TW200842185A - Polyphosphate-containing aqueous dispersion solution, flame retardant using the same and method for flame-retarding fibers using the same - Google Patents

Abstract

Disclosed is an aqueous dispersion containing an organic phosphorus compound, a polyphosphate salt, a surface active agent and water. This aqueous dispersion is useful as an antiflaming agent which is capable of imparting a fiber, especially a CDP (cationic dyeable polyester) fiber or a blended fiber containing a CDP fiber with excellent durable antiflaming properties, while having excellent dispersion stability.

Description

200842185 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a dispersion-stabilized aqueous dispersion containing polyphosphate which imparts excellent flame retardancy to a synthetic fiber structure, and a flame retardant thereof And flame retardant processing of fibers, as well as flame retarded fibers. [Prior Art] Conventionally, as a method of imparting flame retarding properties to fibers by post-processing, a method in which a halogen-based compound is dispersed in water to form a flame-retardant and flame-retardant processing of the fibers is known. A representative example of the halogen compound is brominated naphthenes such as 1,2,5,6,9,10-hexabromocyclododecane (Patent Documents 1 and 2). It is known that the flame-retardant property of a halogen-based compound is generally high, but if the flame-retarded fiber is burned, a harmful halogenated gas is generated, which causes a harmful effect on the human body or the natural environment. Therefore, in recent years, the use of a halogen-based compound as a flame-retardant system has been carried out. Therefore, there is a proposal to replace a halogen-based compound, a flame-retardant using an organophosphorus compound such as an organic phosphate as a flame-retardant, and a flame-retardant processing method of the fiber (Patent Documents 3 to 8). When such a flame retardant for fibers is used, a surfactant is generally used, and it is often used as an aqueous dispersion. However, among these phosphorus-based compounds, in particular, when a phosphite or a phosphate is used, it is difficult to disperse and re-agglomeration has occurred, and it is not possible to stabilize the dispersion as a dispersion. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. [Problem to be Solved by the Invention] An object of the present invention is to provide an organophosphorus compound which can be stably dispersed by imparting excellent flame retardancy to durability. An aqueous dispersion, a flame retardant and a flame retardant processing method using the same. MEANS FOR SOLVING THE PROBLEMS In order to solve the above problems, the inventors of the present invention have conducted intensive studies, and as a result, have found that polyphosphates can stably decentralize organophosphorus compounds, and have completed the present invention. That is, the present invention relates to the following (1) to (1 5). (1) An aqueous dispersion containing an organic phosphorus compound, a polyphosphate, a surfactant, and water; (2) The aqueous dispersion according to the above (1), wherein the aqueous dispersion contains 1 to 90% by weight. % polyphosphate; 200842185 (3) Aqueous fractions as described in (1) or (2) above, a salt of ammonia or an amine of polyphosphate-based polyphosphoric acid, or a sub-genus of poly-acid (4) The aqueous dispersion according to any one of the above (1) to (3) wherein polyphosphate is ammonium polyphosphate or sodium polyphosphate; (5) as described above (1)~ (Aqueous dispersion according to any one of the above), wherein the aqueous dispersion contains an organic phosphorus compound in a total amount of from 1 to 90% by weight; (6) as in the above (1) to (5) A description of the aqueous dispersion of the organic phosphorus compound from the following general formula (I) [Chemical Formula 1] R^O-P-OR13 (i) or12 [wherein, R i , R ! 2, R i 3 each independently represents a hydroxyl group, an amine group, a thiol group, a carboxyl group, a ureido group, a (C1-C4) alkyl group, a bis((M_c4)alkylamino group, a diphenylamino group, an aryl group, a phenoxy group. Or (Ci_C4) hospital white spoon-substituted aryl group] phosphite as shown, by the following formula (II) [Formula 2] Ο

II (IX) R2i〇—P—OR23 OR22 [wherein, R 2 2, R 23 each independently represent a hydroxyl group, an amine group, a -6 - 200842185 , a di(C1-C4 )alkylamine (C1-C4 ) a phosphate represented by an alkoxy-substituted cyano group, a carboxyl group, a ureido group, a (C1-C4)alkyl group, a diphenylamino group, an aryl group, a phenoxy group or an aryl group, and has the following formula (III) ) 【化3】

^31' -〒一民33 "32 (III) [wherein R3l, R32, R33 are each independently cyano, carboxy, ureido, (C1-C4)alkyl, diphenylamino, A phosphine oxide represented by an aryl group, a phenoxy group or an aryl group, is represented by the following formula (IV): R4i-P-R43 R42 (IV) wherein R41, R42 and R43 are each independently a phosphine represented by a cyano group, a carboxyl group, a ureido group, a (C1-C4)alkyl group, a diphenylamino group, an aryl group, a phenoxy group or an aryl group, and the following formula (V) Substituted by a hydroxyl, amine, or bis(C1-C4)alkylamine (C1-C4) alkoxy group: can be represented by a hydroxyl group, an amine group, a di(C1-C4)alkylamine (C1-C4) alkane Oxygen substitution 200842185 化(R51〇)n-1 (NHR52)3-n (V) [wherein R51 and R52 each independently represent a trans group, an amine group, an amino group, a carboxyl group, or a ureido group. , (C1-C4)alkyl, di(C1-C4)-terminated amino, diphenylamino, aryl, phenoxy or (C1-C4)alkoxy substituted aryl, η表系0 At least one compound selected from the group consisting of o-acidic amines represented by an integer of ～2; (7) The aqueous dispersion liquid according to the above (6), 1111, 1112, 1113 of the formula (I), 1121, 1122, 1123 of the formula (11), R31 of the formula (ill), rule 32, R33, and R41, R42, and R43 of the formula (iv) R51 and R52 of the formula (V) are each independently an aryl group or an unsubstituted aryl group which may be substituted by a (C1-C4) or aryl group (8) as in the above (1) to (7) The aqueous dispersion according to any one of the above (1) to (8), wherein the hydrazine contains an ultraviolet absorbing agent; (9) a flame retardant, wherein the aqueous dispersion according to any one of the above (1) to (8) is used; (1) The flame-retardant according to the above (10), wherein the flame-retardant agent is a fiber-based polyester fiber; (1 2) the resistance according to the above (1 1) a flame-retardant, wherein the polyester fiber is a cationic dyeable polyester fiber or a blended fiber containing a cationic dyeable polyester fiber; -8 - 200842185 (1 3 ) The flame retardant according to the above (1 2), wherein the blending agent a fiber-based cationic dyeable polyester fiber and a blended fiber of the other polyester fiber; (1) A flame retardant processing method of the fiber, comprising the method according to any one of the above (1) to (8) Dispersion was treated polyester fiber; and (15) - kind of fibers, which lines were processed by a flame trap method described in (14). Advantageous Effects of Invention The flame retardant of the present invention using an aqueous dispersion containing an organic phosphorus compound, a polyphosphate, a surfactant, and water is excellent in dispersion stability and can be used for fibers, especially cationic dyeable polyester fibers or The blended fiber of the cationic dyeable polyester fiber and other polyester fibers is subjected to high-performance flame retardant processing with durability. When the flame retardant of the aqueous dispersion of the present invention is used together with the dye for dyeing cloth or fibers, no spots are formed and a uniform dye can be obtained. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. The aqueous dispersion of the present invention contains an organophosphorus compound 'polyphosphate, a surfactant, and water. The organophosphorus compound is an organophosphorus compound containing a trivalent or pentavalent phosphorus atom in the molecule. Preferable examples thereof include a phosphite represented by the above formula (I), a phosphate represented by the formula (II)-9-200842185, and a phosphine represented by the formula (III). At least one compound of guanamine phosphate represented by formula (V). One of the compounds of the formula (1), (IV) or (V) may be used. Further, a compound contained in one formula may be used. Preferably, one to five compounds are generally used in the above formula (I), R11, Rl2, Rl3, R22, and R23, R3 of the formula (III), and r41, r42, r43, and formula (V) of R32. Of the aryl group substituted with r51, I group, cyano group, carboxyl group, ureido group, (C1-C4) alkane 3-amino group, diphenylamino group, aryl group or phenoxy anthracene as (C1-C4) And an alkyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group may be mentioned as a (C1-C4) alkoxy group, and examples thereof include a methylpropoxy group, an isopropoxy group, and a n-butoxy group. Isobutoxide. The aryl group may, for example, be a substitution position of a substituent of a phenyl group or a biphenyl group, and is not particularly limited to any position. As an aryl group which may be substituted by a hydroxyl group, an amine group, a cyano group, a carboxy-alkyl group, a di(C1-C4)alkylamino group, a diphenoxy group or a (C1-C4) alkoxy group, a methylphenyl group , ethylphenyl, n-propylphenyl, isophenyl, hydroxyphenyl, methoxyphenyl, ethoxy, aminophenyl, N,N-dimethylaminophenyl, N, ▲ (II) and (III) which are selected from the group consisting of phosphine and the group of the formula (IV), may be used in combination of two or more. To two or more compounds, R21, R33 of the formula (II), and the formula (IV) 152 may be, for example, a hydroxyl group, an amine g, or a di(C1-C4) alkane (C1-C4) alkoxy group. The thiol group, the base, the third butyl group and the like are mentioned. An oxy group, an ethoxy group, a decyl group, a tert-butoxy group or the like, a naphthyl group or the like. Further, the aryl group may be a substitutable compound, a ureido group or a (C1-C4 group amino group, an aryl group or a benzene group), and examples thereof include a phenyl group, a propylphenyl group, a dimethylphenyl group, and a phenoxyphenyl group. , N-diethylaminophenyl-10 - 200842185, N,N-diphenylaminophenyl, cyanophenyl, carboxyphenyl, biphenyl, naphthyl, etc. (C1-C4)alkyl or aryl substituted aryl or unsubstituted aryl, such as phenyl, methylphenyl, dimethylphenyl, biphenyl, naphthyl, especially phenyl, A The organophosphorus compound represented by the above formulas (I) to (V) may be a commercially available compound or may be prepared by a usual production method. The organophosphorus compound used in the liquid may be a phosphonic acid (for example, phenylphosphonic acid or the like) or a sulfonic acid (for example, diphenylsulfonic acid, etc.) in addition to the compounds represented by the above formulas (I) to (V). The polyphosphate used in the aqueous dispersion of the present invention is used to stabilize the dispersion. As the polyphosphate, there may be mentioned An ammonium or amine salt of polyphosphoric acid such as ammonium phosphate or triethylamine polyphosphate; or an alkali metal or alkaline earth metal salt of polyphosphoric acid such as sodium polyphosphate or magnesium polyphosphate. Among them, ammonium polyphosphate is preferred. Sodium polyphosphate, particularly preferably ammonium polyphosphate. The average degree of polymerization of phosphoric acid in the polyphosphate is preferably from 3 to 3 000: ^ right, particularly preferably from about 3 to about 2000. These polyphosphates can be used in the city. The compound sold (Sumitomo Chemical Co., Ltd., Pure Chemical Co., Ltd., etc.) can also be prepared by using a usual manufacturing method. Further, it is also possible to use polyphosphate to be covered by melanin or by house. For the scaly coater, a commercially available one may be used. -11 . 200842185 The surfactant used in the aqueous dispersion of the present invention may, for example, be a cationic surfactant, a nonionic surfactant, and/or The anionic surfactant is preferably a nonionic surfactant, an anionic surfactant, or a mixed nonionic surfactant and an anionic surfactant. As an anionic surfactant, Examples thereof include alkyl sulfates such as higher alcohol sulfate salts, higher alkyl ether sulfate salts, and sulfated fatty acid esters; alkylsulfonates such as alkylbenzenesulfonates and alkylnaphthalenesulfonates; An alkyl phosphate such as a higher alcohol phosphate salt or an alkylene oxide adduct phosphate salt of a higher alcohol. Further, an alkyl aryl sulfonate, a polyoxyalkylene alkyl ether sulfate, or a polyoxidation may be mentioned. An alkyl ester phosphate, a polyoxyalkylene alkyl ether carboxylate, a polycarboxylate, a Turkish red oil, a petroleum sulfonate, an alkyl diphenyl ether sulfonate, etc. wherein 'the preferred anionic interface The active agent is of the following formula (1 〇 7 )

【化6】 R

0(CH2CH20)n-S03H (107) [In the formula, R represents a hydrogen atom, a (C6-C18) alkyl group, a styryl group or a benzyl group, and η represents an integer of 丨~15] a polyoxyethylene phenyl ether. A sulfate salt or an alkylene oxide adduct phosphate salt of a local alcohol (for example, manufactured by First Industrial Pharmaceuticals Co., Ltd.: plaisurf). Further, in the general formula (1〇7), it is convenient to carry the sS as a free acid, but as the relative cation of the salt, a base-12-200842185 metal (for example, a clock, a nano, a hydrazine, etc.), a money, etc. may be mentioned. Preferably it is nano or money. Among the surfactants represented by the formula (107), particularly preferred are R-based (C6-C12) linear alkyl groups, n-based compounds having 4 to 12, more preferably R-based fluorenyl groups, η a compound of system 7. The nonionic surfactant may, for example, be a polyoxyethylene styrenated phenyl ether such as polyoxyethylene distyrenated phenyl ether or polyoxyethylene tristyrenated phenyl ether, preferably the following General formula (108) [Chemical 7]

The compound shown or a mixture thereof. In the general formula (1 〇8), m ' is 1 to 3 ' η ' is a mixture of 8 to 3 0 〇 as a compound represented by the formula (1 0 8 ), and for example, Noigen ΕΑ-87 (No. A Industrial Pharmaceutical Co., Ltd.) and so on. In the formula of the present specification, Me represents a methyl group. These surfactants may be used singly or in combination, and the anionic or nonionic surfactant may be used in a plurality of types, or may be used by mixing one or more kinds of anionic and nonionic surfactants. The above surfactant can be used by using a commercially available compound or by a usual production method. In the aqueous dispersion of the present invention, for the purpose of improving light fastness - 13-200842185, an ultraviolet absorber may also be contained. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays, and examples thereof include a salicylic acid system, a benzophenone system, a benzotriazole system, a hindered amine system, and a triterpenoid system. A compound represented by a cinnamic acid compound, an oxime compound or a benzoxazole compound which absorbs ultraviolet rays and emits fluorescence, that is, a so-called fluorescent whitening agent. The structural formula of the preferred ultraviolet absorber is represented by the formulas (101) to (106) of F. -14- 200842185 【化8】

R12

(105)

In the above formula (106) of the benzotriazole-based ultraviolet absorber, Ri5 represents a linear or branched alkyl group of (C1 to C12), cumyl group, preferably (C1 to C12). a linear or branched alkyl group, particularly preferably a linear or branched alkyl group of (C3 to C6), more preferably a branched alkyl group of (C3 to C5), and examples -15 to 200842185, such as isopropyl Base, isobutyl, second butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl.

Ri6 represents a straight or branched chain of a hydroxyl group, a linear or branched alkyl group of (C1 to C12), a linear or branched alkoxy group of (C1 to C12) or a benzyloxy group, preferably (C1 to C12). The alkyl group is preferably a linear or branched alkyl group of (C1 to C6), more preferably a linear or branched alkyl group of (C 1 to C 3 ), and examples thereof include a methyl group, an ethyl group, and a positive alkyl group. Propyl, isopropyl. R17 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group of (C1 to C12) or a linear or branched alkoxy group of (C1 to C12), preferably a hydrogen atom or a linear chain of (C1 to C3). The branched alkyl group may, for example, be the same group as the linear or branched alkyl group of (C 1 to C 3 ) in the above r16. More preferably, it is a hydrogen atom. R18 represents a hydrogen atom or a hydroxyl group, preferably a hydroxyl group. X represents a hydrogen atom or a chlorine atom, more preferably a chlorine atom. Particularly preferred combinations of R15 to R18 and X are R15-based tertiary butyl group, R16-based methyl group, Rw-based hydrogen atom 'R18-based hydroxyl group, and X-based chlorine atom. The ultraviolet absorber other than the benzotriazole-based compound represented by the above formula (106) may, for example, be a diphenyl group represented by the above formula (1 0 1 ), formula (102) or formula (103). a ketone-based compound and a triterpenoid compound represented by the formula (104) (wherein R9 and Ri〇 each independently represent a hydrogen atom, a hydroxyl group or a (C1 to C5) alkyl group), and the formula (105) a benzotriazole-based and benzophenone-based complex compound (wherein R!1 represents a methyl group, an ethyl group or an isopropanyl group]. Rl2 represents a hydroxyl group, a methoxy group, an ethoxy group or a cardoxy group. The group, Rl3 represents a hydrogen atom, a trans group, a methoxy group or an ethoxy group, R14 represents a hydrogen atom-16-200842185 or a hydroxyl group, and χ represents a hydrogen atom or a chlorine atom). Among the above ultraviolet absorbers, a benzotriazole type represented by the formula (106) is particularly preferred. The above ultraviolet absorbing agent can be used by using a commercially available compound or by a usual production. The aqueous dispersion of the present invention is used as a flame-retardant, and the flame-retardant is also included in the present invention. As a preferred aspect of the aqueous flame-retardant dispersion of the present invention, the aqueous dispersion contains a total amount of 1 to 90% by weight of the organophosphorus compound, preferably 5 to 70% by weight, particularly preferably 1 In the range of 0 to 50% by weight, 0.1 to 90% by weight of polyphosphate is contained, preferably 0.5 to 50% by weight, particularly preferably 1 to 30% by weight. The content of the surfactant contained in the aqueous dispersion of the present invention is usually 5 to 200% by weight, preferably 10%, based on the total amount of the organic phosphorus compound and the ultraviolet absorber when the ultraviolet absorber is contained. ~100% by weight, particularly preferably in the range of 1 〇 to 50% by weight. When the ultraviolet absorber is not contained, the amount of the organophosphorus compound is usually from 5 to 200% by weight, preferably from 10 to 100% by weight, particularly preferably from 10 to 50% by weight. Inside. When the aqueous dispersion of the present invention contains an ultraviolet absorber, the content thereof is usually from 1 to 10% by weight, preferably from 1 to 8% by weight, particularly preferably from 0 to 1% by weight in the aqueous dispersion. ~5 wt% range. The preparation method of the aqueous dispersion of the present invention is not particularly limited, and examples thereof include a method of pulverizing in an aqueous dispersion medium, etc., and a method of stirring the powder. The average particle diameter of the fine particles of the dispersoid dispersed in the aqueous dispersion of the present invention is measured by a Shimadzu laser diffraction type particle size distribution device SALD-2000, and is preferably 20 μm or less. In the aqueous dispersion of the present invention, it is possible to contain a protective effect of polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starch paste, etc. for further improving storage stability, as long as the effect is not impaired. Colloidal agent, flame retardant for improving flame retardant effect, antioxidant, etc. Further, an alkali agent, an acid, a fat, a higher alcohol, a higher fatty acid, a lower alcohol, an organic solvent, a penetration enhancer, a polyol, a preservative, a chelating agent, a pH adjuster, a wetting agent may be added as needed. , defoamers, mildew inhibitors, pigments or pigments. The flame retardant using the aqueous dispersion of the present invention is preferably used for fibers; the flame-processed fiber is preferably a polyester fiber, especially a CDP (positively usable polyester) fiber, or a CDP fiber. Blended with other fibers, especially polyester fibers. Examples of the CDP fibers or polyester fibers include polyethylene terephthalate, polybutylene terephthalate, polyoxyethoxybenzoic acid vinegar, polyethylene naphthalate, and cyclohexane. a fiber of a polyester such as alkylene dimethylene terephthalate; and a dicarboxylic acid component or propylene glycol which is copolymerized with the polyester, such as adipic acid, adipic acid or sulfoisophthalic acid; A fiber obtained by a diol component such as butanediol, cyclohexanedimethanol or diethylene glycol, but not limited thereto. Also included in the fibers of the present invention are yarns, woven fabrics, knitted fabrics, and nonwoven fabrics such as -18-200842185. A flame-retardant processing method of a fiber characterized by using the aqueous dispersion of the present invention is also included in the present invention. In order to flame-retard the fiber, a method such as a dip dyeing method or a pad dyeing method can be used. For example, in the case of using the dip dyeing method, the disperse dye of the fiber, the disperse cationic dye or the like and the aqueous dispersion of the present invention are at a temperature in the range of 110 to 150 ° C, preferably 120 to 140 ° C. The processing is performed for about 10 to 60 minutes. Further, dyeing and flame retarding processing can be performed in multiple stages. Further, a dye such as a fluorescent dye may be added as needed. When the padding method is used, the fiber structure is padded and then subjected to heat treatment such as dry heat treatment or steaming treatment (saturated atmospheric steam treatment, superheated steam treatment, high pressure steam treatment, etc.). In any of the dry heat treatment and the steam heat treatment, the heat treatment temperature is usually from 110 to 210 ° C, preferably from 170 to 210 ° C. If the heat treatment temperature exceeds 21 (TC), the polyester synthetic fiber may be yellowed or embrittled. If necessary, the same bathing method and padding method may be used. In this case, the fiber is subjected to the same bathing method. After flame-retardant processing, it can be reworked by padding. By using two methods, higher flame resistance can be imparted. The present invention will be more specifically illustrated by the following examples, but the invention is not The "parts" and "%" described in the examples are "parts by weight" and "% by weight" unless otherwise specified. Phosphorus compounds dispersed in an aqueous dispersion The particle size distribution of the particles is measured by the Shimadzu laser diffraction type particle size distribution meter device SALD - 2000 to -19 - 200842185, and the median diameter is described as the average particle diameter. Further, the following examples and comparisons The compound of the following formula (201) is RM and the compound of the above formula (I). The compound is commercially available, etc. The compound of the following formula (202) is R21. a compound of the formula (Π). It is commercially available from the company. The compound of the following formula (203) is a compound of the formula (III). This compound was synthesized by the method described in the publication No. 1 45 0 95. TPPO (trade name; a compound of the following formula (204), a compound of the formula (IV), which is a compound of the formula (IV). This compound is synthesized by the method described in the publication No. 43 40 5 (product name; Beixing) The compound of the following formula (2 05) is a compound of the above formula (II), which is a compound of the above formula (II). The method described in the publication No. 2004-43405 synthesizes p-TCP (trade name; Da Ba chemical) The compound of the following formula (206) is a compound of the above formula (II), which is a compound of the above formula (II). The structural formula of the compound for synthesis by the method described in JP-A-2004-434〇5 is a phenyl group. The upper UTP of R&D; Ruang and R2 is a phenyl group. The upper U TPP of the phenyl group (the big eight chemical group R32, the R33 is a phenyl group, and the compound can be made by the special opening). The above formula of R42 and R43 is a phenyl group which can be commercially available as TPP >, and the compound is commercially available as TPP > Element 22 and R23 are 4-methylbenzene: Further, the compound is commercially available as a system. The rule 22 and R23 are methyl groups. Further, the present compound is commercially available as -20-200842185 TCP (trade name; manufactured by Daiba Chemical Co., Ltd.). The compound of the following formula (207) is a compound in which R21 is a naphthyl group, and r22 and r23 are a phenyl group. The compound of the formula (II) can be synthesized by the method described in JP-A No. 2,006-7,0417. Further, the compound is NDPP (trade name; manufactured by Daiba Chemical Co., Ltd.). The following formula (208) is a compound of the above formula (V) wherein R51 and R52 are a phenyl group and n = 2. This compound is disclosed in JP-A-2000-145. As described, it can be obtained by reacting diphenylchlorophosphate with aniline in the presence of an amine catalyst in an organic solvent. The compound of the following formula (209) is R51 and R52 is a phenyl group, n = a compound of the above formula (V) which is obtained by reacting phosphonium chloride with aniline in an organic solvent as described in JP-A-49-53241. The compound of the formula 2 12) is an anionic surfactant represented by the above formula (107) wherein R is a n-decyl group and η is 7. A 30% aqueous solution of the compound is commercially available as Hitenol®-05 (trade name; manufactured by Dai-ichi Kogyo Co., Ltd.). In the present example, a 30% aqueous solution of a commercially available product was used as it is. The compound (213) is a UV absorber represented by the above formula (106) wherein R15 is a third butyl group, R16 is a methyl group, R17 is a hydrogen atom, and Ris is a hydroxyl group, and X is a chlorine atom. This compound is commercially available as EVERS ORB 73 (trade name; manufactured by Everlight Chemical Industrial Corporation). Noigen EA-87 (product - 21 - 200842185; manufactured by Daiichi Kogyo Co., Ltd.) was used as the nonionic surfactant. The nonionic surfactant is commercially available as a mixture of compounds of the above formula (108) wherein m' is 1 to 3 and η' is 8 to 30. [Chem. 9 — 1]

^ν°-Γ〇^3〇-〇-Γ°Ό

-22- 200842185 【化9-2】

(212) (213) The ammonium polyphosphate in the examples was prepared by using Sumitomo Chemical Co., Ltd. Example 1 Preparation of an aqueous dispersion having an average particle diameter of 0.89 3 μm using a sand mill, and the composition shown in Table 1 was used. The mixture was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 0.89 3 μηη. -23- 200842185 [Table 1] Composition Water 6 3.8% Formula (201) (Compound of Formula (I)) 2 0.0% Formula (2 1 3 ) (UV Absorber) 4.0% Sodium Polyphosphate 3.0% Noigen EA -87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total 10 0.0% Example 2 Preparation of aqueous dispersion with an average particle size of 0.8 99 μπι Using a sand mill, crushing, The modulation has a sputum. The aqueous dispersion of the present invention having a wet particle size of .8 99 μηι is applied to the mixture of the compositions described in Table 2 [Table 2] Composition Water 6 3.8% Formula (201) (Compound of Formula (I)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Sodium polyphosphate 3.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoaming! l 0.2% Antifungal agent 0.1% Total 10 0.0% 24-200842185 Example 3 Preparation of aqueous dispersion of average particle size 9. 9 1 9 μηη Using a sand mill, the mixture of the compositions described in Table 3 was wet-pulverized to prepare an average particle diameter of 0.91 9 μm The aqueous dispersion of the present invention. [Table 3] Composition water 6 1.8% Formula (201) (Compound of the formula (I)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Sodium tripolyphosphate 5.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% wetting agent 0.5% defoamer 0.2% fungicide 0.1% total 10 0.0% Example 4 Preparation of an aqueous dispersion with an average particle size of 0.8 7 7 μηη using a sand mill, in Table 4 The mixture of the composition described was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 0.87 μm. -25- 200842185 [Table 4] Composition water 6 7.1% Formula (201) (Compound of formula (I)) 2 0.0% Formula (213) (UV absorber) 4.0% Sodium polyphosphate 3.0% Newcol 707SF 5.1% Wetting agent 0.5% Defoamer 0.2% Mildew inhibitor 0.1% Total 10 0.0% Newcol 707SF : Nonionic surfactant activity made by Nippon Emulsifier Co., Ltd.

Example 5 Preparation of aqueous dispersion having an average particle diameter of 7.45 3 μηι The mixture of the compositions shown in Table 5 was wet-pulverized using a sand mill to prepare an aqueous dispersion of the present invention having an average particle diameter of 7.453 μm.

-26- 200842185 _[Table 5]_ _ Composition _ _Water 6 6.8% Formula (2 0 2 ) (Compound of formula (11)) 20.0% Formula (213) (UV absorber) 4.0% Ammonium polyphosphate 3.0%

Noigen EA- 87 2.6%

Hitenol NE-05 5 . 8 % wetting agent 0.5 % defoamer 0.2% antifungal agent 0.1% total 10 0.0% Example 6 Preparation of an aqueous dispersion with an average particle size of 7.8 83 μπι using a sand mill, in Table 6 The mixture of the compositions described was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 7.8 8 3 μm. _[Table 6]_ Composition Water 6 3.8% Formula (2 0 2 ) (Compound of formula (11)) 20.0% Formula (2 1 3 ) (UV absorber) 4.0% Sodium polyphosphate 3.0%

Noigen EA-87 2.6%

Hitenol NE-05 5.8 % wetting agent 0.5% defoamer 0.2% fungicide 0.1% total 10 0.0% -27- 200842185 Example 7 Preparation of an aqueous dispersion with an average particle size of 7.2 3 2 μηη Using a sand mill, The mixture of the compositions described in Table 7 was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 7.23 2 μηη. [Table 7] Composition water 6 7.1% Formula (202) (Compound of formula (II)) 2 0.0% Formula (213) (UV absorber) 4.0% Ammonium polyphosphate 3.0% Plysurf 5.1% Wetting agent 0.5% Defoaming Agent 0.2% fungicide 0.1% total 10 0.0%

Plysurf: a higher alcohol alkylene oxide adduct phosphate salt manufactured by Daiichi Kogyo Co., Ltd. Example 8 Preparation of an aqueous dispersion having an average particle diameter of 6.8 6 6 μm using a sand mill, as described in Table 8 The composition mixture was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 6.8 66 μm. -28- 200842185 [Table 8] Composition amount water 6 1.8% Formula (202) (Compound of formula (II)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Ammonium tripolyphosphate 5.0% Noigen ΕΑ-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total 10 0.0% Example 9 Preparation of aqueous dispersion with an average particle size of 0.924 μηι Using a sand mill, on the table The mixture of the compositions described in 9 was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 0.924 μm. [Table 9] Composition amount water 6 3.8% Formula (203) (Compound of the formula (III)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Ammonium polyphosphate 3.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% wetting agent 0.5% defoamer 0.2% fungicide 0.1% total 10 0.0% Example 1 〇-29- 200842185 Average particle size 〇. 9 5 9 μιη of aqueous dispersion is prepared using sanding The mixture of the composition described in Table 10 was wet-pulverized to prepare an aqueous dispersion of the present invention having an average particle diameter of 9.59 μm. _[Table 10]_ _ Composition _ Water 6 3.8% Formula (204) (Compound of formula (IV)) 20.0% Formula (213) (UV absorber) 4.0% Ammonium polyphosphate 3.0%

NoigenEA-87 2.6%

Hitenol NE-0 5 5.8 % wetting agent 0.5% defoamer 0.2% antifungal agent 0.1% total 100.0% Example 1 1 Preparation of an aqueous dispersion with an average particle size of 0.8 8 9 μηη Using a sand mill, Table 1 1 The mixture of the compositions described above was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 8·8 8 9 μηη. -30- 200842185 _[Table η]_ _ group _ _ amount of water 6 3.8% Formula (2 0 5 ) (compound of formula (11)) 20.0 ° /. Formula (2 1 3 ) (UV absorber) 4.0% ammonium polyphosphate 3.0%

Noigen EA- 8 7 2.6%

Hitenol NE-0 5 5 . 8 % wetting agent 0.5 % defoamer 0.2% antifungal agent 0.1% total _ 10 0.0% Example 1 2 Average particle size 〇. 9 2 1 μηη of aqueous dispersion is prepared using sanding The mixture of the compositions described in Table 12 was wet-pulverized to prepare an aqueous dispersion of the present invention having an average particle diameter of 0.921 μm. _[Table 12]_ _ Composition _ Water 6 6.8% Formula (2 0 1 ) (Compound of Formula (I)) 10.0% Formula (2 0 2 ) (Compound of Formula (11)) 10.0% Formula ( 2 1 3 ) (UV absorber) 4.0% ammonium polyphosphate 3.0%

Noigen EA- 8 7 2.6%

Hitenol NE- 0 5 5 . 8 % wetting agent 0.5 % defoamer 0.2% fungicide 0.1% total _10 0.0% -31 - 200842185 Example 1 3 Preparation of an aqueous dispersion with an average particle size of 0.931 μπι using sanding The mixture of the compositions described in Table 13 was wet-pulverized to prepare an aqueous dispersion of the present invention having an average particle diameter of 93·93 1 μm. [Table 13] Composition amount water 6 3.8% Formula (20 1 ) (compound of the formula (I)) 10.0% Formula (203) (compound of the formula (111)) 10.0% Formula (2 1 3 ) (UV absorption) 4.0% Ammonium polyphosphate 3.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoaming! l 0.2% Antifungal agent 0.1% Total 10 0.0% Example 1 4 Average particle size 4.6 76 Preparation of aqueous dispersion of μπι The mixture of the compositions described in Table 14 was wet-pulverized using a sand mill to prepare an aqueous dispersion of the present invention having an average particle diameter of 4.67 6 μηα. -32- 200842185 _[Table 14]_ _ Composition _ _Water 6 6.8% Formula (2 0 2 ) (Compound of formula (11)) 10.0% Formula (2 0 3 ) (Compound of formula (111) 10.0% Formula (213) (UV absorber) 4.0% Ammonium polyphosphate 3.0%

Noigen EA- 8 7 2.6%

Hitenol NE-0 5 5.8 % Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total _10 0.0% Example 1 5 Preparation of aqueous dispersion with an average particle size of 0.901 μπι Using a sand mill, Table 15 The mixture of the compositions described in the above was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 90.91 μm. _[Table 15]_ _ Composition _ _Water 6 6.8% Formula (202) (Compound of Formula (II)) 10.0% Formula (205) (Compound of Formula (II)) 10.0% Formula (2 1 3 ) (UV absorber) 4.0% ammonium polyphosphate 3.0%

Noigen EA-87 2.6%

Hitenol NE- 0 5 5 . 8 % wetting agent 0.5 % defoamer 0.2% fungicide 0.1% total 10 0.0% -33- 200842185 Example 1 6 Preparation of aqueous dispersion with average particle size 〇· 9 2 2 μηη The mixture of the compositions described in Table 16 was wet-pulverized using a sand mill to prepare an aqueous dispersion of the present invention having an average particle diameter of 0.92 2 μηη. [Table 16] Composition - Water 6 3.8% Formula (201) (Compound of the formula (I)) 10.0% Formula (207) (Compound of the formula (11)) 10.0% Formula (2 1 3 ) (UV absorption) 4.0% Ammonium polyphosphate 3.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total 10 0.0% Example 1 7 Average particle size 〇. 9 2 Preparation of 5 μm aqueous dispersion The mixture of the compositions described in Table 17 was wet-pulverized using a sand mill to prepare an aqueous dispersion of the present invention having an average particle diameter of 0.92 5 μηη. -34- 200842185 [Table 17] Composition amount water 6 3.8% Formula (202) (Compound of the formula (II)) 10.0% Formula (207) (Compound of the formula (II)) 10.0% Formula (2 1 3 ) (Ultraviolet absorber) 4.0% Ammonium polyphosphate 3.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total 10 0.0% Example 1 8 Average particle size〇 Preparation of an aqueous dispersion of 9 1 5 μηη A mixture of the compositions described in Table 18 was subjected to a pulverization using a sand mill to prepare a dispersion. The aqueous particle of the present invention having an average particle diameter of 0.9 1 5 μηη [Table 18] Composition amount water 6 3.8% Formula (202) (Compound of the formula (II)) 15.0% Formula (206) (General formula (Π) compound ) 5.0% Formula (2 1 3 ) (UV absorber) 4.0% Ammonium polyphosphate 3.0% Noigen ΕΑ-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoamer 0.2% Anti-mildew U 0.1% Total 10 0.0% -35- 200842185 Example 1 9 Preparation of aqueous dispersion of average particle size 〇·8 1 8 μηι Using a sand mill, the mixture of the compositions described in Table 19 was wet-pulverized to have a Q 8 The aqueous dispersion of the present invention having an average particle diameter of 1 8 μm. [Table 19] Composition of water 6 3.8% Formula (20 8 ) (Compound of formula (V)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Ammonium polyphosphate 3.0% Noigen EA-87 2.6 % Hitenol NE-05 5.8% wetting agent 0.5% defoamer 0.2% fungicide 0.1% total 10 0.0% Example 2 0 Average particle size 9. 9 1 8 μηι of aqueous dispersion is prepared using a sand mill, right The mixture of the compositions described in Table 20 was subjected to wet pulverization to prepare an aqueous dispersion of the present invention having an average particle diameter of 9·9 18 μm. -36- 200842185 [Table 20] Composition Water 6 3.8% Formula (209) (Compound of Formula (V)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Ammonium polyphosphate 3.0% Noigen EA -87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoamer 0.2% Antifungal agent 0.1% Total 10 0.0% Comparative Example 1 Average particle size 〇.8 94 μιη aqueous dispersion is prepared without polyphosphate, use In a sand mill, the mixture of the groups described in Table 21 was subjected to wet pulverization to prepare an aqueous dispersion liquid having an average particle diameter of 0.894 μm. [Table 2 1 ] Composition amount water 6 6.8% Formula (201) (Compound of the formula (I)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Noigen ΕΑ-87 2.6% Hitenol NE-05 5.8% wetting agent 0.5% defoamer 0.2% antifungal agent 0.1% total 10 0.0% Comparative Example 2 -37- 200842185 Average particle size 〇. 9 0 0 μηι Aqueous dispersion is prepared without polyphosphate, using sanding The mixture of the compositions described in Table 22 was wet-pulverized to prepare an aqueous dispersion for comparison having an average particle diameter of 0·900 ml·1111. _[Table 22]_ Composition _ _* Water 6 5.9% Formula (209) (Compound of Formula (V)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% tackifier 0.9% wetting agent 0.5% defoamer 0.2% fungicide 0.1% total ____ 10 0.0% Comparative Example 3 Average particle size 〇 · 9 2 8 μηη of aqueous dispersion without modulation The phosphate was subjected to wet pulverization using a sand mill's composition of the composition described in Table 2 to prepare an aqueous dispersion for comparison having an average particle diameter of 928·928 μm. -38- 200842185 _"Table 23]_ _ Composition _ _ Quantity - 7Jc 6 9.2% Formula (201) (Compound of the formula (I)) 20.0% Formula (213) (UV absorber) 4.0%

Newcol 707SF 5.1% Tackifier 〇·9% Wetting agent Defoamer 〇·2% Mold inhibitor 〇· 1 % Total 10 0,0% Comparative Example 4 Aqueous dispersion with average particle size 9· 9 1 8 μ m The mixture was prepared by wet pulverizing a mixture of the compositions described in Table 24 using a sand mill without using a polyphosphate to prepare an aqueous dispersion for comparison having an average particle diameter of 〇·1 18 μm. _[Table 24]_ Composition ___ Μ_ Water 6 9.2% Formula (2 0 1 ) (Compound of formula (I)) 20.0% Formula (213) (UV absorber) 4.0%

Newcol 707SF 3.0%

DemolSNB 2.1 % tackifier 0.9% wetting agent 0.5% defoamer 0.2% fungicide 0.1% total _ 10 0.0% D em ο 1 SNB: Kawang Co., Ltd. surfactant -39 - 200842185 Comparative Example 5 The aqueous dispersion having a diameter of 4·949 μm was prepared by using a sand mill to wet-pulverize a mixture of the compositions described in Table 25 using a sand mill to prepare a comparative aqueous dispersion having an average particle diameter of 4.949 μΐΠ. liquid. ___[Table 25]_______ _Composition ^一^ - -^_ 7j^ 6 6.8 % Formula (2 0 2 ) (compound of formula (11)) 20.0% Formula (213) (UV absorber) 4·0%

Noigen E A- 8 7 2·6/〇

Hitenol NE-05 5 * 8 〇/o Wetting agent 〇·5% Defoamer 〇·2 % Anti-mold agent ο ·1 % g Ju 10 10 0.0% Comparative Example 6 Average particle size 4 · 8 9 4 μηι The dispersion was prepared without wet polyphosphate, and the mixture of the compositions described in Table 26 was wet-pulverized using a sand mill to prepare an aqueous dispersion for comparison having an average particle diameter of 4·8 94 μm. -40- 200842185 [Table 26] Composition Water 6 5.9% Formula (202) (Compound of Formula (II)) 2 0.0% Formula (2 1 3 ) (UV Absorber) 4.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% tackifier 0.9% wetting agent 0.5% defoamer 0.2% anti-mildew! 1 0.1% total 10 0.0% Comparative Example 7 Preparation of aqueous dispersion with average particle size of 3.9 5 9 μηη without polyphosphate The mixture of the compositions described in Table 27 was wet-pulverized using a sand mill to prepare an aqueous dispersion for comparison having an average particle diameter of 3.999 μm. _[Table 27]_ _ group _ _ quantity water 6 9.2% formula (2 0 2 ) (compound of formula (11)) 20.0% formula (2 1 3 ) (ultraviolet absorber) 4.0%.

Newcol 707SF 3.0%

Demol SNB 2.1 % tackifier 0.9 % wetting agent 0.5% defoamer 0.2% fungicide 0.1% total 10 0.0% -41 - 200842185 Comparative Example 8 Water with an average particle size of 4 · 4 5 5 μ m In the 5-week process, the polyphosphate was not used, and the mixture of the compositions described in Table 28 was wet-pulverized using a sand mill to prepare a comparative aqueous dispersion having an average particle diameter of 4 · 4 5 5 μΐΠ. . _一_[Table 28]__ _Composition ___ _1_ 7jc 7 0.1% Formula (202) (Compound of formula (II)] 20.0% Formula (213) (UV absorber) 4.0%

Plysurf 5.1% wetting agent 〇·5% defoamer 0.2% antifungal agent 0.1% total __10 0.0% Comparative Example 9 Average particle size 〇. 9 2 8 μιη aqueous dispersion is prepared without polyphosphate, using sanding The mixture of the compositions described in Table 29 was wet-pulverized to prepare an aqueous dispersion for comparison having an average particle diameter of 0.928 μm. •42- 200842185 『Table 29】 Composition water 6 6.8% Formula (203) (Compound (通式) compound) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total ____ 10 0.0% Comparative Example 10 Preparation of aqueous dispersion with average particle size of 0 · 9 8 9 μ m without polyphosphate, use The sand mill's wet-pulverized the mixture of the groups described in Table 30 to prepare an aqueous dispersion for comparison of average particle diameters of 989·989 μΠ1. Γ Table 30] Composition water 6 6.8% Formula (204) (Compound of formula (IV)) 2 0.0% Formula (2 1 3 ) (UV absorber) 4.0% Noigen EA-87 2.6% Hitenol NE-0 5 5.8% wetting agent 0.5% defoamer 0.2% antifungal agent 0.1% total _____ 10 0.0% Comparative Example 11 -43- 200842185 Average particle size 〇· 8 93 μπι of aqueous dispersion is prepared without polyphosphate, using sand In the mill, the mixture of the compositions described in Table 31 was subjected to wet pulverization to prepare an aqueous dispersion for comparison having an average particle diameter of 0.89. [Table 3 1 ] Composition ........... Denier water 6 6.8% Formula (2 0 5 ) (Compound (通式) compound) 2 0.0% Formula (2 1 3 ) (UV absorption) 4.0% Noigen ΕΑ-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Antifoaming agent 0.2% Antifungal agent 0.1% Total __- 10 0.0% Comparative example 1 2 Average particle size 〇· 9 2 7 μ The aqueous dispersion of m was prepared by wet pulverizing a mixture of the compositions described in Table 32 using a sand mill to prepare a comparative aqueous dispersion having an average particle diameter of 927 927 μΠ1. -44- 200842185 [Table 32] Composition amount water 6 6.8% Formula (201) (Compound of the formula (I)) 10.0% Formula (202) (Compound of the formula (II)) 10.0% Formula (2 1 3 ) (UV absorber) 4.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoamer 0.2% Total 10 0.0% Comparative Example 1 3 Average particle size 〇. 9 0 1 μ m of aqueous dispersion The mixture was prepared by wet pulverizing the mixture of the groups described in Table 3 using a sand mill without using a polyphosphate to prepare an aqueous dispersion for comparison of average particle diameters of 901.901 μm. [Table 33] Composition amount water 6. 6.8% Formula (201) (compound of the formula (I)) 10.0% Formula (203) (compound of the formula (III)) 10.0% Formula (2 1 3 ) (UV absorber) ) 4.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoamer 0.2% Anti-mold! 0.1 0.1% Total 10 0.0% Comparative Example 1 4 -45- 200842185 Water with an average particle size of 0.861 μιη The dispersion was prepared without using a poly-o-acid salt, and the mixture of the compositions described in Table 34 was subjected to wet pulverization using a sand mill to prepare an aqueous dispersion for comparison having an average particle diameter of 0.86. [Table 34] Composition ___ _* Water 6 6.8% Formula (202) (Compound of the formula (Π)) 10.0% Formula (203) (Compound of the formula (III)) 10.0% Formula (213) (UV absorption) Agent) 4.0% Ν 〇ige η Ε A -87 2.6% Hitenol ΝΕ-05 5.8% Wetting agent 0.5% Defoaming! ί 0.2% Antifungal agent 0.1% Total 10 0.0% Comparative Example 1 5 Average particle size 〇· 9 Preparation of 5 1 μm aqueous dispersion without using polyphosphate, using a sand mill, wet-pulverizing the mixture of the compositions described in Table 35 to prepare a comparison of average particle diameters of 0 · 9 5 1 μηη Aqueous dispersion. -46- 200842185 _[Table 35]_ _ Composition _ _Water 6 6.8% Formula (202) (compound of formula (II)) 10.0% Formula (205) (compound of formula (II)) 10.0% (213) (UV absorber) 4.0%

Noigen EA-87 2.6%

Hitenol NE-05 5.8 % wetting agent 0.5% defoamer 0.2% fungicide 0.1% total 10 0.0% Comparative Example 1 6 The aqueous dispersion with an average particle size of 0.944 μη is prepared without polyphosphate, using a sand mill, The mixture of the compositions described in Table 3 was wet-pulverized to prepare an aqueous dispersion for comparison having an average particle diameter of 0.944 μm. _[Table 36]_ _ Composition _ Water 6 6.8% Formula (2 0 1 ) (Compound of Formula (I)) 10.0% Formula ( 207 ) (Compound of Formula (II)) 10.0% Formula (2 1 3) (UV absorber) 4.0%

Noigen EA-87 2.6%

Hitenol NE- 0 5 5.8 % wetting agent 0.5 % defoamer 0.2% fungicide 0.1% total 10 0.0% -47- 200842185 Comparative Example 1 7 The aqueous dispersion with an average particle size of 0.943 μη is prepared without polyphosphate. In the sand mill, the mixture of the compositions described in Table 3 was wet-pulverized to prepare an aqueous dispersion having an average particle diameter of 0·943 μm. [Table 37] Composition amount water 6 6.8% Formula (202) (Compound of the formula (II)) 10.0% Formula (206) (Compound of the formula (II)) 10.0% Formula (2 1 3 ) (UV absorber) ) 4.0% Noigen EA-87 2.6% Hitenol NE-05 5.8% Wetting agent 0.5% Defoamer 0.2% Mold inhibitor 0.1% Total __ 10 0.0% Comparative example 1 8 Average particle size 〇 · 9 2 0 μ m The aqueous dispersion liquid was prepared by using a sand mill to wet-pulverize a mixture of the compositions described in Table 38 using a sand mill to prepare an aqueous dispersion for comparison having an average particle diameter of 〇92〇μΠ1. -48- 200842185 _[Table 38]_ _ Composition _ _Water 6 6.8% Formula (2 0 2 ) (Compound of Formula (11)) 15.0% Formula (206) (Compound of Formula (II)) 5.0 % Formula (213) (UV absorber) 4.0%

Noigen EA-87 2.6%

Hitenol NE-05 5.8 % wetting agent 0.5% defoamer 0.2% antifungal agent 0.1% total 10 0.0% Comparative Example 1 9 The average particle size of 0.8 99 μιη of aqueous dispersion is prepared without polyphosphate, using a sand mill, The mixture of the compositions described in Table 3 was subjected to wet pulverization to prepare an aqueous dispersion for comparison having an average particle diameter of 0.899 μm. _[Table 39]_ _ group _ _ amount water 6 6.8% formula ( 20 8 ) (compound of formula (V)) 20.0% formula (2 1 3 ) (ultraviolet absorber) 4.0%

Noigen EA-87 2.6%

Hitenol NE- 0 5 5.8 % wetting agent 0.5 % defoamer 0.2% fungicide 0.1% total 10 0.0% Comparative Example 2 0 -49- 200842185 Aqueous dispersion with an average particle size of 0.9 2 8 μηη without polyphosphate The mixture of the compositions described in Table 40 was wet-pulverized using a sand mill to prepare an aqueous dispersion for comparison having an average particle diameter of 0.92 8 μπα. ____[Table 40]_ __Group ___Quantity Water 6 6.8% Formula (209) (Compound of Formula (V)) 20.0% Formula (213) (UV Absorber) 4.0%

Noigen EA-87 2.6%

Hitenol NE-05 5.8% wetting agent 0.5% defoamer 0.2% antifungal agent 0.1% total 10 0.0% Example 2 1 and Comparative Example 2 1 Flame retardant processing of polyester/CDP blended fiber cloth with aqueous dispersion The aqueous dispersion prepared in Examples 1 to 20 and Comparative Examples 1 to 20 was dyed by the dip dyeing and bathing method, respectively, and the cloth of 40% of the blended CDP and other polyesters containing 50% of the blended fibers was dyed and dried on the same day. Temple @ line flame retardant processing. That is, as a dyebath, a dispersion solution of 0.72% owf (by weight of fiber) of a disperse dye and a cationic dye solution of 92% owf and each of the aqueous dispersions prepared in Examples 1 to 2 or Comparative Examples 1 to 2 0 The liquid, the respective bath ratio (relative to the amount of liquid used in the grey fabric) is 1: 20, and the treatment is carried out at 13 (TC for 40 minutes - 50 - 200842185. The dye used is · 24% as a disperse dye) Kayalon microester yellow eight (^-!^, 0.24% of Cayalon microester red AQ-LE, 0.24% of Cayalon microester blue AQ-LE; as a cationic dye 0.46% of Kaya Kulilu (1^)^(:71) yellow 31^-£〇, 0.24°/) Kayakulilu red GL-ED, 0.22% Kayakulilu blue GSL-ED. Then, right Each fabric was subjected to reduction washing, followed by heat treatment at 180 ° C for 30 seconds. Further, according to JIS K 3 3 7 1, a weakly alkaline first detergent having a ratio of lg/L was used, and the bath ratio was 1 · · 40, Washing each cloth with water at 60 °C ± 2 °C for 15 minutes, then washing at 40 °C ± 2 °C for 3 times for 5 minutes, centrifugal dehydration for 2 minutes, then, 60 Hot air drying at °C ±5 °C One cycle was carried out for 5 cycles. The blended fiber cloth of 40 types obtained by the above operation was used as a test piece, and the burning test was performed thereon. Further, the above-mentioned reduction washing means that 2 g/L was prepared. An aqueous solution of bisulfite, 2 g/L of caustic soda, and 1 g/L of surfactant was heated to 80 ° C, and then flame-treated fabric was added and treated for 20 minutes. Test Example 1 Cohesiveness test 1 · Re-coagulation test of test method A 1) Method The aqueous dispersions prepared in Examples 1 to 20 and Comparative Examples 1 to 20 were placed at room temperature for 14 days, and the test was carried out. There was a re-agglomerated bottom agglomerate (precipitate), and the following evaluation was performed. The results are shown as Evaluation A and are shown in Tables 41-1 and 41-2 below. 2) Evaluation 〇: There is no agglomeration at the bottom, and it may be easily redispersed when shaking. X: There is agglomeration at the bottom. It is impossible to easily disperse and separate when shaking: Separation into 2 layers 2. Test method B re-cohesive test 1) Method 3 ml of the aqueous dispersion prepared in Examples 1 to 20 and Comparative Examples 1 to 20 was placed in a centrifuge (rotation number 5 0 0 rp m ) for 20 minutes, and then the bottom agglomerates were tested to carry out the following Cohesion evaluation. The results are shown as Evaluation B and are shown in Table 41-1 and Table 41_2 below. 2) Evaluation The agglomerates at the bottom were punctured with a glass rod, and the length from the interface between the precipitate and the water to the bottom was regarded as a, and the length from the interface between the precipitate and the water as the glass rod was regarded as X. ◎ : X 二 a (glass rod easily reaches the bottom) 〇: x^a/2 Δ: a/2>x>0 x : x = 0 Test Example 2 -52- 200842185 Dispersibility Test 1. Test Method 10 ml The aqueous dispersion prepared in Examples 1 to 20 and Comparative Examples 1 to 20 was placed at 60. The evaluation of dispersibility was carried out in the following room in a constant temperature room for 7 days. The results are shown in Table 4, Table 1 and Table 4 to 2 below. 2. Evaluation: If the dispersion to be placed is stirred, then Dispersion X: Separated into two layers, and did not disperse even under stirring. Test Example 3 Flame Retardancy Test 1 · Test Method Using the aqueous dispersions prepared in Examples 1 to 20 and Comparative Examples 1 to 2 In Example 2 1 and Comparative Example 2, the blended fiber fabric treated by the dip-dyeing bath treatment was used as a test piece according to the fire law j IS B 109 1 A-1 method (45 degree micro-flame lamp method). The combustion test was carried out, and the following evaluations were carried out. The results are shown in Table 4 丨 1 and Table 4 丨 2 below. 〇: Measurements were performed 5 times, and the afterflame time was 3 seconds or less X: -53- 200842185 [Table 41_1] Flame Retardant Flame Retardability Dispersibility AB Untreated Fabric X Example 1 〇〇 ◎ Example 2 〇〇 ◎ Example 3 〇〇 〇 Example 4 〇〇 ◎ 〇 Example 5 〇〇 ◎ 〇 Example 6 〇〇〇〇 Example 7 〇〇〇〇 Example 8 〇〇 ◎ 〇 Example 9 〇〇 ◎ 〇 Example 1 〇〇〇 ◎ 〇 Example 1 1 〇〇 ◎ 〇 Example 1 2 〇. 〇 ◎ 〇 Example 1 3 〇〇 ◎ 〇 Example 1 4 〇 〇 ◎ 〇 Example 1 5 〇〇 ◎ 〇 Example 1 6 〇〇 ◎ 〇 Example 1 7 〇〇 ◎ 〇 Example 1 8 〇〇 ◎ 〇 Example 1 9 〇〇 ◎ 〇 Example 20 〇〇 ◎ 〇 -54- 200842185 [Table 41-2] Flame-retardant flame-retardant re-cohesive dispersibility AB Comparative Example 1 〇 separation ◎ X Comparative Example 2 〇 separation ◎ X Comparative Example 3 〇 Division ◎ X Comparative Example 4 〇 separation ◎ X Comparative Example 5 〇XX 〇Comparative Example 6 〇XX 〇Comparative Example 7 〇XX 〇Comparative Example 8 〇XX 〇Comparative Example 9 〇XX 〇Comparative Example 1 〇〇XX 〇Comparative Example 1 1 〇XX 〇Comparative Example 12 〇Separation ◎ X Comparative Example 13 〇 Separation ◎ X Comparative Example 1 4 〇 XX 〇 Comparative Example 1 5 〇 XX 〇 Comparative Example 1 6 〇 Separation ◎ X Comparative Example 1 7 X 〇 ◎ 〇 Comparative Example 1 8 〇 XX 〇 Comparative Example 19 〇 XX 〇Comparative Example 20 〇XX 〇 by Table 41-1 The results of Table 41-2 are known as 'blended fiber fabrics flame-retarded by the aqueous dispersions of Examples 1 to 20 prepared using polyphosphate and Comparative Examples 1 to 16 prepared without polyphosphate. And the blended fiber fabric of the flame retardant processing of the aqueous dispersion of 1 8 to 20 is a flame-retardant system-55-200842185 lattice, and the presence or absence of the polyphosphate does not affect the flame-retardant property of the aqueous dispersion. However, the flame-retardant property of the blended fiber fabric which was flame-retarded by the aqueous dispersion of Comparative Example 17 was X. In the evaluation A of the re-cohesiveness test, 'the aqueous dispersions of Examples 1 to 20 of the present invention containing the polyphosphate are all hydrazine, and Comparative Examples 1 to 20 containing no polyphosphate. In the aqueous dispersion, except for Comparative Example 17, all were X or separated, and re-agglomeration occurred. Further, in Evaluation B, the aqueous dispersions of Examples 1 to 20 of the present invention were all 〇 or ◎. In the evaluation of the dispersibility test, the aqueous dispersions of Examples 1 to 20 of the present invention are all in the form of hydrazine, and the aqueous dispersions of Comparative Examples 1 to 4, 1, 2, 13 and 16 are contained. The case of the compound of the formula (I) is X, and the aqueous dispersion of the present invention using a polyphosphate, particularly the compound of the formula (I), exhibits high effectiveness in the dispersion stability system. As described above, the test results using the aqueous dispersion of the present invention as a flame-retardant showed that the excellent flame-retarding property of the aqueous dispersion of the present invention can be maintained while having high dispersibility. Further, when the aqueous dispersion of the present invention is used as a flame-retardant, it is possible to repeat the five-cycle water washing or the like, and the above-described performance can be remarkably maintained, and the durability is extremely excellent. INDUSTRIAL APPLICABILITY It is apparent from the above that according to the present invention, it is possible to provide an aqueous dispersion of a non-halogen flame retardant which imparts excellent durability to fibers, particularly a blended fiber of CDP and other polyesters. Flame performance. -56-

Claims (1)

200842185 X. Patent application scope 1 · An aqueous dispersion containing organic dish compounds, polyphosphates, surfactants and water. 2. The aqueous dispersion of claim 1 wherein the aqueous dispersion contains from 1 to 90% by weight of polyphosphate. 3. An aqueous dispersion according to claim 1 or 2 wherein the polyphosphate is a salt of an ammonia or an amine of polyphosphoric acid or a salt of an alkali metal or an alkaline earth metal of a polyphosphoric acid. 4. An aqueous dispersion according to claims 1 to 3 wherein the polyphosphate is ammonium polyphosphate or sodium polyphosphate. The aqueous dispersion according to any one of claims 1 to 4, wherein the aqueous dispersion contains a total amount of the organic phosphorus compound in an amount of from 1 to 90% by weight. 6. The aqueous dispersion according to any one of the above-mentioned claims, wherein the organophosphorus compound is from the following formula (I): R^O-P-〇R13 〇R12 (I Wherein RM, R12, and R13 each independently represent a hydroxyl group, an amine group, a cyano group, a carboxyl group, a urea group, a (C1-C4) alkyl group, a bis(CM-C4)alkylamino group, a diphenyl group. a phosphite represented by an amino group, an aryl group, a phenoxy group or a (C1-C4)alkoxy-substituted aryl group, the following formula (II) -57- 200842185 [Chemical 2] ΟIIR21〇-0 Ruler 23OR22 (工工) [wherein, R2 1, R2 2, and R23 each independently represent a cyano group, a carboxyl group, a urea group, a (C 1 - C 4 ) alkyl group, a diphenylamino group, an aryl group, a phenoxy group. Phosphate represented by a group or an aryl group, the following formula (III) [Chemical Formula 3] 〇II R31-P-33R32 (HI) [wherein, R31, R32, and R33 each independently exhibit a cyano group or a carboxyl group. a phosphine oxide represented by a ureido group, a (C1-C4)alkyl group, a diphenylamino group, an aryl group, a phenoxy group or an aryl group, which has the following formula (IV): —P—43R42 (IV) [wherein, R4I, R42, and R43 are each independently shown: The hydroxy, amine, or bis(C1-C4)alkylamine (C1-C4) alkoxy group may be substituted by a hydroxyl group, an amine group, a di(C1-C4)alkylamine: C1-C4) alkoxy group. Substituted by hydroxyl, amine, -58- 200842185 cyano, carboxyl, ureido, (C1-C4)alkyl, di(C1-C4)alkylamino, diphenylamino, aryl, benzene a phosphine represented by an oxy group or a (C1-C4)alkoxy-substituted aryl group, and the following formula (V): 5(R5i〇)n-P-(NHR52)3-n (V) Wherein R51 and R52 each independently represent a hydroxyl group, an amine group, a cyano group, a carboxyl group, a urea group, a (C1-C4) alkyl group, a di(C1-C4)alkylamino group, a diphenylamine group. At least one compound selected from the group consisting of a phosphine phosphate represented by a aryl group, an aryl group, a phenoxy group or a (C1_C4) alkoxy group-substituted aryl group, and η represents an integer of 0 to 2. 7. The aqueous dispersion according to claim 6, wherein R11, R12, Rl3 of the formula (I), R21, R22, R23 of the formula (III), and R31, R32 and R33 of the formula (III) R41, R42, R43 of the formula (IV) and R51 and R52 of the formula (V) are each independently an aryl group or an unsubstituted aryl group which may be substituted with a (CM-C4)alkyl group or an aryl group. 8. The aqueous dispersion according to any one of claims 1 to 7, which further comprises an ultraviolet absorber. A flame retardant which uses the aqueous dispersion of any one of claims 1 to 8. 1 0. The flame retardant according to item 9 of the patent application, which is used for fibers. -59- 200842185 1 1 A flame retardant according to the first aspect of the invention, wherein the fiber is a polyester fiber. A flame retardant according to the invention of claim 11, wherein the polyester fiber is a cationic dyeable polyester fiber or a blended fiber containing a cationic dyeable polyester fiber. 1 3 . The flame-retardant according to claim 12, wherein the blended fiber is a blend of a cationic dyeable polyester fiber and other polyester fibers. 1 4. A flame retardant processing method for fibers, which is included in the application The aqueous dispersion of any one of the above items 1 to 8 is used to treat the polyester fiber. 15. A fiber, which is flame retarded by the method of claim 14 of the patent application. -60- 200842185 Seven designated representatives: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: none