WO2008047897A1

WO2008047897A1 - Halogen-free flameproofing agent and method for flameproofing fiber by using the same

Info

Publication number: WO2008047897A1
Application number: PCT/JP2007/070417
Authority: WO
Inventors: Hidehiro Arai
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 2006-10-20
Filing date: 2007-10-19
Publication date: 2008-04-24
Also published as: KR20090077890A; JPWO2008047897A1

Abstract

Disclosed is an aqueous dispersion containing one to three phosphorus compounds selected from the group consisting of phosphine oxides represented by the general formula (1) below, phosphines represented by the general formula (2) below and phosphites represented by the general formula (3) below, or alternatively such phosphorus compounds and a phosphoric acid ester represented by the general formula (4) below, and a surface active agent. This aqueous dispersion is capable of imparting fibers, especially CDP (cationic dyeable polyester) fibers or blended fibers containing CDP fibers with excellent durable flameproof properties. (In the formula (1), R11, R12 and R13 independently represent a phenyl group or the like.) (In the formula (2), R21, R22 and R23 independently represent a phenyl group or the like.) (In the formula (3), R31, R32 and R33 independently represent a phenyl group or the like.) (In the formula (4), R41, R42 and R43 independently represent a phenyl group or the like.)

Description

Specification

Non-halogen flameproofing agent and method for flameproofing fiber using the same

Technical field

[0001] The present invention provides an aqueous dispersion capable of imparting a flameproof performance with excellent durability to a synthetic fiber structure, a non-halogen flameproofing agent using the aqueous dispersion, and prevention of fibers using the same. The present invention relates to a flame treatment method and a flame-proofed fiber.

Background art

[0002] Conventionally, as a method for imparting flameproofing performance to a fiber by post-processing treatment, a method in which a halogen compound is dispersed in water to form a flameproofing agent and the fiber is flameproofed using this is known. ing. Representative examples of the halogen compounds include brominated cycloalkanes such as 1, 2, 5, 6, 9, 10 hexapromocyclododecane (Patent Documents 1 and 2).

[0003] The strength of flame retardants of rosin-based compounds, which are generally known to be high, generates harmful halogenated gases when the flame-treated fibers burn, which is harmful to the human body and the natural environment. There are problems such as effects. Therefore, in recent years, the use of halogen compounds as flame retardants has been restricted.

[0004] Therefore, a flameproofing agent using a phosphorus compound such as an organic phosphate as a flameproofing agent instead of a halogenated compound and a flameproofing method for fibers using the same have been proposed! References 3-8).

[0005] However, when these phosphorus compounds are used, sufficient flameproof performance can be imparted to fibers, in particular, blended fibers of CDP (cation dyeable polyester) fibers and polyester fibers. There was no.

Patent Document 1: Japanese Patent Publication No.53-8840

Patent Document 2: JP-A-1 213474

Patent Document 3: Japanese Patent Laid-Open No. 10-298188

Patent Document 4: JP-A-10-212669

Patent Document 5: Japanese Patent Laid-Open No. 2001-254268 Patent Document 6: JP 2000-328445 Koyuki

Patent Document 7: Japanese Patent Application Laid-Open No. 2004-225176

Patent Document 8: Japanese Unexamined Patent Publication No. 2006-70417

DISCLOSURE OF THE INVENTION ORPH1

Problems to be solved by the invention

[0006] Provided are a flameproofing agent and a flameproofing processing method capable of imparting durable and excellent flameproofing performance to conventional fibers, in particular, blended fibers of CDP fibers and polyester fibers.

Means for solving the problem

[0007] As a result of diligent research conducted by the present inventors to solve the above-mentioned problems, the use of an aqueous dispersion containing a specific phosphorus compound as a flameproofing agent makes it possible to provide flameproofing performance with excellent durability. Has been found to be able to be imparted to fibers, and the present invention has been achieved.

[0008] That is, the present invention relates to the following;!) To 19).

1). 1 to 3 selected from the group consisting of phosphine oxide represented by general formula (1), phosphine represented by general formula (2) and phosphite represented by general formula (3) An aqueous dispersion containing a phosphorus compound and a surfactant.

[Chemical 1]

Ri 13

12 (1)

(Wherein R R and R are each independently a (C1 C8) alkyl group or a hydroxyl group)

11 12 13

, Amino group, cyano group, carboxyl group, ureido group, (CI-C4) alkyl group, di (C1-C4) alkylamino group, diphenylamino group, aryl group, phenoxy group or (C1-C4) alkoxy group Te! /, You may! / ) ^R 21― P― R23

R ₂₂ (2)

(In the formula, R 1, R 2 and R are each independently a hydroxyl group, amino group, cyan group,

21 22 23

Aryl, optionally substituted by a syl group, ureido group, (C1-C4) alkyl group, di (C1-C4) alkylamino group, diphenylamino group, aryl group, phenoxy group or (C1-C4) alkoxy group. Indicates a group. )

[Chemical 3

R ₃ iO— P— OR ₃₃

OR ₃₂ ( ³ >

31 32 33

2) One type of phosphorus selected from the group consisting of phosphine oxides represented by general formula (1), phosphines represented by general formula (2) and phosphites represented by general formula (3) The aqueous dispersion as described in 1) above containing a compound.

3). The aqueous dispersion according to 1) or 2) above, which further contains a phosphate ester represented by the general formula (4) as a phosphorus compound.

[Chemical 4

0

II

R ₄ iO— P— OR ₄₃

41 42 43

Sil group, ureido group, (C1-C4) alkyl group, di (C1-C4) alkylamino group, diphenol An aryl group which may be substituted by a nilamino group, an aryl group, a phenoxy group or a (C 1 -C 4) alkoxy group. )

4) One type of phosphorus selected from the group consisting of phosphine oxides represented by general formula (1), phosphines represented by general formula (2) and phosphites represented by general formula (3) The aqueous dispersion according to any one of the above ;!) to 3) containing a compound and a phosphate ester represented by the general formula (4).

5). Furthermore, the aqueous dispersion according to 1) to 4) above, which contains an ultraviolet absorber.

Yes

6). Phosphine oxide represented by general formula (1), phosphine represented by general formula (2), phosphite represented by general formula (3) and phosphoric acid represented by general formula (4) The aqueous dispersion according to any one of 1) to 5) above, wherein the phosphorous compound selected from the group consisting of esters is contained in a total amount in the aqueous dispersion;! To 90% by weight.

7) One type of phosphorus selected from the group consisting of phosphine oxides represented by general formula (1), phosphines represented by general formula (2) and phosphites represented by general formula (3) The aqueous dispersion according to 6) above, wherein the compound is contained in the aqueous dispersion in an amount of 0.;! To 89.9% by weight.

8). The aqueous dispersion according to 7) above, further containing 0.1 to 89.9% by weight of the phosphate represented by the general formula (4) in the aqueous dispersion.

9) The aqueous dispersion according to any one of 1) to 8) above, wherein the surfactant is a nonionic surfactant and / or a cation surfactant.

10) The aqueous dispersion according to any one of the above;!) To 9) containing 0.;! To 10% by weight of an ultraviolet absorber in the aqueous dispersion.

1 1). When the surfactant is contained in the amount of the phosphorus compound relative to the amount of the phosphorus compound, the surfactant is contained in an amount of 5 to 200% by weight based on the total amount of the phosphorus compound and the ultraviolet absorber. G) The aqueous dispersion according to any one of 10).

12) .Selected from the group consisting of the phosphine oxide represented by the general formula (1) described in 1) above, the phosphine represented by the general formula (2) and the phosphite represented by the general formula (3) 1 A composition comprising a seed to three phosphorus compounds and a surfactant.

13) Further, the above 12 containing a phosphoric acid ester represented by the general formula (4) described in 2) above. ).

14) A flameproofing agent using the aqueous dispersion according to any one of the above ;!) to 11).

15) The flameproofing agent according to 14) above, which is used for fibers.

16) The flameproofing agent according to 15) above, wherein the fiber is a polyester fiber.

17) Polyester fiber strength The flameproofing agent according to 16) above, which is a cation dyeable polyester fiber or a blended fiber containing a cation dyeable polyester fiber.

18) A method for flameproofing a fiber, characterized in that the polyester fiber is treated with the aqueous dispersion described in the above;

19) A fiber which has been flameproofed by the method described in 18) above.

The invention's effect

[0009] Fibers, in particular cationic dyeable polyester fibers or cationic dyeable polyester fibers, and other polyester fibers can be obtained by using a flameproofing agent using an aqueous dispersion containing the specific phosphorus compound of the present invention and a surfactant. Durable and high-performance flameproofing can be applied to the blended fiber.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] The present invention is described in detail below.

The aqueous dispersion of the present invention is selected from the group consisting of the phosphine oxide represented by the general formula (1), the phosphine represented by the general formula (2), and the phosphite represented by the general formula (3). Contains 1 to 3 phosphorus compounds and a surfactant. In addition to the phosphorus compound, a phosphate represented by the general formula (4) may be used. In the present invention, one phosphorus selected from the group consisting of the phosphine oxide represented by the general formula (1), the phosphine represented by the general formula (2), and the phosphite represented by the general formula (3). And an aqueous dispersion containing a compound and a surfactant, a phosphine oxide represented by the above general formula (1), a phosphine represented by the general formula (2), and a phosphine represented by the general formula (3). An aqueous dispersion containing a phosphorous ester represented by the general formula (4) and a surfactant as the phosphorous compound and a phosphorous compound selected from the group consisting of phytes is preferred.

[0011] R 1, R 2, R 3 in the general formula (1), R 1, R 2, R 3 in the general formula (2), R 1, R 3 in the general formula (3)

11 12 13 21 22 23 31

, R 1, R 4, R 3, R 4 in the general formula (4), (CI—C8) as an alkyl group Examples include (CI C8) linear or branched alkyl group and (C3-C8) cyclic alkyl group. For example, methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, t butyl group Group, n pentyl group, n hexyl group, n octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the (C1 C4) alkyl group include a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n butyl group, an isobutyl group, and a t butyl group. Examples of the di (C14) alkylamino group include N, N dimethylamino group, N, N jetylamino group, N, N di-n-propylamino group, N, N diisopropylamino group, N, N di-n-butylamino group. Group, N, N diisobutylamino group, N, N di-t-butylamino group, N-methyl, N-ethylamino group, N-methyl, N-n-propylamino group, N-ethyl, N-isopropylamino group, N-isopropyl, N — N-butylamino group, N-ethyl, N-isobutyramino group, N-n-propyl, N-t-butylamino group, and the like. Examples of the aryleno group include a phenyl group, a biphenyl group, and a naphthyl group. Examples of the (C1-C4) alkoxy group include a methoxy group, an ethoxy group, an npropoxy group, an isopropoxy group, an nbutoxy group, an isobutoxy group, and a tbutoxy group.

[0012] Hydroxyl group, amino group, cyano group, carboxyl group, ureido group, (C1-C4) alkyl group, di (CI-C4) alkylamino group, diphenylamino group, aryl group, phenoxy group or (C1-C4 ) Substituted by alkoxy groups! /, May! /, Aryl groups include, for example, phenyl, methylphenyl, ethenylphenyl, n-propylphenyl, i-propylphenyl, dimethylphenyl Group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, aminophenyl group, N, N dimethylaminophenyl group, N, N jetylaminophenyl group, N, N diphenyl Examples thereof include an aminophenyl group, a cyanophyl group, a carboxyphenyl group, a biphenyl group, and a naphthyl group. Of these, a phenyl group, a methylphenyl group, and a naphthyl group are particularly preferable, in which a phenyl group, a methylphenyl group, a dimethylphenyl group, a biphenyl group, and a naphthyl group are preferable. The substitution position of the substituent in the aryl group is not particularly limited, and may be any position where substitution is possible.

[0013] The phosphorus compounds represented by the general formulas (1) to (4) may be commercially available compounds, or may be prepared by a usual production method. Among the phosphorous compounds contained in the aqueous dispersion of the present invention, the phosphoxide represented by the general formula (1) may be used.

[0014] The surfactant contained in the aqueous dispersion of the present invention includes a cationic type, a nonionic type and / or an anionic type surfactant, and includes a nonionic type, an anionic type or a nonionic type. It is preferable to use a mixture with an anionic surfactant. The surfactant is used to disperse the aforementioned phosphorus compound.

Examples of the anionic surfactant include alkyl sulfate salts such as higher alcohol sulfates, higher alkyl ether sulfates and sulfated fatty acid esters; alkylbenzene sulfonates and alkylnaphthalene sulfonates. Alkyl sulfonates; alkyl phosphate salts such as higher alcohol phosphate salts and higher alcohol alkylene oxide adduct phosphate salts. Alkynoarylarylsulfonate salts, polyoxyalkylene alkyl ether sulfate salts, ether ether carboxylate salts, polycarboxylate salts, funnel oil, petroleum sulfonates, and alkyl diphenyl ether sulfonate salts.

Among these, preferred anionic surfactants include the following general formula (107)

[Chemical 5]

(107)

(Wherein R represents a hydrogen atom, a (C6-C18) alkyl group, a styryl group or a benzyl group, n represents an integer of 1 to 15), and a sulfate ester salt of polyoxyethylene phenyl ether represented by Or the following general formula (301)

R 0 (CH CH O) PO (OH) (OR) (301)

5 2 2 η 6

(Wherein R is an alkyl group or alkylaryl group, R is a hydrogen atom or R 0 (CH CH O) represents a group, R represents an alkyl group or an alkylaryl group, and n represents a positive integer. The phosphoric acid ester of polyoxyethylene alkyl aryl ether represented by In general formula (107) and general formula (301), they are described as free acids for convenience, but examples of counter cations in the salt include alkali metals (for example, lithium, sodium, potassium, etc.), ammonium, etc. Or, ammonium is preferred.

The surfactant represented by the general formula (107) is preferably a straight-chain alkyl group in which R is (C1 to C12), n force S4 to 12; R is a nonyl group, and n is 7 Is more preferred

Yes

Examples of the surfactant represented by the general formula (301) include Prisurf AL (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0017] Nonionic surfactants as surfactants contained in the aqueous dispersion of the present invention include polyoxyethylene styrenated phenyl ethers such as polyoxyethylene distyrenated phenyl ethers or polyoxyethylenes. And ethylene tristyrenated phenyl ether, and the following general formula (108)

[Chemical 6]

The compound represented by (108) or a mixture thereof is preferred. In the general formula (108), m ′ is !!-3 and n is 8-30. Examples of the mixture of the compound represented by the general formula (108) include Neugen EA-87 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0018] The above surfactants may be used alone or in combination. Even if a plurality of types of anionic or nonionic surfactants are mixed, a plurality of types of anionic and nonionic types are used. Ion type surfactants can be mixed and used! /. The above surfactant may be a commercially available compound or may be prepared by a usual production method.

[0019] The aqueous dispersion of the present invention may contain an ultraviolet absorber for the purpose of improving light fastness! /. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays, for example, salicylic acid type, benzophenone type, benzotriazole type, hindered amine type, triazine type, cinnamic acid type compound, stilbene type compound, or benzoxazo compound. Examples thereof include so-called fluorescent brighteners, which are compounds that emit ultraviolet light by absorbing ultraviolet rays, typified by the organic compounds.

[0020] Preferable! /, Structural formulas of the ultraviolet absorbers are shown below as formulas (101) to (; 106).

[Chemical 7]

(106)

[0021] In the general formula (106), which is a benzotriazole-based ultraviolet absorber, R 1 represents (C1 to C 12) represents a linear or branched alkyl group or a Tamyl group, and a (C1 to C12) linear or branched alkyl group is preferred. More preferred are (C3 to C6) linear or branched alkyl groups, and still more preferred are (C3 to C5) branched alkyl groups such as isopropyl, isobutyl, sbutyl, t A butyl group, a 1 methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, and a 1 ethylpropyl group.

R is a hydroxy group, a linear or branched alkyl group of (C1-C12), (C1-C12)

16

A linear or branched alkyl group or a benzyloxy group of (C1 to C12), and a linear or branched alkyl group of (C1 to C6) is more preferred. And more preferably a (C1-C3) linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, an npropyl group, and an isopropyl group.

R is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group of (C1 to C12) or (C1

17

To C12) represents a linear or branched alkoxy group, and a hydrogen atom or a linear or branched alkyl group of (C1 to C3) is preferred. For example, (C1 to C3) in R above

16

And a group similar to the linear or branched alkyl group. More preferably, hydrogen atoms are used.

R represents a hydrogen atom or a hydroxyl group, preferably a hydroxyl group.

18

X represents a hydrogen atom or a chlorine atom, and a chlorine atom is more preferred! /.

Particularly preferred combinations of R to R and X are R force ¾-butyl group, R force S methyl group, R

15 18 15 16 17 is a hydrogen atom, R is a hydroxyl group and X is a chlorine atom.

18

Examples of the ultraviolet absorber other than the benzotriazole compound represented by the general formula (106) include a benzophenone compound represented by the formula (101), the formula (102), or the formula (103), a general formula (104 ) (Wherein R and R are independently

9 10

A hydrogen atom, a hydroxyl group or an alkyl group of (C1 to C5), or a benzotriazole-based and benzophenone-based compound represented by the general formula (105) (wherein R is a methyl group,

11

Til or Tamyl, R is hydroxyl, methoxy, ethoxy or benzyloxy

12

R is a hydrogen atom, hydroxyl group, methoxy group or ethoxy group, R is a hydrogen atom or hydroxyl group

13 14

Group, X represents a hydrogen atom or a chlorine atom). [0023] Among the above-described ultraviolet absorbers, a benzotriazole-based one represented by the general formula (106) is particularly preferable.

The above ultraviolet absorber may be a commercially available compound or may be prepared by a usual production method.

[0024] The aqueous dispersion of the present invention is used as a flameproofing agent, and the composition containing the specific phosphorus compound and the surfactant is also included in the present invention. The flameproofing agent is also included in the present invention. Here, the composition includes an aqueous dispersion, or a mixture of the specific phosphorus compound and the surfactant described above before preparation into an aqueous dispersion.

[0025] A preferred embodiment of the flameproof aqueous dispersion of the present invention is selected from the group consisting of compounds of the general formula (1), general formula (2), general formula (3) and general formula (4). Phosphorus compounds are generally contained in the aqueous dispersion in a total amount of !! to 90% by weight, preferably 5 to 70% by weight, particularly preferably 10 to 50% by weight.

[0026] As described above, the aqueous dispersion of the present invention contains one phosphorus compound selected from the group consisting of the compounds represented by the general formula (1), the general formula (2), and the general formula (3). And one containing a phosphorus compound selected from the group consisting of compounds of general formula (1), general formula (2) and general formula (3) and a compound of general formula (4) I like it!

One type of phosphorus compound selected from the group consisting of compounds of general formula (1), general formula (2) and general formula (3) was contained in the aqueous dispersion in an amount of 0 .;! To 89.9% by weight. Those are preferred. Furthermore, it is preferable that the compound of the general formula (4) is contained in an aqueous dispersion in an amount of 0.;! To 89.9% by weight.

The phosphorus compounds represented by the general formula (1) may be selected from a plurality of compounds represented by the same general formula.

[0027] When the aqueous dispersion of the present invention contains an ultraviolet absorber, its content is usually 0 .;

10% by weight, preferably 0.;! To 8% by weight, particularly preferably 0.;! To 5% by weight

Yes

The content of the surfactant contained in the aqueous dispersion of the present invention is usually 5 to 200% by weight, preferably, based on the amount of the phosphorus compound and, if an ultraviolet absorber is contained, the total amount thereof. Is in the range of 10 to 100% by weight, particularly preferably 10 to 50% by weight. [0028] The aqueous dispersion of the present invention includes polyvinylinorenoreconole, methinoresenorelose, canolepoxymethinoresenololose, starch paste for enhancing storage stability within the range not impairing the effect thereof. Protective colloid agents such as: flameproofing aids for enhancing the flameproofing effect; antioxidants and the like may be included as necessary. Furthermore, if necessary, alkaline agents, acids, fats and oils, higher alcohols, higher fatty acids, lower alcohols, organic solvents, penetration enhancers, polyhydric alcohols, preservatives, chelating agents, pH adjusters, wetting agents Further, an antifoaming agent, a fungicide, a pigment or a pigment may be added and used.

[0029] The aqueous dispersion of the present invention is prepared by adding a phosphorus compound and a surfactant, and further, if necessary, an ultraviolet absorber to water, and wet-pulverizing the resulting mixture using, for example, a sand grinder. Thus, an aqueous dispersion containing particles having an appropriate average particle diameter can be prepared.

In general, when the fiber is post-processed with a flameproofing agent, the particle size of the flameproofing agent used is a very important factor for the flameproofing performance, and the smaller the flameproofing agent particle size, the higher the flameproofing performance of the fiber. Can be granted. For example, it is known that if the dispersibility is poor, the flame retardant reaggregates and the particle size increases. In particular, when durability is required for the flameproofing performance of the flameproofing agent, the particle size of the flameproofing agent should be small so that the flameproofing agent can sufficiently diffuse inside the fiber. Fine particles having an average particle size of 2 m or less are preferred. In the present invention, by using a surfactant as a dispersant, a phosphorus compound, and further an ultraviolet absorber are dispersed in water as fine particles having an average particle diameter of 2πι or less in a stable and high concentration state. That's the power S.

[0030] The aqueous dispersion of the present invention is preferably used as a flameproofing agent for fibers. As a fiber for flameproofing, polyester fiber, particularly CDP fiber, or CDP fiber and other polyester fiber is used. Blended fiber is preferred.

Examples of CDP fibers and polyester fibers include polyethylene fibers such as polyethylene terephthalate, polybutylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, and cyclohexanedimethylene terephthalate;

, Isophthalic acid, adipic acid, sulfoisophthalic acid and other dicarboxylic acid components, propylene glycolanol, butylene glycolanol, cyclohexane dimethanolol, diethylene glycolol Examples thereof include fibers obtained by additionally copolymerizing diol components such as, but are not limited thereto.

Further, the structure of these fibers may be any form such as yarn, woven fabric, knitted fabric, and non-woven fabric.

[0031] A method for flameproofing a fiber using the aqueous dispersion of the present invention as a flameproofing agent is also included in the present invention. In order to flame-proof the fibers, methods such as dip dyeing bathing and padding can be used. For example, when the dip dyeing bath method is used, a dispersion dye such as a fiber and a dispersion-type cationic dye and the aqueous dispersion of the present invention are used in combination at a temperature in the range of 110 to 150 ° C, preferably 120 to 140 ° C. Process for about 10 to 60 minutes. If necessary, dyes such as fluorescent dyes can be further removed.

[0032] When using the padding method, the fiber structure is subjected to heat treatment such as dry heat treatment or steam heat treatment (using saturated atmospheric steam treatment, superheated steam treatment, high pressure steam treatment, etc.) after padding. In both the dry heat treatment and the steam heat treatment, the heat treatment temperature is usually 110 to 210 ° C, preferably 170 to 210 ° C. If the heat treatment temperature exceeds 210 ° C, polyester synthetic fibers may be yellowed or embrittled.

If necessary, the dip dyeing bath method and the padding method may be used in combination. In this case, the fiber should be flameproofed by the dip dyeing bath method and then reprocessed by the padding method. Higher flameproofing performance can be imparted by using two kinds of methods together.

[0033] Power to further explain the present invention by the following examples The present invention is not limited to these examples. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified. The particle size distribution of particles such as a phosphorus compound dispersed in the aqueous dispersion was measured with a Shimadzu laser diffraction particle size distribution analyzer SALD-200, and the median diameter was described as an average particle diameter. The structural formulas of the compounds used in the following Examples and Comparative Examples are collectively described below.

[0034] [Chemical 8-1]

[Chemical 8-2]

{212) In the above formula, Me represents a methyl group, Ph represents a phenyl group, and Et represents an ethyl group.

The compound of the above formula (201) is a compound of the above general formula (2) in which R 1, R 2 and R 3 are phenyl groups.

21 22 23

A compound. This compound can be synthesized by the method described in JP-A-2004-43405. This compound is commercially available as TPP (trade name; manufactured by Hokuko Chemical Co., Ltd.).

The compound of the above formula (202) is a compound of the above general formula (1) in which R 1, R 2 and R 3 are phenyl groups.

11 12 13

A compound. This compound can be synthesized by the method described in JP-A-62-145095, for example. This compound is commercially available as TPPO (trade name; manufactured by Hokuko Chemical Co., Ltd.).

The compound of the above formula (203) is R 1, R 2 and R 4, which is a methylphenyl group.

21 22 23

It is a compound of general formula (2). This compound is commercially available from Wako Pure Chemical Industries, Ltd. The compound of the above formula (204) is a compound of the above general formula (3) in which R 1, R 2 and R 3 are phenyl groups. A compound. This compound is commercially available from Wako Pure Chemical Industries, Ltd.

The compound of the above formula (205) is R 1, R 2 and R 6 which are methyl phenyl groups.

31 32 33

It is a compound of general formula (3). This compound is commercially available from Wako Pure Chemical Industries, Ltd. In the compound of the above formula (207), R is a naphthyl group, R and R force S phenyl group

41 42 43

It is a compound of general formula (4). This compound can be synthesized by the method described in JP-A-2006-70417. This compound is commercially available as NDPP (trade name; manufactured by Daihachi Chemical Co., Ltd.).

The compound of the above formula (208) is R 1, R 2 and R 6 which are methyl phenyl groups.

41 42 43

It is a compound of general formula (4). This compound can be synthesized by the method described in JP-A-2004-43405. This compound is commercially available as TCP (trade name; manufactured by Daihachi Chemical Co., Ltd.).

In the compound of the above formula (209), R is a diphenyl group, R and R force S phenyl group

41 42 43

It is a compound of the general formula (4) and is commercially available as # 5 (trade name; manufactured by Daihachi Chemical Co., Ltd.).

The compound of the above formula (211) is a compound of the above general formula (4) in which R 1, R 2 and R 3 are phenyl groups.

41 42 43

A compound. This compound is commercially available as TPP (trade name; manufactured by Daihachi Chemical Co., Ltd.) o

The compound of the above formula (220) is R and R force S phenyl group, R force S methyl group.

11 12 13

It is a compound of general formula (1) and is commercially available from Sigma-Aldrich Corporation. The above formula (

221) is a compound of the above general formula (1) wherein R 1 and R 2 force S phenyl group, R 1 is ethyl group

11 12 13

And is commercially available from Sigma-Aldrich Corporation. The compound of the above formula (222) is a compound of the above general formula (1) in which R and R force are S phenyl groups, and R is a cyclohexyl group.

11 12 13

A compound. This compound can be prepared, for example, by subjecting a compound marketed as DPCP (trade name: manufactured by Hokuko Chemical Co., Ltd.) to air oxidation or oxidation using hydrogen peroxide.

The compound of the above formula (223) is R 1, R 2 and R 6 which are methyl phenyl groups

11 12 13

It is a compound of formula (1). This compound is, for example, a compound commercially available as TPTP (trade name: manufactured by Hokuko Chemical Co., Ltd.), oxidized with air or hydrogen peroxide. It can be prepared by attaching to.

The compound of the above formula (224) is R 1, R 2, and R 4 power 3 -octyl group.

11 12 13

It is a compound of this. This compound is commercially available as TOPO (trade name: manufactured by Hokuko Chemical Co., Ltd.).

The compound of the above formula (210) is resorcinol bis (diphenyl phosphate) and is commercially available as RDP.

[0036] The compound of the above formula (213) has an R force ¾ butyl group, an R force S methyl group, R is a hydrogen atom, R

15 16 17

Is an ultraviolet absorber represented by the general formula (106) wherein X is a hydroxyl group and X is a chlorine atom.

18

is there. This compound is commercially available as EVERSORB73 (trade name; manufactured by Everlight Chemical Industrial Corporation)!

The compound of the above formula (212) is an anionic surfactant represented by the above general formula (107), wherein R is an n nonyl group and n is 7. A 30% aqueous solution containing the compound is commercially available as Hytenor Nore NE-05 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). In this example, a commercially available 30% aqueous solution was used as it was.

Neugen EA-87 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the nonionic surfactant. As described above, this nonionic surfactant is commercially available as a mixture of compounds represented by the general formula (108) wherein m ′ is !!-3 and n ′ is 8-30.

In the examples, commercially available products may be used as appropriate for the wetting agent, antifoaming agent, and force-proofing agent.

[0037] Example 1

Preparation of aqueous dispersion of mean grain monster 0. 893 «m

A mixture having the composition shown in Table 1 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.893 m.

Ml

*

Water 56.9%

Formula (201) (—Compound of general formula (2)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0% Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Yaki + 100. 0% Example 2

Preparation of aqueous dispersion of mean grain monsters 0.899 «m

A mixture having the composition shown in Table 2 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.899 m.

Water 56.9%

Formula (202) (—Compound of general formula (1)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 3

Preparation of aqueous dispersion of mean grain monsters 0.919 «m

A mixture having the composition described in Table 3 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.919 m. *

Water 56.9%

Formula (203) (—Compound of Formula (2)) 15. 0%

Formula (207) (—Compound of Formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

Haitenol NE— 05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 4

Preparation of an aqueous dispersion with an average particle size of 0.959 u m

A mixture having the composition shown in Table 4 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.959 m.

«

Water 56.9%

Formula (204) (—Compound of Formula (3)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen ΕΑ— 87 2. 6%

Haitenol ΝΕ— 05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1% Together

[0041] Example 5

Preparation of aqueous dispersion of mean grain monster 0.8883 «m

A mixture having the composition shown in Table 5 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.883 m.

M5

Λ

Water 56.9%

Formula (205) (—Compound of general formula (3)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100 · 0%

[0042] Example 6

Preparation of aqueous dispersion of average grain monster 0. 866 «m

A mixture having the composition described in Table 6 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.866 m. *

Water 59. 9%

Formula (201) (—Compound of general formula (2)) 15. 0%

Formula (211) (—Compound of general formula (4)) 15. 0% Formula (213) (UV absorber) 1 · 0%

Neugen ΕΑ—87 2.6%

High Tenor ΝΕ— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 7

924〃m 7 cattle

A mixture having the composition shown in Table 7 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.924 m.

Ml water 59.9%

Formula (202) (—Compound of general formula (1)) 15.0%

Formula (211) (—Compound of general formula (4)) 15.0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2.6%

High Tenor NE— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 8

Preparation of 0.959 «m aqueous dispersion

The mixture having the composition described in Table 8 was wet-ground using a sand grinder, 0.959 An aqueous dispersion of the invention having an average particle size of m was prepared.

m

ft

Water 59.9%

Formula (204) (—Compound of general formula (3)) 15.0%

Formula (211) (—Compound of general formula (4)) 15.0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2.6%

High Tenor NE— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 9

889〃m 7 cattle

A mixture having the composition shown in Table 9 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.889 m. *

Water 59.9%

Formula (201) (—Compound of Formula (2)) 15.0%

Formula (208) (—Compound of Formula (4)) 15.0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2.6%

High Tenor NE— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1% Antifungal agent 0.1%

Total 100.0% Example 10

Preparation of aqueous dispersion of 0.901 «m

A mixture having the composition shown in Table 10 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.901 m. Λ

Water 59.9%

Formula (202) (—Compound of general formula (1)) 15.0%

Formula (208) (—Compound of Formula (4)) 15.0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2.6%

High Tenor NE— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 11

Preparation of 0.892 «m aqueous dispersion

A mixture having the composition shown in Table 11 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.892 m.

*

Water 59.9%

Formula (204) (—Compound of general formula (3)) 15.0% Formula (208) (Compound of General Formula (4)) 15.0?

Formula (213) (UV absorber) 1.0 ^C

Neugen EA-87 2.6%

Haiteno-Nole NE— 05 5.8

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.l ° / c

Example 12

894〃m 7 cattle

A mixture having the composition shown in Table 12 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.894 m.

M1Z water 59.9%

Formula (202) (—Compound of general formula (1)) 15.0%

Formula (204) (—Compound of general formula (3)) 15.0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2.6%

High Tenor NE— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 13

Preparation of an aqueous dispersion of 0.921 «m A mixture having the composition described in Table 13 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.921 m.

¾13

Λ

Water 59. 9%

Formula (202) (—Compound of general formula (1)) 10. 0%

Formula (204) (—Compound of general formula (3)) 10. 0%

Formula (211) (—Compound of Formula (4)) 10. 0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100 · 0% Comparative Example 1

963〃m 7 cattle

A mixture having the composition described in Table 14 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.963 11 m.

¾1

Λ

Water 56.9%

Formula (207) (—Compound of Formula (4)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5% Antifoam 0.1%

Antifungal agent 0.1%

Yaki + 100.0% Comparative Example 2

Preparation of 0.966 am aqueous dispersion

A mixture having the composition shown in Table 15 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.966 11 m.

¾15

'.

Water 59.9%

Formula (208) (—Compound of general formula (4)) 30.0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2.6%

High Tenor NE— 05 5.8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100 · 0% Comparative Example 3

Preparation of 0.935 «m aqueous dispersion

A mixture having the composition described in Table 16 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.935 11 m.

¾16

Λ

Water 56.9%

Formula (209) (—Compound of general formula (4)) 30.0% Formula (213) (UV absorber) 4 · 0%

Neugen ΕΑ—87 2. 6%

High Tenor ΝΕ— 05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Comparative Example 4

998〃m 7 cattle

A mixture having the composition described in Table 17 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.99811 m.

Mil water 56. 9%

Formula (210) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Comparative Example 5

Preparation of aqueous dispersion of mean grain monster 0.945 «m

A mixture having the composition described in Table 18 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.94511 m. M18

ft

Water 59. 9%

Formula (211) (—Compound of general formula (4)) 30. 0%

Formula (213) (UV absorber) 1 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% Example 14 and Comparative Example 6

7 Cattle ¾ liquid according to polyester / _CDP knitted ¾ ^

Using the aqueous dispersions prepared in Examples 1 to 13 and Comparative Examples 1 to 5 and using the same dyeing bath treatment method, a blended fiber fabric containing 50% each of CDP and other polyester (CDP / PET blend fabric) Ii) 40cm square each was dyed and fireproofed at the same time.

That is, a dye solution of disperse dye 0 · 72% owf (on weight of fiber) and caton dye 0.92% owf as a dyeing bath and each aqueous dispersion prepared in Examples 1 to 13 and Comparative Examples 1 to 5 Each was treated at 130 ° C for 60 minutes at a bath ratio (volume of liquid to dough used) of 1:20.

The dyes used are disperse dyes: Power Yalon Microester Yellow AQ—LE 0 • 24%, Power Yalon Microester Red AQ—LE 0.24%, Power Yaron Microester Blue AQ—LE 0.24%; Cationic Dye As follows: Caklinole Yellow 3RL—ED 0.46%, Cakolinole Red GL—ED 0.24%, Cakolinole Blue GSL—ED 0.22%.

Thereafter, each fabric was subjected to reduction cleaning, followed by heat treatment at 180 ° C. for 30 seconds. Furthermore, in accordance with JIS K 3371, weak alkaline first-class detergent is used at a rate of lg / L. The bath ratio was 1:40, and each fabric was washed with water for 15 minutes at 60 ° C ± 2 ° C, then rinsed 3 times for 5 minutes at 40 ° C ± 2 ° C, and centrifuged for 2 minutes. Thereafter, hot air drying at 60 ° C ± 5 ° C was taken as one cycle, and this was performed for 5 cycles.

Eight kinds of blended fiber fabrics obtained by the above operation were used as test pieces, and these were subjected to a flammability test.

In addition, the above reduction cleaning means preparing an aqueous solution of hydrosulfite 2g / L, caustic soda 2g / L, and surfactant lg / L, heating to 80 ° C, and then adding a flame-proofed fabric. For 20 minutes.

[0056] Test Example 1

瞧 'experience

Use the aqueous dispersions prepared in Examples 1 to 13 or Comparative Examples 1 to 5, and apply them to Example 14 or Comparative Example 6! / To flameproofed polyester / CDP blended fiber fabrics! A flame retardant test was conducted. The results are shown in Table 19.

[0057] (1) Test method

Tests were conducted using the JIS L 1091 A-1 method (45 degree microburner method) of the Fire Service Act, and the following evaluations were made.

1) Evaluation 8: Pass rate

The case where the after flame time was 3 seconds or less was regarded as acceptable, and the value obtained by dividing the number of times of acceptance during the measurement by the number of measurements was described as the acceptance rate. The fractional part is rounded off and the unit is%. The higher the acceptance rate, the higher the flameproof performance. The parentheses after the pass rate shown in Table 19 are the number of passes and the number of measurements used to calculate the pass rate, and are expressed as “(pass times / measurement times)”.

2) Evaluation B: Average afterflame time

The average afterflame time was calculated by dividing the total afterflame time measured in Test A by the number of measurements. The unit is seconds. The shorter the average afterflame time, the higher the flameproof performance.

3) Evaluation C: Average combustion area

The average burning area was calculated by measuring the burning area of the test piece and dividing the sum by the number of measurements. The unit is cm ^2. The smaller the average combustion area, the higher the flameproof performance. [0058] (2) Test results

A flame retardant test was conducted, and the results of evaluation A, B and C are shown in Table 19.

[0059] [Table 1] Table 19

[0060] As is apparent from the results in Table 19, the pass rate of evaluation A is 75 to 100% for fabrics flameproofed with the aqueous dispersions prepared in Examples of the present invention;! In contrast, the fabric flameproofed with the aqueous dispersions prepared in Comparative Examples 1-5 was 0-69%, and the fabric flameproofed with the aqueous dispersion of the present invention had a pass rate. high. Regarding the average afterflame time of evaluation B, it was prepared in Comparative Examples 1 to 5 while the fabric flameproofed with the aqueous dispersion prepared in Examples 1 to 13 was 0.5 to 2.9. Fabrics that are flameproofed with an aqueous dispersion are 4.;! ~ 18.3 and have a long average afterflame time. Further, the average burning area of evaluation C was prepared in Comparative Examples 1 to 5 while the fabric flameproofed with the aqueous dispersion prepared in Examples 1 to 13 was 3.6 to 4.7. The flame-treated fabric with an aqueous dispersion is 7.;! ~ 33.6 and the average burning area Is also big.

[0061] As is apparent from Table 19, as in the aqueous dispersions prepared in Examples;! To 11 and 13, the phosphorus compound of the general formula (4) and the compound of the general formula (1) When combined with one phosphorus compound selected from the group consisting of the compound of formula (2) and the compound of general formula (3), a high flameproofing effect is obtained.

[0062] Example 15

Preparation of aqueous dispersion of mean grain monsters 0.899 «m

A mixture having the composition shown in Table 20 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.899 m.

20 Water 55.9%

Formula (201) (—Compound of Formula (2)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100. 0%

[0063] Example 16

Preparation of aqueous dispersion of mean grain monster 0.991 m

A mixture having the composition described in Table 21 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.912 11 m.

¾21

Λ

Water 56.9% Formula (202) (Compound of general formula (1))

Formula (213) (UV absorber) 4.0 ^C

Neugen EA- 87 2. 6 ° / c

Haiteno-Nole NE— 05 5. 8

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0. l ° / c

Example 17

894〃m night word 周 CO

Yes

A mixture having the composition shown in Table 22 was wet-ground using a sand grinder 0 to prepare an aqueous dispersion of the present invention having an average particle size of 0.894 m.

Z2 water 56.9%

Formula (203) (—Compound of general formula (2)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 18

Preparation of aqueous dispersion of average grain monster 0. 909 «m

A mixture having the composition described in Table 23 was wet-ground using a sand grinder. An aqueous dispersion of the invention having an average particle size of m was prepared.

M23

Λ

Water 56.9%

Formula (204) (—Compound of general formula (3)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100 · 0% Example 19

898〃m 7 cattle

A mixture having the composition described in Table 24 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.898 m.

MZ4 Water 55.9%

Formula (205) (—Compound of general formula (3)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100. 0% Comparative Example 7

Preparation of aqueous dispersion of mean grain monster 0. 957 m

A mixture having the composition described in Table 25 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.957 11 m.

¾25

Λ

Water 56.9%

Formula (207) (—Compound of Formula (4)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0% Comparative Example 8

954〃m 7 cattle

A mixture having the composition described in Table 26 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.954 11 m.

¾26

Λ

Water 56.9%

Formula (208) (—Compound of Formula (4)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8% Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Yaki + 100. 0% Comparative Example 9

Preparation of aqueous dispersion of mean grain monster 0. 978 am

A mixture having the composition described in Table 27 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.9791 m.

'.

Water 56.9%

Formula (209) (—Compound of general formula (4)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Comparative Example 10

Preparation of aqueous dispersion of average grain monster 0. 998 u m

A mixture having the composition described in Table 28 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.99811 m.

¾28

Λ

Water 56.9% Formula (210) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Comparative Example 11

945〃m 7 cattle

A mixture having the composition described in Table 29 was wet-ground using a sand grinder to prepare a comparative aqueous dispersion having an average particle size of 0.94511 m.

¾29

'.

Water 56.9%

Formula (211) (—Compound of general formula (4)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 20 and Comparative Example 12

Flameproofing of polyester ZCDP blend fiber fabrics with aqueous dispersions.

Using the aqueous dispersions prepared in Examples 15 to 19 and Comparative Examples 7 to 11, Examples 14 and In the same manner as in Comparative Example 6, the mixed dyed fiber fabric (CDP / PET mixed fabric B) containing 50% each of CDP and other polyesters was dyed and simultaneously prevented by the dip dyeing bath treatment method. Flame processed.

[0073] Test Example 2

Tatsuo

The aqueous dispersions prepared in Examples 15 to 19 and Comparative Examples 7 to 11 were used in Example 20 or Comparative Example 12 for flameproofing polyester / CDP blended fiber fabrics. ! / In the same manner as in Test Example 1, a flame retardancy test was conducted. The results are shown in Table 30.

[0074] [Table 2] Table 3 0

[0075] As is apparent from the results in Table 30, the pass rate of evaluation A was 100% for all the fabrics flameproofed with the aqueous dispersion prepared in Examples 15 to 19 of the present invention. On the other hand, the fabrics flame-proofed with the aqueous dispersion prepared in Comparative Examples 7 to 11 containing a phosphate type compound such as the compound of the general formula (4) alone are 0 to 82%, and A fabric that has been flameproofed with an aqueous dispersion has a higher acceptance rate. The average afterflame time of evaluation B was 0.5 to 0.9 for the fabric flame-proofed with the aqueous dispersion prepared in Examples 15 to 19, whereas the average afterflame time was prepared in Comparative Examples 7 to 11 The flame-proof fabric with the aqueous dispersion was 2.5 to 18.3, and the latter has an average after-flame time that is about 3 to 37 times longer. Further evaluation The average combustion area of C The fabric fire-treated with the aqueous dispersion prepared in 15 to 19 is 3.6 to 3.9, whereas the fabric fire-treated with the aqueous dispersion prepared in Comparative Examples 7 to 11 is 4. 7 to 33.6, the latter 1.2 to 9.3 times the average burning area.

Example 21

Preparation of aqueous dispersion of mean grain monster 0. 502 «m

A mixture having the composition described in Table 31 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.502 m.

*

Water 56.9%

Formula (220) (—Compound of general formula (1)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 22

Preparation of aqueous dispersion of mean grain monster 0. 602 «m

A mixture having the composition described in Table 32 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.602 m.

32

Λ

Water 56.9%

Formula (221) (—Compound of general formula (1)) 30. 0%

Formula (213) (UV absorber) 4 · 0% Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Yaki + 100. 0% Example 23

Preparation of aqueous dispersion of average grain monster 0.867 «m

A mixture having the composition described in Table 33 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.867 m.

¾33 Wed 56.9%

Formula (220) (—Compound of general formula (1)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Synthesis 100.0% Example 24

Preparation of aqueous dispersion of mean grain monster 0.766 um

A mixture having the composition described in Table 34 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.776 m. M

*

Water 56.9%

Formula (221) (—Compound of general formula (1)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Neugen EA—87 2. 6%

High Tenor NE—05 5. 8%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 25

Preparation of water tank dispersion with average particle size of 0.872

A mixture having the composition described in Table 35 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.872, im.

¾35

«Ά

Water 56.3%

Formula (221) (—Compound of general formula (1)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL 9.0%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100. 0% Example 26

Preparation of aqueous dispersion of mean grain monster 0. 888 «m

A mixture having the composition described in Table 36 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.888 m.

Table 36

Λ

Water 56.3%

Formula (202) (—Compound of general formula (1)) 15. 0%

Formula (204) (—Compound of Formula (3)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL 9.0%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 27

997〃m 7 cattle

A mixture having the composition described in Table 37 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.999 m.

M21

*

Water 56.3%

Formula (202) (—Compound of general formula (1)) 15. 0%

Formula (207) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL 9.0% Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Yaki + 100. 0%

[0083] Example 28

Flameproofing of polyester ZCDP blend fiber fabrics with aqueous dispersions.

Example 2; A blended fiber fabric containing 50% of CDP and other polyesters (CD P) in the same dyeing bath treatment method as in Example 14 using the aqueous dispersion prepared in! -27. / PET mixed fabric B) 40cm square was dyed and fireproofed at the same time.

[0084] Test Example 3

瞧 'experience

Example 2; A flame retardant test was conducted in the same manner as in Test Example 1 on the polyester / CDP blended fiber fabric subjected to flameproofing in Example 28 using the aqueous dispersion prepared in! -27. The results are shown in Table 38.

[0085] [Table 3] Table 3 8

[0086] Example 29

Preparation of aqueous dispersion of mean grain monster 0. 688 «m

A mixture having the composition shown in Table 39 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.688 m. ¾39

ft

Water 56.9%

Formula (222) (—Compound of Formula (1)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 30

622〃m 7 cattle

A mixture having the composition described in Table 40 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.622 m.

Water 56. 9%

Formula (223) (—Compound of general formula (1)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 31

Preparation of aqueous dispersion of mean grain monster 0. 660 «m A mixture having the composition described in Table 41 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.660 m. *

Water 56.9%

Formula (224) (—Compound of general formula (1)) 30. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100 · 0%

[0089] Example 32

7 Cattle ¾ liquid according to polyester / _CDP knitted ¾ ^

Using the aqueous dispersion prepared in Examples 29-31, a blended fiber fabric (CD P / PET) containing 50% each of CDP and other polyesters by the same dyeing bath treatment method as in Example 14. Mixed dough A) 40cm squares were dyed and fireproofed at the same time.

[0090] Test Example 4

Tatsuo

A flame retardancy test was conducted in the same manner as in Test Example 1 on the polyester / CDP blended fiber fabric subjected to flameproofing in Example 32 using the aqueous dispersion prepared in Examples 29-31. The results are shown in Table 42.

[0091] [Table 4] Table 4 2

Example 33

-o. 9oi〃m 牛 Cattle at night

A mixture having the composition described in Table 43 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.901 m.

43

a ^ i

Water 56.9%

Formula (222) (—Compound of Formula (1)) 15. 0%

Formula (211) (—Compound of general formula (4)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 34

Preparation of aqueous dispersion of mean particle monster 0. 769 «m

A mixture having the composition described in Table 44 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.769 m.

M Water 56.9%

Formula (223) (—Compound of general formula (1)) 15.0%

Formula (211) (—Compound of general formula (4)) 15.0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 35

862〃m 7 cattle

A mixture having the composition described in Table 45 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.862 m.

¾ 5 Water 56.9%

Formula (224) (—Compound of general formula (1)) 15.0%

Formula (211) (—Compound of general formula (4)) 15.0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

Total 100.0% Example 36

Preparation of 0.878 um aqueous dispersion A mixture having the composition described in Table 46 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.887 m.

¾ 6

Λ

Water 56.9%

Formula (202) (—Compound of general formula (1)) 15. 0%

Formula (222) (—Compound of Formula (1)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100% 0 Example 37

004〃m 7 cattle

A mixture having the composition described in Table 47 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 1.004 m. *

Water 56.9%

Formula (202) (—Compound of general formula (1)) 15. 0%

Formula (223) (—Compound of general formula (1)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1% Together

[0097] Example 38

Preparation of an aqueous dispersion with an average particle size of 0.988 am

A mixture having the composition shown in Table 48 was wet-ground using a sand grinder to prepare an aqueous dispersion of the present invention having an average particle size of 0.988 m.

¾ 8

Λ

Water 56.9%

Formula (202) (—Compound of general formula (1)) 15. 0%

Formula (224) (—Compound of general formula (1)) 15. 0%

Formula (213) (UV absorber) 4 · 0%

Price Surf AL Na Salt 8 · 4%

Wetting agent 0.5%

Antifoam 0.1%

Antifungal agent 0.1%

100 · 0%

[0098] Example 39

Flameproofing of polyester ZCDP blend fiber fabrics with aqueous dispersions.

Using the aqueous dispersions prepared in Examples 33 to 38, a blended fiber fabric (CD P / PET) containing 50% each of CDP and other polyesters by the same dyeing bath treatment method as in Example 14. Mixed dough B) 40cm square was dyed and fireproofed at the same time.

[0099] Test Example 5

Tatsuo

Using the aqueous dispersions prepared in Examples 33 to 38, flame retardancy tests were conducted in the same manner as in Test Example 1 for the flame retardant polyester / CDP blended fiber fabrics of Example 39! /! It was. The results are shown in Table 49. [0100] [Table 5]

Table 4 9

[0101] As is apparent from Tables 47 to 49 showing the results of Test Examples 3 to 5, the pass rate of Evaluation A is 100% for all fabrics flameproofed with the aqueous dispersion of the present invention. Regarding the average afterflame time of B, the fabric flameproofed with the aqueous dispersion of the present invention is 0.7 to 0.9, and the average burning area of evaluation C is also 3.6 to 4. 6 shows the superior performance of the flameproofing agent of the present invention compared to the results of the untreated fabric!

[0102] As described above, all the test results using the aqueous dispersion of the present invention show the excellent flameproof performance of the present invention. Further, it is apparent that the flameproofing agent of the present invention retains the above-mentioned performance and is extremely excellent in durability despite repeated washing with water for 5 cycles.

Industrial applicability

[0103] According to the present invention, it is possible to provide an aqueous dispersion of a non-halogen flameproofing agent capable of imparting durable and excellent flameproofing performance to fibers, in particular, blended fibers of CDP and other polyesters. S can.

Claims

The scope of the claims

One to three phosphorus systems selected from the group consisting of phosphine oxides represented by general formula (1), phosphines represented by general formula (2) and phosphites represented by general formula (3) An aqueous dispersion containing a compound and a surfactant.

[Chemical 1

(Wherein R 1, R 2 and R 3 are each independently a (C1 C8) alkyl group or a hydroxyl group

11 12 13

Substituted by amino group, cyano group, carboxyl group, ureido group, (CI-C4) alkyl group, di (C1-C4) alkylamino group, diphenylamino group, aryl group, phenoxy group or (C1-C4) alkoxy group Te! /, You may! / )

[Chemical 2]

R ₂₁ ― P― R ₂₃

R ₂₂ ( ² )

21 22 23

[Chemical 3]

0— P— OR

OR ₃₂ (In the formula, R 1, R 2 and R are each independently a hydroxyl group, amino group, cyan group,

31 32 33

An aryl group optionally substituted by a syl group, a ureido group, a (C1-C4) alkyl group, a di (C1-C4) alkylamino group, a diphenylamino group, an aryl group, a phenoxy group, or a (C1-C4) alkoxy group. Indicates a group. )

[2] One phosphorus system selected from the group consisting of phosphine oxides represented by general formula (1), phosphines represented by general formula (2), and phosphites represented by general formula (3) The aqueous dispersion according to claim 1, comprising a compound.

[3] The aqueous dispersion according to claim 1 or 2, further comprising a phosphate ester represented by the general formula (4) as the phosphorus compound.

[Chemical 4

II

R ₄ iO— P— OR ₄₃

41 42 43

[4] One phosphorus system selected from the group consisting of phosphine oxides represented by general formula (1), phosphines represented by general formula (2) and phosphites represented by general formula (3) The aqueous dispersion according to any one of claims 1 to 3, comprising a compound and a phosphate ester represented by the general formula (4).

[5] The aqueous dispersion according to any one of claims 1 to 4, further comprising an ultraviolet absorber.

[6] Phosphine oxide represented by general formula (1), phosphine represented by general formula (2), general formula

A total amount of a phosphorus compound selected from the group consisting of the phosphite represented by (3) and the phosphate ester represented by the general formula (4) in the aqueous dispersion;! To 90% by weight; ! ~ 5 of 5 //, aqueous dispersion according to one item.

[7] The phosphine oxide represented by the general formula (1), the phosphine represented by the general formula (2), and one 7. The aqueous dispersion according to claim 6, wherein the aqueous dispersion contains 0.;! To 89.9% by weight of one phosphorus compound selected from the group consisting of phosphites represented by the general formula (3). .

8. The aqueous dispersion according to claim 7, further comprising 0.1 to 99.9% by weight of the phosphate represented by the general formula (4) in the aqueous dispersion.

[9] The aqueous dispersion according to any one of claims 1 to 8, wherein the surfactant is a nonionic surfactant and / or a cation surfactant.

[10] The aqueous dispersion according to any one of [10] to [9], wherein the ultraviolet absorber is contained in the aqueous dispersion in an amount of 0 .;

[11] The surfactant is contained in an amount of 5 to 200% by weight based on the total amount of the phosphorus compound and the ultraviolet absorber when the ultraviolet absorber is contained relative to the amount of the phosphorus compound. ;! To 10! /, Aqueous dispersion according to any one of the above.

[12] The phosphine oxide represented by the general formula (1) according to claim 1, the phosphine represented by the general formula (2) and the phosphite represented by the general formula (3). A composition comprising 1 to 3 types of phosphorus compounds and a surfactant.

[13] The composition according to claim 12, further comprising a phosphate ester represented by the general formula (4) according to claim 2.

[14] A flameproofing agent using the aqueous dispersion according to any one of [1];

15. The flameproofing agent according to claim 14, which is used for fibers.

16. The flameproofing agent according to claim 15, wherein the fiber is a polyester fiber.

17. The flameproofing agent according to claim 16, which is a blended fiber containing polyester fiber strength S, cationic dyeable polyester fiber or cationic dyeable polyester fiber.

[18] A method for flameproofing a fiber, characterized in that the polyester fiber is treated with the aqueous dispersion according to any one of!

[19] A fiber which has been flame-proofed by the method according to claim 18.