metal, nor chlorine and bromine, capable of imparting excellent flame retardancy with a small amount of its addition, and to provide a method for flame-retardant processing of fiber materials using the flame-retardant processing agent. SOLUTION: This liquid flame-retardant processing agent is one selected from the group consisting of solution obtained by dissolving a cyclic phosphazene compound (A) in a solvent, an emulsion obtained by dispersing the phosphazene compound in water, and an emulsion obtained by dispersing the above solution in water, wherein the phosphazene compound is selected from cyclic phosphazenes represented by the general formula (1) (wherein, m is a 3-10 integer; Qs are each a group independently selected from aryloxy groups, alkoxy groups and amino group.). The other objective method for flame- retardant processing using the above agent is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to flammable fibers,
The present invention relates to a liquid flame retardant capable of easily imparting flame retardancy to a combustible fibrous substance such as paper, sheet, nonwoven fabric, etc. in a small amount, and a flame retardant processing method using the same.

[0002]

2. Description of the Related Art Fibers, papers, sheets, non-woven fabrics, and the like have been conventionally used in daily life as materials for clothes, curtains, carpets, furniture, wallpapers, and the like. It is flame-retarded in various ways to avoid fire hazards. However, materials that have been flame-retarded using chlorine- or bromine-based compounds, which have been the main flame-retardant substances alone, or in combination with heavy metal compounds such as antimony oxide, have been used during processing or incineration as waste materials. For example, toxic chlorine-based or bromine-based gas such as dioxin is generated. In addition, when these gases evolve in a fire,
It acts as a poison for the human body and is dangerous. When heavy metals are added, the heavy metals come into contact with the human body on a daily basis, which is harmful to health. Therefore, a flame retardant that does not contain heavy metals and does not generate these chlorine-based or bromine-based gases during combustion or processing has been required.

In order to meet these demands, metal hydroxides and phosphorus-based flame retardants (phosphate esters, ammonium polyphosphates, phosphazenes, etc.) have recently been used as flame retardants containing no chlorine or bromine.

[0004] Metal hydroxides such as aluminum hydroxide and magnesium hydroxide exhibit a flame retardant effect when impregnated into wood or the like, but all have poor water resistance due to water solubility and are easily peeled off, so that fibers, paper, It is not suitable for materials having a large surface area and a small thickness, such as sheets and nonwoven fabrics. In addition, there are disadvantages such as impaired processing properties and texture required for those materials. Further, conventional phosphorus-based flame retardants are said to have a flame-retardant effect, but because they are strong in hydrophilicity, they are apt to damp, and it is not preferable to mix or apply them to clothing, household goods, furniture, etc. . In addition, nitrogen-based guanidine salts such as guanidine sulfate, which are often used for temporary flame-retardant processing, have high water solubility and are affected by humidity,
After processing, it tends to absorb moisture and stick, or to produce white powder.
Some of them have many drawbacks, such as corrosion of metals such as iron.

[0005] Various studies have been made on phosphazene compounds which do not contain chlorine, bromine and heavy metals, are water-insoluble, and have a phosphorus and nitrogen skeleton as a flame retardant. For example, in the case of plastic products, Japanese Unexamined Patent Publication (Kokai) No. 4-148551 discloses a flame-retardant electrical insulating composition comprising polyolefin, metal hydroxide and phosphazene, and Japanese Unexamined Patent Publication (Kokai) No. 6-263908 discloses an ethylene vinyl acetate copolymer. A foamable flame-retardant polyolefin resin composition comprising a coalescable, an inorganic flame retardant, a phosphazene and a urea derivative is disclosed in JP-A-7-292233, and a flame-retardant resin composition comprising a polycarbonate resin, a phosphazene and a fluorine resin. However, in JP-A-9-53009, a flame-retardant resin composition comprising an aromatic polycarbonate, a graft copolymer and phosphazene is disclosed. In JP-A-9-71708, a rubber-reinforced styrene, polyphenylene ether and phosphazene are used. Each flame-retardant resin composition It is draft. However,
Even if a fibrous material such as fiber, paper, sheet, or nonwoven fabric is used as a raw material or after it is processed into a product, a method that does not lose its texture easily and is not hygroscopic and has a flame retardant property has not been developed.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a liquid flame-retardant agent which does not contain heavy metals, chlorine or bromine and provides excellent flame retardancy with a small amount of addition. An object of the present invention is to provide a method for flame retarding fibrous materials.

[0007]

SUMMARY OF THE INVENTION The present invention imparts flame retardancy to fibrous materials, such as fibers, papers, sheets, and nonwoven fabrics, which are frequently used, without losing the natural characteristics such as the original texture of the material. As a result of intensive research on the method, the phosphazenes described in the claims were dissolved, or a dispersed emulsion was sprayed, transferred, brushed or applied by means of immersion, etc. The present inventors have found a method for imparting flame retardancy by infiltrating the surface or even into the interior, and have completed the present invention.

That is, the first aspect of the present invention is to provide the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) The present invention relates to a liquid flame retardant selected from the group consisting of a solution in which the cyclic phosphazene compound (A) is dissolved in a solvent, an emulsion obtained by dispersing in a water, and an emulsion obtained by dispersing a solution in a solvent in water. In the second aspect of the present invention, the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Cyclic phosphazene compound (A) and the following general formula (2)

Embedded image (Wherein, n is an integer of 1 to 20, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group, and an amino group). Liquid flame-retardant agent selected from the group consisting of a solution of the obtained chain phosphazene compound (B) in a solvent, an emulsion dispersed in water, and an emulsion dispersed in water of a solution dissolved in the solvent. About. The third aspect of the present invention is the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Liquid flame retardant containing a cyclic phosphazene compound (A) and silicone oil. A fourth aspect of the present invention is to provide the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Cyclic phosphazene compound (A) and the following general formula (2)

Embedded image (Wherein, n is an integer of 1 to 20, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group, and an amino group). The present invention relates to a liquid flame retardant containing a chain phosphazene compound (B) and silicone oil. A fifth aspect of the present invention is the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) And a liquid flame-retardant agent selected from the group consisting of a solution obtained by dissolving a solution containing a cyclic phosphazene compound (A) and silicone oil in a solvent, and an emulsion dispersed in water. A sixth aspect of the present invention provides the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Cyclic phosphazene compound (A) and the following general formula (2)

Embedded image (Wherein, n is an integer of 1 to 20, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group, and an amino group). The present invention relates to a liquid flame-retardant agent selected from the group consisting of a solution obtained by dissolving a solution containing at least the linear phosphazene compound (B) and silicone oil in a solvent and an emulsion dispersed in water.
A seventh aspect of the present invention is the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. A) a solution obtained by dissolving a cyclic phosphazene compound (A ′) selected from the cyclic phosphazenes represented by the formula (1) in a solvent, an emulsion obtained by dispersing in a water, and an emulsion obtained by dispersing a solution dissolved in a solvent in water. A liquid flame retardant selected from the group consisting of: An eighth aspect of the present invention provides the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. A) a cyclic phosphazene compound selected from the cyclic phosphazenes represented by the following general formula (2):

Embedded image (In the formula, n is an integer of 1 to 20, Q is a phenoxy group, an m-tolyloxy group, or a p-tolyloxy group, and a phenoxy group, an m-tolyloxy group, and a p-tolyloxy group in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2n. A) a solution obtained by dissolving a linear phosphazene compound (B ′) selected from the chain phosphazenes represented by the following formula (B ′) in a solvent, an emulsion prepared by dispersing in a water, and an emulsion prepared by dispersing a solution dissolved in a solvent in water. A liquid flame retardant selected from the group consisting of: A ninth aspect of the present invention is a compound represented by the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. The present invention relates to a liquid flame retardant containing a cyclic phosphazene compound (A ') selected from the cyclic phosphazenes represented by the formula (1) and silicone oil. A tenth aspect of the present invention is to provide the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. A) a cyclic phosphazene compound selected from the cyclic phosphazenes represented by the following general formula (2):

Embedded image (In the formula, n is an integer of 1 to 20, Q is a phenoxy group, an m-tolyloxy group, or a p-tolyloxy group, and a phenoxy group, an m-tolyloxy group, and a p-tolyloxy group in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2n. The present invention relates to a liquid flame retardant containing a chain phosphazene compound (B ') selected from the chain phosphazenes represented by the formula (1) and silicone oil. An eleventh aspect of the present invention provides the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. Liquid flame retardant composed of a solution obtained by dissolving a solution containing a cyclic phosphazene compound (B ') selected from the cyclic phosphazenes represented by the formula (I) and silicone oil in a solvent, or an emulsion obtained by dispersing the solution in water. Related to processing agents. A twelfth aspect of the present invention is the following general formula (1)

Embedded image (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. A) a cyclic phosphazene compound selected from the cyclic phosphazenes represented by the following general formula (2):

Embedded image (In the formula, n is an integer of 1 to 20, Q is a phenoxy group, an m-tolyloxy group, or a p-tolyloxy group, and a phenoxy group, an m-tolyloxy group, and a p-tolyloxy group in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2n. A) a solution containing a chain phosphazene compound (B ′) selected from the chain phosphazenes represented by the formula (I) and silicone oil dissolved in a solvent or an emulsion obtained by dispersing the solution in water. Related to flame retardants. A thirteenth aspect of the present invention relates to the liquid flame-retardant agent according to any one of claims 1 to 12, which contains a fluororesin and / or a rubber. A fourteenth aspect of the present invention relates to a method for flame retarding fibrous materials, comprising applying the flame retardant agent according to any one of claims 1 to 13 to fibrous materials.

In the cyclic phosphazene compound (A) and the chain phosphazene compound (B) used in the present invention, Q in the general formulas (1) and (2) is an aryloxy group, an alkoxy group, an amino group and a dialkylamino group. Having a group independently selected from the group consisting of
The following can be exemplified as typical examples of Q.

The aryloxy group includes, for example,
Unsubstituted or methyl, ethyl, n-propyl, i
so-propyl group, tert-butyl group, tert-octyl group, methoxy group, ethoxy group, 2,3-dimethyl group, 2,4-dimethyl group, 2,5-dimethyl group, 2,6
-Dimethyl group, 3,5-dimethyl group, hydroxy group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, phenyloxy group substituted with phenyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an iso group.
Examples thereof include -propoxy group, n-butoxy group, iso-butoxy group, and the like, and preferably have 1 to 8 carbon atoms. Examples of the amino group include an NH ₂ group; a monoalkylamino group such as a methylamino group and an ethylamino group (alkyl may be linear or branched); a dialkylamino group such as a dimethylamino group and a diethylamino group (alkyl is a linear And the two alkyls may be different alkyls, or may be the same alkyls).

The cyclic phosphazene compound (A) and the chain phosphazene compound (B) are represented by the following general formula (3)

Embedded image (Wherein X is a halogen atom, m is an integer of 3 to 10) and / or the following general formula (4)

Embedded image (Wherein X is a halogen atom and n is an integer of 1 to 20) with an alkali metal phenolate and / or an alkali metal alcoholate and / or an amine in an organic solvent. To be obtained.

As an example of a method for synthesizing halogenated phosphazenes, for example, Yokoyama [Nippon Kagaku Magazine Vol.
No. p118 (1959)], phosphorus pentachloride and ammonium chloride in monochlorobenzene,
The reaction gives a mixture of cyclic and linear chlorophosphazenes, which is recrystallized from petroleum ether to give mp. Hexachlorophosphazene of white rhombic crystals at 112 to 113 ° C. [m = 3 in the general formula (3)] is obtained.

The solvent of the phosphazene compound used for preparing the flame retardant of the present invention is not particularly limited, and any solvent can be used as long as the phosphazene compound can be dissolved or dispersed. For example, ketones such as acetone and methyl ethyl ketone, ethers and cyclic ethers such as ethyl ether and tetrahydrofuran, aliphatic hydrocarbons such as paraffin and isoparaffin, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl lactate And alcohols such as ethyl alcohol and mixtures thereof.

The silicone oil mixed with the phosphazene compound of the present invention includes dimethyl silicone oil,
Examples include straight silicone oils such as methylphenyl silicone oil and methyl hydrogen silicone oil, modified silicone oils such as amino-modified silicone oil, and silicone oil adjusted to emulsion.

The fluororesin and / or rubber which can be used by mixing with the phosphazene compound of the present invention includes polytetrafluoroethylene, tetrafluoroethylene-
Perfluoro-based polymers such as perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, and tetrafluoroethylene-perfluoroalkyl vinyl ether-based fluororubbers; and perfluoropolymers such as tetrafluoroethylene and hexafluoropropylene Copolymers of fluoro-type monomers and other copolymerizable monomers, polymers and copolymers of vinylidene fluoride, and the like, of which perfluoro-type ones are particularly excellent due to their structure It shows incombustibility, heat resistance and weather resistance. When these fluororesins and / or rubbers are blended as a liquid such as a dispersion type, an emulsion type, or a solution type, they exhibit not only flame retardancy but also excellent water repellency and oil repellency, and also exhibit antifouling properties. It has an anti-drip effect on chemical fibers such as polyester and rayon.

The substance imparting flame retardancy is not particularly limited as long as it is flammable, but the object can be easily achieved by means of spraying, coating, impregnating, etc. with the liquid flame retardant of the present invention. Fibrous materials such as fibers, non-woven fabrics, woven fabrics,
Paper, wood, etc. are typical. Specifically, natural fibers such as cotton, hemp, and wool; chemical fibers such as nylon, polyester, rayon, and acrylic; and blended fibers thereof, and cloths, nonwoven fabrics, and nonwoven fabrics made from the fibers. Interior products such as clothing, curtains, goodwill, tablecloths, bedspreads, paper and sheets for wallpaper and decoration, interior wood such as sheets,
Examples of flammable substances commonly used in daily life, such as furniture wood, interior wood, and construction wood.

The flame retardant according to the present invention may be used by mixing the above-mentioned phosphazenes or in combination with another flame retardant.

Antioxidants which may be added in addition to the compounds according to the invention include, for example, 2,6-di-ter
t-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-te
rt-butyl-4-ethylphenol, 2,6-di-t
tert-butyl-4-n-butylphenol, 2,6-
Di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol, 2
-(Α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-dinonyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol,
2,4-dimethyl-6- (1'-methyl-undeca-
1'-yl) -phenol, 2,4-dimethyl-6
(1'-methyl-trideca-1'-yl) -phenol and mixtures thereof, 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, , 4-Dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol and mixtures thereof, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-diphenol -Tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl- 4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, , 5-di -tert- butyl-4
Hydroxyphenyl stearate, bis (3,5-di-
tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5- Triazine, 2-octylmercapto-4,6-bis (3,5-di-ter
t-butyl-4-hydroxyanilino) -1,3,5-
Triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di -Tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,3 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl)- 1,3,5-triazine, 1,3
5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,
3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate and the like, and 2,2'-methylenebis (6-ter
t-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-ethylidenebis (4,6-di-ter
t-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6-di-tert)
-Butylphenol), 4,4'-methylenebis (6-
tert-butyl-2-methylphenol), 1,1-
Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3
3'-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate] and 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4 , 6-trimethylbenzene, 1,4
-Bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4) -Hydroxybenzyl) -phenol and the like.

Light stabilizers which may be added in addition to the compounds according to the invention include, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
-(3 ', 5'-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (5'-ter
t-butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,
3,3-Tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-butyl-
2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4 '-Octoxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- [3'-tert-butyl-2 '
-Hydroxy-5 '-(2'-octyloxycarbonylethylphenyl)]-5-chlorobenzotriazole and the like: 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy- , 4
-Benzyloxy, 4,2 ', 4'-trihydroxy-, 2'-hydroxy-4,4'-di-methoxy- or 4- (2-ethylhexyloxy) -2-hydroxybenzophenone derivative, etc .: tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoylresorcinol), 2,4-di-tert-butylphenylresorcinol, 3,5-di-tert-butyl- 4-hydroxybenzoate, hexadecyl-3,5-di-ter
t-butyl-4-hydroxybenzoate, etc .: ethyl
α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, etc .: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) adipate and the like: 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxyoxanilide, 2,2'-
Dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-
Di-tert-butyl oxanilide, 2-ethoxy-
2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5
-Tert-butyl-2'-ethoxyoxanilide and the like:
2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-
(Hydroxy-4-octyloxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl ) -4,6-bis (2,
4-dimethylphenyl) -1,3,5-triazine and the like.

Examples of the metal deactivator which may be added in addition to the compound in the present invention include, for example, N, N'-di-phenyloxalic acid diamide, N-sartilal-N'-
Salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-ter
t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,3-triazole, bis (benzylidene) oxalic acid hydrazide,
Isophthalic dihydrazide, N, N'-diacetal-
Adipic dihydrazide, N, N'-bissalicyloyl oxalic acid dihydrazide, N, N'-bissalicyloylthiopropionic acid dihydrazide and the like can be mentioned.

The flame retardant agent of the present invention is useful for building interior materials such as wallpaper, interior materials such as covers and rugs such as curtains, carpets and sofa covers, and materials for clothing such as aprons. Even after it becomes a product, it can be easily flame-retarded, and even after the flame-retardant treatment, it is safe for the human body without losing the texture of the material. It is unique in that it does not emit chlorine or bromine compounds such as dioxin.

Production of Flame Retardant and Evaluation of Flame Retardancy The flame retardancy of the fiber was evaluated according to JIS K7201 according to LO.
I (critical oxygen index). The flame retardancy of wood was evaluated by a simple combustion test.

[0023]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited thereto.

Synthesis Example 1 87.5 g of 48% NaOH in a 1 L flask equipped with a stirrer, a thermometer, a fractionation receiver for measuring moisture, and a reflux condenser.
(1.05 mol), 220 mL of toluene and 98.8 g (1.05 mol) of phenol were charged and heated under stirring to carry out azeotropic dehydration (64 mL of recovered water) to remove the water in the flask, thereby performing Na salification of phenol. . This is 80
C. and cooled to 25.0 g of N, N-dimethylformamide.
(0.342 mol), and a toluene solution of hexachlorophosphazene [58.0 g (0.167 mol) of hexachlorophosphazene, toluene 2
75 mL] was added dropwise over 2 hours, and a stirring reaction was carried out at the same temperature for 10 hours. After the reaction is completed, 200 m
After adding L to dissolve the inorganic salt, the organic layer was separated using a separating funnel. The organic layer is neutralized with 5% sulfuric acid, washed with water,
The toluene was distilled off to obtain 113.4 g (yield 98%) of hexaphenoxyphosphazene as pale yellow crystals. Melting point is 11
2-113 ° C.

Synthesis Example 2 Chlorophosphazene mixture [general formula (1) m = 3] in place of hexachlorophosphazene under the same conditions as in Synthesis Example 1.
74.7% by weight, m = 49.9% by weight, m = 5 or more 11.8% by weight, and a chain phosphazene represented by the general formula (2) 2.6% by weight]. . As a result, 111.1 g (96% yield) of brown waxy polyphenoxyphosphazene was obtained.

Synthesis Example 3 48% NaOH 41.7 in a 500 mL flask equipped with a stirrer, a thermometer, a fractionation receiver for measuring moisture, and a reflux condenser.
g (0.5 mol), 220 mL of toluene, and 47.5 g (0.5 mol) of phenol, and heated under stirring to carry out azeotropic dehydration (recovered water: 30 mL) to remove water in the flask, and perform chlorination of phenol with Na. Was. 80 ℃
And cooled to 12.5 g of N, N-dimethylformamide.
(0.171 mol), and a toluene solution of hexachlorophosphazene [58.0 g (0.167 mol) of hexachlorophosphazene, toluene 2
75 mL] over 1 hour, and a stirring reaction was carried out at the same temperature for 5 hours. Next, 28% CH ₃ ONa (CH ₃ OH
Solution) (101.5 g, 0.53 mol) was added dropwise over 2 hours, and a stirring reaction was performed at the same temperature for 30 hours. After the reaction was completed, 200 mL of water was added to the flask to dissolve the inorganic salt, and then the organic layer was separated using a separating funnel. The organic layer was neutralized with 5% sulfuric acid, washed with water, and toluene was distilled off to obtain 82.2 g (yield 97%) of crude trimethoxytriphenoxyphosphazene (light yellow oil).

Synthesis Example 4 A chlorophosphazene mixture [general formula (1) m = 3] was used in place of hexachlorophosphazene under the same conditions as in Synthesis Example 3.
74.7% by weight, m = 49.9% by weight, m = 5 or more 11.8% by weight, and a chain phosphazene represented by the general formula (2) 2.6% by weight]. . As a result, 81.3 g (96% yield) of an alkoxyphenoxyphosphazene mixture (light yellow oil) was obtained.

Synthesis Example 5 87.5 g of 48% NaOH in a 1 L flask equipped with a stirrer, a thermometer, a fractionation receiver for measuring moisture, and a reflux condenser.
(1.05 mol), toluene 220 mL, mixed phenols [m-cresol: p-cresol: phenol = 4: 2: 4 (molar ratio)] 107.9 g (1.05 total in total)
mol), heated under stirring and azeotropically dehydrated (recovered water 6
4 mL) to remove water in the flask, and the mixed cresol was salified with Na. This is cooled to 80 ° C.
-Methyl-2-pyrrolidone (25.0 g) was charged and stirred at 80 ° C. with a toluene solution of hexachlorophosphazene [58.0 g (0.167 mol) of hexachlorophosphazene.
l), toluene 275 mL] was added dropwise over 2 hours, and a stirring reaction was performed at the same temperature for 10 hours. After the reaction was completed, 200 mL of water was added to the flask to dissolve the inorganic salt, and then the organic layer was separated using a separating funnel. The organic layer was neutralized with 5% sulfuric acid, washed with water, and toluene was distilled off to obtain 120.5 g of liquid tolyloxyphosphazene (yield 97%).

Synthesis Example 6 A chlorophosphazene mixture [general formula (1) m = 3] was used in place of hexachlorophosphazene under the same conditions as in Synthesis Example 5.
74.7% by weight, m = 49.9% by weight, m = 5 or more: 11.8% by weight, chain phosphazenes represented by the general formula (2): 2.6% by weight]. went. As a result, 118.0 g (yield 95%) of a liquid phosphazene mixture was obtained.

Preparation Example 1 Preparation of hexaphenoxyphosphazene-containing flame retardant. 50
After 200 g of acetone was added to a 0 mL round bottom flask, 20.0 g of hexaphenoxyphosphazene obtained in Synthesis Example 1 was added, and the mixture was stirred at room temperature. When hexaphenoxyphosphazene was completely dissolved, it was transferred to a glass bottle to obtain a hexaphenoxyphosphazene-containing flame retardant.

Preparation Examples 2 to 6 In the same manner as in Preparation Example 1, a phosphazene-containing flame retardant was prepared by using the phosphazene obtained in Synthesis Examples 2 to 6 in place of the hexaphenoxyphosphazene obtained in Synthesis Example 1. Obtained.

Preparation 7 Preparation of hexaphenoxyphosphazene-containing flame retardant processing agent.
A 300 mL round bottom flask was charged with Shin-Etsu Chemical's Silicon Oil KF-96-10010.0 g, and 5.0 g of hexaphenoxyphosphazene was added, followed by stirring at room temperature. When hexaphenoxyphosphazene was completely dissolved, 100 g of acetone was added little by little with stirring. After completion of the addition, stirring was continued for 10 minutes to obtain a hexaphenoxyphosphazene-containing flame retardant.

Preparation Example 8 Preparation of Phenoxymethoxyphosphazene-Containing Flame-Retardant Processing Agent A 500 mL round bottom flask was charged with 25 g of phenoxymethoxyphosphazene, and lipophilic 504 g of Daiichi Kogyo Sorgen and Neugen ET-14 manufactured by Daiichi Kogyo Seiyaku.
72 g was added, and 200 g of water was added little by little with stirring to obtain a phenoxymethoxyphosphazene-containing emulsion type flame retardant.

Preparation Example 9 Preparation of phenoxymethoxyphosphazene-containing flame retardant processing agent. After adding 50 g of Shin-Etsu Chemical silicon oil KF96-10 to a 500 mL round-bottom flask, 5 g of lipophilic glyceryl monostearate and 2.5 g of POE cetyl ether were added, and after stirring for 5 minutes, 35 g of phenoxymethoxyphosphazene was added. After adding and stirring for 30 minutes, 150 g of water is added little by little with stirring to obtain a phenoxymethoxyphosphazene-containing emulsion type flame retardant.

Preparation Example 10 A flame-retardant spray was prepared according to the following formulation. Stock solution: Phenoxymethoxyphosphazene 10% by weight Isoparaffin 60% by weight Propylene glycol monomethyl ether 20% by weight Xylene 10% by weight Aerosol: Stock solution 47% by weight LPG · L-0.39 53% by weight

Examples 1 to 9 A cotton cloth of 6.5 cm width × 100 cm length was dipped in the phosphazene-containing flame retardant obtained in Preparation Examples 1 to 5 for 5 seconds, pulled up and air-dried for 20 minutes. The flame retardancy test samples of Examples 1 to 9 were used.

COMPARATIVE EXAMPLE 1 A cotton fabric without treatment was used as a sample.

Example 10 A cloth made of polyester having a width of 6.5 cm and a length of 100 cm was hung down with the upper end fixed, and the spray obtained in Adjustment Example 10 was sprayed until the whole was sufficiently wet, and hot air at 60 ° C. was blown. Send and dry.

Comparative Example 2 A sample of the polyester cloth of Example 10 without spraying was used as a sample.

[0040]

[Table 1]

Examples 11 to 12 and Comparative Example 3 A cypress wood piece of 10 × 3.5 × 0.6 cm was immersed in the flame retardant obtained in Preparation Example 10 for 10 minutes, and then air-dried at room temperature for 2 days. It was a piece of wood. Using the flame retardant obtained in Preparation Example 7, the same treatment as in Example 11 was performed to obtain a wood piece of Example 12. The piece of wood was exposed to a burner adjusted to a constant flame for 30 seconds, and the residual flame time until the flame completely disappeared from the piece of wood after separation from the flame was measured. In Comparative Example 3, the same test was performed on untreated wood chips. The results of these tests are shown in Table 2 below.

[0042]

[Table 2]

Example 13 A Teflon-containing flame retardant obtained by adding 5 parts of a 60% Teflon (registered trademark) emulsion to 95 parts of the flame retardant obtained in Preparation Example 9 was used. Length 100
cm cloth is dipped for 5 seconds, pulled up and air-dried for 20 minutes to obtain a flame-retardant test sample of Example 11. Oxygen index 29

[0044]

According to the present invention, it is possible to provide a novel liquid flame retardant which does not contain heavy metals, chlorine or bromine and exhibits a flame retardant effect even in a small amount, and a method for flame retarding fibrous materials using the same.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 13/44 D06M 13/44 D21H 21/34 D21H 21/34 // C08L 85/02 ZAB C08L 85/02 ZAB (72) Inventor Yoshinori Omae 1-3-3 Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo F-term (reference) in Chemipro Kasei Co., Ltd. 4H028 AA38 AA40 AA43 AA48 AA49 AB01 BA02 BA04 BA05 4J002 CP032 CQ011 EW156 FD132 FD136FD136 4L033 AC05 BA83 4L055 AG77 AG86 AG97 AH26 FA11 FA22 GA44

Claims (14)

[Claims] [Claim 1] The following general formula (1) (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) A liquid flame-retardant agent selected from the group consisting of a solution in which the cyclic phosphazene compound (A) is dissolved in a solvent, an emulsion obtained by dispersing in a water, and an emulsion obtained by dispersing a solution in a solvent in water. 2. The following general formula (1): (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Cyclic phosphazene compound (A) and the following general formula (2) (Wherein, n is an integer of 1 to 20, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group, and an amino group). Liquid flame-retardant agent selected from the group consisting of a solution of the obtained chain phosphazene compound (B) in a solvent, an emulsion dispersed in water, and an emulsion dispersed in water of a solution dissolved in the solvent. . 3. The following general formula (1): (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Liquid flame retardant containing cyclic phosphazene compound (A) and silicone oil. 4. The following general formula (1): (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Cyclic phosphazene compound (A) and the following general formula (2): (Wherein, n is an integer of 1 to 20, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group, and an amino group). Liquid flame-retardant agent containing the isolated chain phosphazene compound (B) and silicone oil. 5. The following general formula (1): (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) A liquid flame-retardant agent selected from the group consisting of a solution obtained by dissolving a solution containing the phosphazene compound (A) and silicone oil in a solvent, and an emulsion dispersed in water. 6. The following general formula (1): (In the formula, m is an integer of 3 to 10, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group and an amino group.) Cyclic phosphazene compound (A) and the following general formula (2): (Wherein, n is an integer of 1 to 20, and Q is a group independently selected from the group consisting of an aryloxy group, an alkoxy group, and an amino group). A liquid flame-retardant agent selected from the group consisting of a solution obtained by dissolving a solution containing at least the linear phosphazene compound (B) and silicone oil in a solvent and an emulsion dispersed in water. 7. The following general formula (1) (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. A) a solution obtained by dissolving a cyclic phosphazene compound (A ′) selected from the cyclic phosphazenes represented by the formula (1) in a solvent, an emulsion obtained by dispersing in a water, and an emulsion obtained by dispersing a solution dissolved in a solvent in water. Liquid flame retardant agent selected from 8. The following general formula (1): (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. ) And a cyclic phosphazene compound (A ′) selected from the cyclic phosphazenes represented by the following general formula (2): (In the formula, n is an integer of 1 to 20, Q is a phenoxy group, an m-tolyloxy group, or a p-tolyloxy group, and a phenoxy group, an m-tolyloxy group, and a p-tolyloxy group in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2n. A) a solution obtained by dissolving a linear phosphazene compound (B ′) selected from the chain phosphazenes represented by the following formula (B ′) in a solvent, an emulsion prepared by dispersing in a water, and an emulsion prepared by dispersing a solution dissolved in a solvent in water. A liquid flame retardant selected from the group consisting of: 9. The following general formula (1): (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. A liquid flame retardant comprising a cyclic phosphazene compound (A ') selected from the cyclic phosphazenes represented by the formula (1) and silicone oil. 10. The following general formula (1): (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. ) And a cyclic phosphazene compound (A ′) selected from the cyclic phosphazenes represented by the following general formula (2): (In the formula, n is an integer of 1 to 20, Q is a phenoxy group, an m-tolyloxy group, or a p-tolyloxy group, and a phenoxy group, an m-tolyloxy group, and a p-tolyloxy group in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2n. A liquid flame retardant comprising a chain phosphazene compound (B ') selected from the chain phosphazenes represented by the formula (1) and silicone oil. 11. The following general formula (1): (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. Liquid flame retardant composed of a solution obtained by dissolving a solution containing a cyclic phosphazene compound (B ') selected from the cyclic phosphazenes represented by the formula (I) and silicone oil in a solvent, or an emulsion obtained by dispersing the solution in water. Processing agent. 12. The following general formula (1): (In the formula, m is an integer of 3 to 10, Q is a phenoxy group, m-tolyloxy group, or p-tolyloxy group, and phenoxy, m-tolyloxy, and p-tolyloxy must be included in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2 m. ) And a cyclic phosphazene compound (A ') selected from the cyclic phosphazenes represented by the following general formula (2): (In the formula, n is an integer of 1 to 20, Q is a phenoxy group, an m-tolyloxy group, or a p-tolyloxy group, and a phenoxy group, an m-tolyloxy group, and a p-tolyloxy group in the same molecule. Contained, but the number of phenoxy groups and the number of m-tolyloxy groups and p-
The total number of tolyloxy groups is 2n. A) a solution containing a chain phosphazene compound (B ′) selected from the chain phosphazenes represented by the formula (I) and silicone oil dissolved in a solvent or an emulsion obtained by dispersing the solution in water. Combustion agent. 13. The liquid flame retardant according to claim 1, further comprising a fluororesin and / or a rubber. 14. A flame-retardant processing method for a fibrous material, comprising applying the flame-retardant agent according to claim 1 to a fibrous material.