CN101528893A - Halogen-free flameproofing agent and method for flameproofing fiber by using the same - Google Patents
Halogen-free flameproofing agent and method for flameproofing fiber by using the same Download PDFInfo
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- CN101528893A CN101528893A CNA2007800390797A CN200780039079A CN101528893A CN 101528893 A CN101528893 A CN 101528893A CN A2007800390797 A CNA2007800390797 A CN A2007800390797A CN 200780039079 A CN200780039079 A CN 200780039079A CN 101528893 A CN101528893 A CN 101528893A
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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
Technical field
The present invention relates to can to synthetic fibrous structure thing give the good fire resistance of weather resistance aqueous liquid dispersion, use the Halogen fireproofing agent of this aqueous liquid dispersion, the fiber that uses the fiber fire prevention working method of this fireproofing agent and carried out fire prevention processing.
Background technology
In the past, as handling the method for fiber being given fire resistance by post-treatment, knownly halogen contained compound was distributed in the water and the machining agent that obtains preventing fires, uses it the fiber method for processing of preventing fires.As the typical example of this halogen contained compound, can enumerate as 1,2,5,6,9 the brominated alkane (patent documentation 1 and 2) that the 10-hexabromocyclododecane is such.
The fire resistance of known halogen contained compound is high usually, and the fiber of processing through fire prevention produces deleterious halogenation gas when burning, this halogenation gas causes problems such as harmful effect to human body and physical environment but exist.Therefore, in recent years, use halogen contained compound to be restricted as fireproofing agent.
So, proposed to use phosphorus compound to replace fireproofing agent that halogen contained compound obtains as fireproofing agent and the fiber fire prevention working method (patent documentation 3～8) of using this fireproofing agent as the organophosphate.
But, when using these phosphorus compounds, can't give sufficient fire resistance to the mixed fibre of fiber, particularly CDP (cationic dye capable of dyeing type polyester) fiber and trevira.
Patent documentation 1: Japanese Patent Publication 53-8840 communique
Patent documentation 2: Japanese kokai publication hei 1-213474 communique
Patent documentation 3: Japanese kokai publication hei 10-298188 communique
Patent documentation 4: Japanese kokai publication hei 10-212669 communique
Patent documentation 5: TOHKEMY 2001-254268 communique
Patent documentation 6: TOHKEMY 2000-328445 communique
Patent documentation 7: TOHKEMY 2004-225176 communique
Patent documentation 8: TOHKEMY 2006-70417 communique
Summary of the invention
The object of the present invention is to provide fireproofing agent and the fire prevention working method that to give good fire resistance to the mixed fibre of existing fiber, particularly CDP fiber and trevira with weather resistance.
The inventor has carried out research extensively and profoundly in order to address the above problem, found that, contain aqueous liquid dispersion that specific phosphorus compound obtains as fireproofing agent by use, can give weather resistance good fire resistance to fiber, and finish the present invention.
That is, the present invention relates to following 1)～19).
1) a kind of aqueous liquid dispersion wherein, contains a kind～3 kinds phosphorus compounds and the tensio-active agent that are selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes,
In the general formula (1), R
11, R
12And R
13Expression (C1-C8) alkyl or can be independently respectively by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group,
In the general formula (2), R
21, R
22And R
23Respectively expression can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group independently,
In the general formula (3), R
31, R
32And R
33Respectively expression can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group independently.
2) above-mentioned 1) described aqueous liquid dispersion wherein, contains the a kind of phosphorus compound that is selected from by in the group of the phosphine oxide of general formula (1) expression, the phosphine of general formula (2) expression and the phosphorous acid ester formation that general formula (3) is represented.
3) above-mentioned 1) or 2) described aqueous liquid dispersion, wherein, the phosphoric acid ester that also contains general formula (4) expression is as phosphorus compound,
In the general formula (4), R
41, R
42And R
43Respectively expression can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group independently.
4) each described aqueous liquid dispersion above-mentioned 1)～3), wherein, contain the a kind of phosphorus compound being selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes and the phosphoric acid ester of general formula (4) expression.
5) each described aqueous liquid dispersion above-mentioned 1)～4) wherein, also contains UV light absorber.
6) each described aqueous liquid dispersion above-mentioned 1)～5), wherein, containing total amount in aqueous liquid dispersion is being selected from by the phosphorus compound in the group of the phosphine oxide of general formula (1) expression, the phosphine of general formula (2) expression, the phosphorous acid ester of general formula (3) expression and the phosphoric acid ester formation that general formula (4) is represented of 1～90 weight %.
7) above-mentioned 6) described aqueous dispersions wherein, contains 0.1～89.9 weight % and is selected from by a kind of phosphorus compound in the group of the phosphine oxide of general formula (1) expression, the phosphine of general formula (2) expression and the phosphorous acid ester formation that general formula (3) is represented in aqueous liquid dispersion.
8) above-mentioned 7) described aqueous liquid dispersion wherein, also contains the phosphoric acid ester of 0.1～89.9 weight % general formula (4) expression in aqueous liquid dispersion.
9) each described aqueous liquid dispersion above-mentioned 1)～8), wherein, tensio-active agent is nonionic surface active agent and/or aniorfic surfactant.
10) each described aqueous liquid dispersion above-mentioned 1)～9) wherein, contains 0.1～10 weight % UV light absorber in aqueous liquid dispersion.
11) each described aqueous liquid dispersion above-mentioned 1)～10) wherein, when the amount with respect to phosphorus compound contains UV light absorber, contains 5～200 weight % tensio-active agents with respect to the total amount of phosphorus compound and UV light absorber.
12) a kind of composition, wherein, contain be selected from by above-mentioned 1) described in the phosphine of phosphine oxide, general formula (2) expression of general formula (1) expression and a kind～3 kinds phosphorus compounds in the group that constitutes of the phosphorous acid ester of general formula (3) expression and tensio-active agent.
13) above-mentioned 12) described composition wherein, also contains above-mentioned 2) described in the phosphoric acid ester of general formula (4) expression.
14) a kind of fireproofing agent, it has used above-mentioned 1)～11) in each described aqueous liquid dispersion.
15) above-mentioned 14) described fireproofing agent, it is used for fiber.
16) above-mentioned 15) described fireproofing agent, wherein, fiber is a trevira.
17) above-mentioned 16) described fireproofing agent, wherein, trevira is cationic dye capable of dyeing type trevira or the mixed fibre that contains cationic dye capable of dyeing type trevira.
18) a kind of fiber fire prevention working method is characterized in that, with above-mentioned 1)～11) in each described aqueous liquid dispersion processing trevira.
19) a kind of by above-mentioned 18) described method carried out the fiber of fire prevention processing.
The invention effect
The fireproofing agent of the aqueous liquid dispersion that contains specific phosphorus compound and tensio-active agent of the application of the invention, the high-performance fire prevention processing that can have weather resistance to the mixed fibre of fiber, particularly cationic dye capable of dyeing type trevira or cationic dye capable of dyeing type trevira and other trevira.
Embodiment
Below, specify the present invention.
Aqueous liquid dispersion of the present invention contains a kind～3 kinds phosphorus compounds and the tensio-active agent that are selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of above-mentioned general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes.Can further the phosphoric acid ester of general formula (4) expression be used with this phosphorus compound.Among the present invention, preferably contain the a kind of phosphorus compound being selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of above-mentioned general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes and the aqueous liquid dispersion of tensio-active agent; With, contain a kind of phosphorus compound being selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of above-mentioned general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes and as the phosphoric acid ester of general formula (4) expression of phosphorus compound and the aqueous liquid dispersion of tensio-active agent.
The R of above-mentioned general formula (1)
11, R
12, R
13, general formula (2) R
21, R
22, R
23, general formula (3) R
31, R
32, R
33, general formula (4) R
41, R
42, R
43Definition in, as (C1-C8) alkyl, can enumerate (C1-C8) straight or branched alkyl, (C3-C8) cycloalkyl for example can be enumerated: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl etc.As (C1-C4) alkyl, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl etc.As two (C1-C4) alkylamino, for example can enumerate: N, N-dimethylamino, N, N-diethylamino, N, N-di amino, N, N-diisopropylaminoethyl, N, N-di-n-butyl amino, N, N-diisobutyl amino, N, N-di-t-butyl amino, N-methyl-N-ethylamino, N-methyl-N-n-propyl amino, N-ethyl-N-sec.-propyl amino, N-sec.-propyl-N-normal-butyl amino, N-ethyl-N-isobutylamino, N-n-propyl-N-tertiary butyl amino etc.As aryl, for example can enumerate: phenyl, xenyl, naphthyl etc.As (C1-C4) alkoxyl group, for example can enumerate: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy etc.
As can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group, for example can enumerate: phenyl, aminomethyl phenyl, ethylphenyl, the n-propyl phenyl, isopropyl phenyl, 3,5-dimethylphenyl, hydroxy phenyl, p-methoxy-phenyl, ethoxyl phenenyl, Phenoxyphenyl, aminophenyl, N, the N-dimethylaminophenyl, N, N-diethylamino phenyl, N, N-diphenyl amino phenyl, cyano-phenyl, carboxyl phenyl, xenyl, naphthyl etc.Wherein, preferred phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, xenyl, naphthyl, preferred especially phenyl, aminomethyl phenyl, naphthyl.Substituting group the position of substitution on aryl is not particularly limited, and can be the optional position that can replace.
The phosphorus compound of above-mentioned general formula (1)～(4) expression can use commercially available compound, also can use by common manufacturing process preparation.
The phosphine oxide of the general formula in the phosphorus compound that contains in the aqueous liquid dispersion of the present invention (1) expression can use multiple compound.
As the tensio-active agent that contains in the aqueous liquid dispersion of the present invention, can enumerate cationic, non-ionic type and/or aniorfic surfactant, preferred non-ionic type, anion surfactant type or non-ionic type mixed use with aniorfic surfactant.This tensio-active agent is used to make described phosphorus compound to disperse.
As aniorfic surfactant, for example can enumerate: alkyl sulfuric ester salt such as higher alcohol sulfate salt, senior alkyl ether sulfuric acid, sulfated fatty acid ester; Alkylsulfonate such as alkylbenzene sulfonate, sulfonated alkyl naphathalene; Alkyl phosphate salts such as the oxirane affixture phosphate ester salt of high alcohol phosphate salt, higher alcohols.In addition, can enumerate alkylaryl sulphonate, polyoxyalkylene alkyl sulfuric acid, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkyl carboxylate salts, polycarboxylate, turkey red oil, sulfonated petro-leum, alkyl diphenyl ether sulphonate salt.
Wherein,, can enumerate the phosphoric acid ester of the polyoxyethylene alkylaryl ether of the sulfuric acid of polyoxyethylene phenyl ether of following general formula (107) expression or following general formula (301) expression as preferred anionic surfactants type tensio-active agent,
R
5O(CH
2CH
2O)
nPO(OH)(OR
6) (301)
In the general formula (107), R represent hydrogen atom, (C6～C18) alkyl, styryl or benzyl, n represents 1～15 integer,
In the general formula (301), R
5Expression alkyl or alkylaryl, R
6Expression hydrogen atom or R
7O (CH
2CH
2O)
nBase, R
7Expression alkyl or alkylaryl, n represents positive integer.In addition, general formula (107), general formula are represented with the form of free acid in (301) for simplicity, as the pairing positively charged ion in the salt, can enumerate basic metal (for example, lithium, sodium, potassium etc.), ammonium etc., preferred sodium or ammonium.
The tensio-active agent of general formula (107) expression, preferred especially R is for (C1～straight chained alkyl C12), n are 4～12 compound, and further preferred R is that nonyl, n are 7 compound.
The tensio-active agent of general formula (301) expression for example can be enumerated: プ ラ イ サ one Off AL (trade(brand)name; Di-ichi Kogyo Seiyaku Co., Ltd.'s system) etc.
Nonionic surface active agent as the tensio-active agent that contains in the aqueous liquid dispersion of the present invention, can enumerate polyoxyethylene vinylbenzene phenyl ether, for example, polyoxyethylene toluylene phenyl ether or polyoxyethylene triphenylethylene phenyl ether etc., compound or its mixture of preferred following general formula (108) expression.
In the general formula (108), m ' is 1～3, n ' is 8～30.As the mixture of the compound of general formula (108) expression, for example can enumerate: ノ イ ゲ Application EA-87 (trade(brand)name; Di-ichi Kogyo Seiyaku Co., Ltd.'s system) etc.
Above-mentioned tensio-active agent can use or mix use separately, and anionic or nonionic surface active agent can use in multiple separately mixing, perhaps multiple anionic are mixed use with multiple nonionic surface active agent.
Above-mentioned tensio-active agent can use commercially available compound, also can use by common manufacturing process preparation.
In the aqueous liquid dispersion of the present invention, can contain the UV light absorber that is useful on the raising light fastness.As this UV light absorber, then be not particularly limited so long as absorb ultraviolet compound, for example can enumerate: with salicylic acid, benzophenone, benzotriazole category, hindered amines, triazines, cinnamic acid compound, diphenylethylene compounds or benzoxazole compounds is the absorption ultraviolet ray of representative and the compound that sends fluorescence, promptly so-called white dyes.
The structural formula of preferred UV light absorber is as shown in the formula shown in (101)～(106).
In the above-mentioned general formula (106) as the benzotriazole category UV light absorber, R
15Expression (C1～straight or branched alkyl C12), cumyl, preferred (the straight or branched alkyl of C1～C12).More preferably (the straight or branched alkyl of C3～C6), further preferred (branched-chain alkyl of C3～C5) for example can be enumerated: sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl.
R
16Expression hydroxyl, (the straight or branched alkyl of C1～C12), (straight or branched alkoxyl group or the benzyloxy of C1～C12), preferred (the straight or branched alkyl of C1～C12), more preferably (the straight or branched alkyl of C1～C6), it is further preferred that (the straight or branched alkyl of C1～C3) for example can be enumerated: methyl, ethyl, n-propyl, sec.-propyl.
R
17Expression hydrogen atom, hydroxyl, (the straight or branched alkyl of C1～C12) or (the straight or branched alkoxyl group of C1～C12), preferred hydrogen atom or (the straight or branched alkyl of C1～C3) for example can be enumerated and above-mentioned R
16In (the same group of straight or branched alkyl of C1～C3).More preferably hydrogen atom.
R
18Expression hydrogen atom or hydroxyl, preferred hydroxyl.
X represents hydrogen atom or chlorine atom, more preferably chlorine atom.
Particularly preferred R
15～R
18With the combination of X be: R
15Be the tertiary butyl, R
16Be methyl, R
17Be hydrogen atom, R
18For hydroxyl and X are the chlorine atom.
As the UV light absorber beyond the benzotriazole compound of above-mentioned general formula (106) expression, can enumerate the benzophenone compound of above-mentioned formula (101), formula (102) or formula (103) expression, the compound in triazine class of general formula (104) expression (in the formula, R
9And R
10Represent independently respectively the benzotriazole category of hydrogen atom, hydroxyl or (C1～C5) alkyl), general formula (105) expression and the complex chemical compound of benzophenone (in the formula, R
11Expression methyl, ethyl or cumyl, R
12Expression hydroxyl, methoxyl group, oxyethyl group or benzyloxy, R
13Expression hydrogen atom, hydroxyl, methoxy or ethoxy, R
14Expression hydrogen atom or hydroxyl, X represents hydrogen atom or chlorine atom).
In the above-mentioned UV light absorber, particularly preferably be the benzotriazole compound of general formula (106) expression.
Above-mentioned UV light absorber can be used commercially available compound, also can use by common manufacturing process preparation.
Aqueous liquid dispersion of the present invention uses as fireproofing agent, and the composition that contains described specific phosphorus compound and tensio-active agent is also included among the present invention.In addition, this fireproofing agent is also included among the present invention.At this, as composition, comprise aqueous liquid dispersion or be prepared into before the aqueous liquid dispersion, described specific phosphorus compound and surfactant mixtures etc.
As the optimal way of fire prevention use dispersion liquid of the present invention, in aqueous liquid dispersion, contain total amount usually and be the phosphorus compound in the group that the compound by general formula (1), general formula (2), general formula (3) and general formula (4) constitutes of being selected from of 1～90 weight %, preferred 5～70 weight %, preferred especially 10～50 weight %.
As previously mentioned, aqueous liquid dispersion of the present invention is preferably and contains the a kind of phosphorus compound that is selected from the group that is made of the compound of general formula (1), general formula (2) and general formula (3), and, contain the a kind of phosphorus compound being selected from the group that constitutes by the compound of general formula (1), general formula (2) and general formula (3) and the compound of general formula (4).
Containing 0.1～89.9 weight % in the preferred aqueous liquid dispersion is selected from by a kind of phosphorus compound in the group of the compound formation of general formula (1), general formula (2) and general formula (3).In addition, the compound that also contains 0.1～89.9 weight % general formula (4) in the preferred aqueous liquid dispersion.
In addition, the phosphorus compound of general formula (1) expression is selected multiple in the compound group that can be represented by same general formula.
When containing UV light absorber in the aqueous liquid dispersion of the present invention, its content is usually in the scope of 0.1～10 weight %, preferred 0.1～8 weight %, preferred especially 0.1～5 weight %.
The content of the tensio-active agent that contains in the aqueous liquid dispersion of the present invention, with respect to the amount of phosphorus compound, when containing UV light absorber with respect to their total amount, usually in the scope of 5～200 weight %, preferred 10～100 weight %, preferred especially 10～50 weight %.
In the aqueous liquid dispersion of the present invention, in the scope of not damaging its effect, can contain protective colloid agent such as being useful on the polyvinyl alcohol that improves stability in storage, methylcellulose gum, carboxymethyl cellulose, starch paste as required; Be used to improve the fire proofing additive of flameproof effect; Antioxidant etc.In addition, as required, can add alkaline agent, acids, grease, higher alcohols, higher fatty acid, lower alcohols, organic solvent, penetration enhancer, polyvalent alcohol, sanitas, sequestrant, pH regulator agent, wetting agent, defoamer, mould inhibitor, pigment or pigment etc. and use.
Aqueous liquid dispersion of the present invention, can be by the preparation of following method: phosphorus compound and tensio-active agent and the UV light absorber used as required are added in the water, use sand mill for example etc. that the mixture that obtains is carried out case of wet attrition and form the aqueous liquid dispersion of the particle that contains the fair average particle diameter.
Generally speaking, when utilizing fireproofing agent that fiber is carried out the post-treatment processing, the particle diameter of the fireproofing agent of use is an important factors for fire resistance, and the particle diameter of fireproofing agent is more little, then can give fiber higher fire resistance.For example, during known bad dispersibility, become big etc. thereby the cohesion particle diameter takes place fireproofing agent again.Particularly the fire resistance at fireproofing agent needs under the situation of weather resistance, fully diffuses to the inside of fiber in order to make fireproofing agent, and the particle diameter of preferred fireproofing agent is little, thereby the following particulate of preferred median size 2 μ m.Among the present invention,, phosphorus compound and UV light absorber stably and with the high density state are disperseed in water with the form of the particulate below the median size 2 μ m by using tensio-active agent as dispersion agent.
Aqueous liquid dispersion of the present invention preferably uses as the fireproofing agent that is used for fiber, as the fiber of the processing of preventing fires, the mixed fibre of preferred polyester fiber, particularly CDP fiber or CDP fiber and other trevira.
As CDP fiber or trevira, for example can enumerate: trevira such as polyethylene terephthalate, polybutylene terephthalate, polyoxy ethoxy benzonitrile acid esters, PEN, poly terephthalic acid cyclohexanedimethanoester ester; And in this polyester glycol component such as di-carboxylic acid composition such as addition copolymerization m-phthalic acid, hexanodioic acid, sulfoisophthalic acid or propylene glycol, butyleneglycol, cyclohexanedimethanol, Diethylene Glycol and the fiber that obtains etc., but be not limited to these.
In addition, as the structure of these fibers, can be any one forms such as cloth, knitted fabrics, non-woven fabrics.
Use aqueous liquid dispersion of the present invention to be also included among the present invention as the fiber fire prevention working method of fireproofing agent.For processing that fiber is prevented fires, can use with bathing methods such as dip method or pad dyeing method.For example, use when bathing dip method, dispersion dyestuff such as fiber, disperse type cationic dye and aqueous liquid dispersion of the present invention are used in combination, under 110～150 ℃, the temperature of preferred 120～140 ℃ of scopes, carry out about 10 minutes～about 60 minutes processing treatment.As required, also can further add dyestuffs such as fluorescence dye.
When using the pad dyeing method, behind the filling fiber structure, carry out dry heat treatment or steaming and handle thermal treatments such as (using saturated atmospheric steam processing, superheated vapour processing, autoclaved etc.).No matter dry heat treatment still is that steaming is handled, and thermal treatment temp is usually all in 110～210 ℃, preferred 170～210 ℃ scope.If thermal treatment temp surpasses 210 ℃, the xanthochromia or the embrittlement that then might produce polyethylene terephthalate.
As required, can will be used in combination with bathing dip method and pad dyeing method.At this moment, can after processing, reprocess by the pad dyeing method by fiber being prevented fires with the bath dip method.By two kinds of methods are used in combination, can give higher fire resistance.
Be described more specifically the present invention by following embodiment, but the invention is not restricted to these embodiment.When " part " and " % " occurring among the embodiment, then expression " weight part " and " weight % " respectively unless otherwise specified.The size-grade distribution of the particle of dispersive phosphorus compound etc. in the aqueous liquid dispersion is used Tianjin, island laser diffraction formula size-grade distribution counter device SALD-2000 to measure, and is represented median size with median particle diameter.In addition, the inductive structure of the compound that uses in following embodiment and the comparative example is expressed as follows.
In the following formula, Me represents that methyl, Ph represent that phenyl, Et represent ethyl.
The compound of above-mentioned formula (201) is R
21, R
22And R
23Compound for the aforementioned formula (2) of phenyl.This compound can be synthetic by the method for TOHKEMY 2004-43405 communique record.This compound is commercially available with trade(brand)name TPP (Co., Ltd.'s system is learned in northern Xinghua).
The compound of above-mentioned formula (202) is R
11, R
12And R
13Compound for the aforementioned formula (1) of phenyl.This compound can be synthetic by the method for for example Japanese kokai publication sho 62-145095 communique record.This compound is commercially available with trade(brand)name TPPO (Co., Ltd.'s system is learned in northern Xinghua).
The compound of above-mentioned formula (203) is R
21, R
22And R
23Compound for the aforementioned formula (2) of 3-aminomethyl phenyl.This compound is by commercially available with the pure medicine of light Co., Ltd. etc.
The compound of above-mentioned formula (204) is R
31, R
32And R
33Compound for the aforementioned formula (3) of phenyl.This compound is by commercially available with the pure medicine of light Co., Ltd. etc.
The compound of above-mentioned formula (205) is R
31, R
32And R
33Compound for the aforementioned formula (3) of 4-aminomethyl phenyl.This compound is by commercially available with the pure medicine of light Co., Ltd. etc.
The compound of above-mentioned formula (207) is R
41Be naphthyl, R
42And R
43Compound for the aforementioned formula (4) of phenyl.This compound can be synthetic by the method for TOHKEMY 2006-70417 communique record.This compound is commercially available with trade(brand)name NDPP (big eight KCC's systems).
The compound of above-mentioned formula (208) is R
41, R
42And R
43Compound for the aforementioned formula (4) of 4-aminomethyl phenyl.This compound can be synthetic by the method for TOHKEMY 2004-43405 communique record.This compound is commercially available with trade(brand)name TCP (big eight KCC's systems).
The compound of above-mentioned formula (209) is R
41Be xenyl, R
42And R
43For the compound of the aforementioned formula (4) of phenyl, commercially available with trade(brand)name #5 (big eight KCC's systems).
The compound of above-mentioned formula (211) is R
41, R
42And R
43Compound for the aforementioned formula (4) of phenyl.This compound is commercially available with trade(brand)name TPP (big eight KCC's systems).
The compound of above-mentioned formula (220) is R
11And R
12Be phenyl, R
13For the compound of the aforementioned formula (1) of methyl, commercially available by Sigma-Aldrich company etc.The compound of above-mentioned formula (221) is R
11And R
12Be phenyl, R
13For the compound of the aforementioned formula (1) of ethyl, commercially available by Sigma-Aldrich company etc.The compound of above-mentioned formula (222) is R
11And R
12Be phenyl, R
13Compound for the aforementioned formula (1) of cyclohexyl.This compound for example can be by carrying out atmospheric oxidation or use hydrogen peroxide to carry out oxidation and make with the commercially available compound of trade(brand)name DPCP (Hokko Chemical Industry Co., Ltd.'s system).
The compound of above-mentioned formula (223) is R
11, R
12And R
13Compound for the aforementioned formula (1) of 4-aminomethyl phenyl.This compound for example can be by carrying out atmospheric oxidation or use hydrogen peroxide to carry out oxidation and make with the commercially available compound of trade(brand)name TPTP (Hokko Chemical Industry Co., Ltd.'s system).
The compound of above-mentioned formula (224) is R
11, R
12And R
13Compound for the aforementioned formula (1) of n-octyl.This compound is commercially available with trade(brand)name TOPO (Hokko Chemical Industry Co., Ltd.'s system).
The compound of above-mentioned formula (210) is Resorcinol two (diphenyl phosphoester), and RDP is commercially available with trade(brand)name.
The compound of above-mentioned formula (213) is R
15Be the tertiary butyl, R
16Be methyl, R
17Be hydrogen atom, R
18For hydroxyl and X is the UV light absorber of aforementioned formula (106) expression of chlorine atom.This compound is commercially available with trade(brand)name EVERSORB73 (EvErLight ChEmicAL INdustriALCorporAtion system).
The compound of above-mentioned formula (212) is that R is that n-nonyl, n are the aniorfic surfactant of 7 aforementioned formula (107) expression.The aqueous solution that contains 30% this compound is commercially available with trade(brand)name Ha イ テ ノ one Le NE-05 (Di-ichi Kogyo Seiyaku Co., Ltd.'s system).Directly use 30% aqueous solution in the present embodiment as commercially available product.
As nonionic surface active agent, use ノ イ ゲ Application EA-87 (trade(brand)name; Di-ichi Kogyo Seiyaku Co., Ltd.'s system).This nonionic surface active agent as previously mentioned, and is commercially available with the form of the mixture that m ' in the aforementioned formula (108) is 1～3, n ' is 8～30 compound.
Among the embodiment, wetting agent, defoamer, mould inhibitor can suitably use commercially available product.
Embodiment 1
The preparation of the aqueous liquid dispersion of median size 0.893 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 1 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.893 μ m.
Table 1
Embodiment 2
The preparation of the aqueous liquid dispersion of median size 0.899 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 2 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.899 μ m.
Table 2
Embodiment 3
The preparation of the aqueous liquid dispersion of median size 0.919 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 3 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.919 μ m.
Table 3
Embodiment 4
The preparation of the aqueous liquid dispersion of median size 0.959 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 4 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.959 μ m.
Table 4
Embodiment 5
The preparation of the aqueous liquid dispersion of median size 0.883 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 5 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.883 μ m.
Table 5
Embodiment 6
The preparation of the aqueous liquid dispersion of median size 0.866 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 6 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.866 μ m.
Table 6
Embodiment 7
The preparation of the aqueous liquid dispersion of median size 0.924 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 7 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.924 μ m.
Table 7
Embodiment 8
The preparation of the aqueous liquid dispersion of median size 0.959 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 8 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.959 μ m.
Table 8
Embodiment 9
The preparation of the aqueous liquid dispersion of median size 0.889 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 9 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.889 μ m.
Table 9
Embodiment 10
The preparation of the aqueous liquid dispersion of median size 0.901 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 10 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.901 μ m.
Table 10
Embodiment 11
The preparation of the aqueous liquid dispersion of median size 0.892 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 11 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.892 μ m.
Table 11
Embodiment 12
The preparation of the aqueous liquid dispersion of median size 0.894 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 12 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.894 μ m.
Table 12
Embodiment 13
The preparation of the aqueous liquid dispersion of median size 0.921 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 13 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.921 μ m.
Table 13
Comparative example 1
The preparation of the aqueous liquid dispersion of median size 0.963 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 14 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.963 μ m.
Table 14
Comparative example 2
The preparation of the aqueous liquid dispersion of median size 0.966 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 15 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.966 μ m.
Table 15
Comparative example 3
The preparation of the aqueous liquid dispersion of median size 0.935 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 16 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.935 μ m.
Table 16
Comparative example 4
The preparation of the aqueous liquid dispersion of median size 0.998 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 17 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.998 μ m.
Table 17
Comparative example 5
The preparation of the aqueous liquid dispersion of median size 0.945 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 18 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.945 μ m.
Table 18
Embodiment 14 and comparative example 6
Utilize the fire prevention processing of the polyester/CDP mixed fibre cloth of aqueous liquid dispersion
Use the aqueous liquid dispersion of embodiment 1～13 and comparative example 1～5 preparation, by bathing the dip dyeing treatment method together, 40 centimeter square are contained each mixed fibre cloth (CDP/PET blending grey cloth A) of 50% of CDP and another kind of polyester dye the processing of preventing fires simultaneously respectively.
Promptly, each aqueous liquid dispersion that the dye solution that uses dispersed dye 0.72%o.w.f (based on fibre weight) and cationic dyestuff 0.92%o.w.f and embodiment 1～13 and comparative example 1～5 prepare carries out processing in 130 ℃ * 60 minutes with bath raio (with respect to the liquid measure of used grey cloth) respectively as dye bath at 1: 20.
In the dyestuff that uses, as dispersed dye is カ ヤ ロ Application マ イ Network ロ エ ス テ Le yellow AQ-LE 0.24%, the red AQ-LE 0.24% of カ ヤ ロ Application マ イ Network ロ エ ス テ Le, the blue AQ-LE 0.24% of カ ヤ ロ Application マ イ Network ロ エ ス テ Le; As cationic dyestuff is カ ヤ Network リ Le yellow 3RL-ED 0.46%, the red GL-ED 0.24% of カ ヤ Network リ Le, the blue GSL-ED0.22% of カ ヤ Network リ Le.
Then, each cloth is reduced washing, then under 180 ℃, carry out thermal treatment in 30 seconds.And then, according to JIS K 3371, use weakly alkaline the 1st kind of lotion, bath raio to be set at 1: 40, descend washing after 15 minutes at 60 ℃ ± 2 ℃ each cloth with the ratio of 1g/L, under 40 ℃ ± 2 ℃, carry out washing in three times 5 minutes and carry out centrifuge dehydration in 2 minutes, afterwards, as 1 circulation, carry out 5 circulations with 60 ℃ ± 5 ℃ warm air dryings.
8 kinds of mixed fibre cloth that will obtain by aforesaid operations carry out the fuel performance test as test film to them.
In addition, above-mentioned reduction washing is following operation: the aqueous solution of preparation hyposulfite 2g/L, caustic soda 2g/L, tensio-active agent 1g/L, be heated to 80 ℃ after, the cloth that adds through fire prevention processing also carries out handling in 20 minutes.
Test example 1
Flame retardant test
The aqueous liquid dispersion that uses embodiment 1～13 or comparative example 1～5 preparation, the polyester/CDP mixed fibre cloth of the processing of preventing fires in embodiment 14 or comparative example 6 are carried out flame retardant test.The result is shown in table 19.
(1) test method
Test according to fire service law JIS L 1091 A-1 methods (45 degree microburner method), and carry out following evaluation.
1) estimates A: qualification rate
Afterflame time is to be qualified below 3 seconds the time, and the numerical value that obtains divided by measuring number of times with the qualified number of times in this mensuration is as qualification rate.Radix point rounds up later on, and unit is %.Qualification rate is high more, and then fire resistance is high more.Content in the bracket after the qualification rate shown in the table 19 is the qualified number of times that uses during qualification rate is calculated and measure number of times, represents with " (qualified number of times/mensuration number of times) ".
2) estimate B: average afterflame time
The total of the afterflame time of measuring with test A is calculated average afterflame time thus divided by measuring number of times.Unit is second.Average afterflame time is short more, and then fire resistance is high more.
3) estimate C: average burning area
The burning area of determination test sheet divided by measuring number of times, calculates average burning area with its summation thus.Unit is cm
2Average burning area is more little, and then fire resistance is high more.
(2) test-results
Carry out flame retardant test, the result that its A, B and C estimate is shown in table 19.
Table 19
From the result of table 19 obviously as can be seen, for the qualification rate of estimating A, with the prevent fires cloth of processing of the aqueous liquid dispersion of embodiments of the invention 1～13 preparation is 75～100%, relative therewith, with the prevent fires cloth of processing of the aqueous liquid dispersion of comparative example 1～5 preparation is 0～69%, thereby the cloth qualification rate height of preventing fires and processing with aqueous liquid dispersion of the present invention.For the average afterflame time of estimating B, with the prevent fires cloth of processing of the aqueous liquid dispersion of embodiment 1～13 preparation is 0.5～2.9, relative therewith, be 4.1～18.3 with the prevent fires cloth of processing of the aqueous liquid dispersion of comparative example 1～5 preparation, average afterflame time is long.In addition, for the average burning area of estimating C, be 3.6～4.7 with the aqueous liquid dispersion of embodiment 1～13 preparation cloth of processing of preventing fires, relative therewith, with the prevent fires cloth of processing of the aqueous liquid dispersion of comparative example 1～5 preparation is 7.1～33.6, and average burning area is also big.
From table 19 obviously as can be seen, aqueous liquid dispersion as embodiment 1～11 and 13 preparations, during a kind of phosphorus compound combination in the group that the phosphorus compound of general formula (4) and the compound that is selected from by the compound of the compound of general formula (1), general formula (2) and general formula (3) are constituted, obtain high flameproof effect.
Embodiment 15
The preparation of the aqueous liquid dispersion of median size 0.899 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 20 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.899 μ m.
Table 20
Embodiment 16
The preparation of the aqueous liquid dispersion of median size 0.912 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 21 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.912 μ m.
Table 21
Embodiment 17
The preparation of the aqueous liquid dispersion of median size 0.894 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 22 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.894 μ m.
Table 22
Embodiment 18
The preparation of the aqueous liquid dispersion of median size 0.909 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 23 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.909 μ m.
Table 23
Embodiment 19
The preparation of the aqueous liquid dispersion of median size 0.898 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 24 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.898 μ m.
Table 24
Comparative example 7
The preparation of the aqueous liquid dispersion of median size 0.957 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 25 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.957 μ m.
Table 25
Comparative example 8
The preparation of the aqueous liquid dispersion of median size 0.954 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 26 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.954 μ m.
Table 26
Comparative example 9
The preparation of the aqueous liquid dispersion of median size 0.978 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 27 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.978 μ m.
Table 27
Comparative example 10
The preparation of the aqueous liquid dispersion of median size 0.998 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 28 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.998 μ m.
Table 28
Comparative example 11
The preparation of the aqueous liquid dispersion of median size 0.945 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 29 to carry out case of wet attrition, preparation has the comparison use dispersion liquid of the median size of 0.945 μ m.
Table 29
Embodiment 20 and comparative example 12
Utilize the fire prevention processing of the polyester/CDP mixed fibre cloth of water spare dispersion liquid
Use the aqueous liquid dispersion of embodiment 15～19 and comparative example 7～11 preparations, with embodiment 14 and comparative example 6 similarly, by bathing the dip dyeing treatment method together, 40 centimeter square are contained each mixed fibre cloth (CDP/PET blending grey cloth B) of 50% of CDP and another kind of polyester dye the processing of preventing fires simultaneously respectively.
Test example 2
Flame retardant test
To the aqueous liquid dispersion that uses embodiment 15～19 and comparative example 7～11 preparations, the polyester/CDP mixed fibre cloth of the processing of in embodiment 20 or comparative example 12, preventing fires, similarly carry out flame retardant test with test example 1.Its result is shown in table 30.
Table 30
From the result of table 30 obviously as can be seen, for the qualification rate of estimating A, with the prevent fires cloth of processing of the aqueous liquid dispersion of embodiments of the invention 15～19 preparation all is 100%, relative therewith, with the prevent fires cloth of processing of the aqueous liquid dispersion of comparative example 7～11 preparation of the phosphate compounds such as compound that contain general formula (4) separately is 0～82%, thereby the cloth qualification rate height of preventing fires and processing with aqueous liquid dispersion of the present invention.For the average afterflame time of estimating B, with the prevent fires cloth of processing of the aqueous liquid dispersion of embodiment 15～19 preparation is 0.5～0.9, relative therewith, with the prevent fires cloth of processing of the aqueous liquid dispersion of comparative example 7～11 preparation is 2.5～18.3, the latter's average afterflame time is long, is about 3～about 37 times.In addition, for the average burning area of estimating C, with the prevent fires cloth of processing of the aqueous liquid dispersion of embodiment 15～19 preparation is 3.6～3.9, relative therewith, with the prevent fires cloth of processing of the aqueous liquid dispersion of comparative example 7～11 preparation is 4.7～33.6, the latter's average burning area is big, is 1.2～9.3 times.
Embodiment 21
The preparation of the aqueous liquid dispersion of median size 0.502 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 31 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.502 μ m.
Table 31
Embodiment 22
The preparation of the aqueous liquid dispersion of median size 0.602 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 32 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.602 μ m.
Table 32
Embodiment 23
The preparation of the aqueous liquid dispersion of median size 0.867 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 33 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.867 μ m.
Table 33
Embodiment 24
The preparation of the aqueous liquid dispersion of median size 0.766 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 34 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.766 μ m.
Table 34
Embodiment 25
The preparation of the aqueous liquid dispersion of median size 0.872 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 35 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.872 μ m.
Table 35
Embodiment 26
The preparation of the aqueous liquid dispersion of median size 0.888 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 36 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.888 μ m.
Table 36
Embodiment 27
The preparation of the aqueous liquid dispersion of median size 0.997 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 37 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.997 μ m.
Table 37
Embodiment 28
Utilize the fire prevention processing of the polyester/CDP mixed fibre cloth of aqueous liquid dispersion
Use the aqueous liquid dispersion of embodiment 21～27 preparations, similarly to Example 14, by with bathing the dip dyeing treatment method, 40 centimeter square are contained CDP and each mixed fibre cloth (CDP/PET blending grey cloth B) of 50% of another kind of polyester dyes the processing of preventing fires simultaneously respectively.
Test example 3
Flame retardant test
To the aqueous liquid dispersion that uses embodiment 21～27 preparations, the polyester/CDP mixed fibre cloth of in embodiment 28, preventing fires processing, similarly carry out flame retardant test with test example 1.Its result is shown in table 38.
Table 38
Embodiment 29
The preparation of the aqueous liquid dispersion of median size 0.688 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 39 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.688 μ m.
Table 39
Embodiment 30
The preparation of the aqueous liquid dispersion of median size 0.622 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 40 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.622 μ m.
Table 40
Embodiment 31
The preparation of the aqueous liquid dispersion of median size 0.660 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 41 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.660 μ m.
Table 41
Embodiment 32
Utilize the fire prevention processing of the polyester/CDP mixed fibre cloth of aqueous liquid dispersion
Use the aqueous liquid dispersion of embodiment 29～31 preparations, similarly to Example 14, by with bathing the dip dyeing treatment method, 40 centimeter square are contained CDP and each mixed fibre cloth (CDP/PET blending grey cloth A) of 50% of another kind of polyester dyes the processing of preventing fires simultaneously respectively.
Test example 4
Flame retardant test
To the aqueous liquid dispersion that uses embodiment 29～31 preparations, the polyester/CDP mixed fibre cloth of in embodiment 32, preventing fires processing, similarly carry out flame retardant test with test example 1.Its result is shown in table 42.
Table 42
Embodiment 33
The preparation of the aqueous liquid dispersion of median size 0.901 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 43 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.901 μ m.
Table 43
Embodiment 34
The preparation of the aqueous liquid dispersion of median size 0.769 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 44 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.769 μ m.
Table 44
Embodiment 35
The preparation of the aqueous liquid dispersion of median size 0.862 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 45 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.862 μ m.
Table 45
Embodiment 36
The preparation of the aqueous liquid dispersion of median size 0.878 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 46 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.878 μ m.
Table 46
Embodiment 37
The preparation of the aqueous liquid dispersion of median size 1.004 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 47 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 1.004 μ m.
Table 47
Embodiment 38
The preparation of the aqueous liquid dispersion of median size 0.988 μ m
Use the mixture of forming shown in the sand mill his-and-hers watches 48 to carry out case of wet attrition, preparation has the aqueous liquid dispersion of the present invention of the median size of 0.988 μ m.
Table 48
Embodiment 39
Utilize the fire prevention processing of the polyester/CDP mixed fibre cloth of aqueous liquid dispersion
Use the aqueous liquid dispersion of embodiment 33～38 preparations, similarly to Example 14, by with bathing the dip dyeing treatment method, 40 centimeter square are contained CDP and each mixed fibre cloth (CDP/PET blending grey cloth B) of 50% of another kind of polyester dyes the processing of preventing fires simultaneously respectively.
Test example 5
Flame retardant test
To the aqueous liquid dispersion that uses embodiment 33～38 preparations, the polyester/CDP mixed fibre cloth of in embodiment 39, preventing fires processing, similarly carry out flame retardant test with test example 1.Its result is shown in table 49.
Table 49
From the result's that shows test example 3～5 table 47～49 obviously as can be seen, for the qualification rate of estimating A, with aqueous liquid dispersion of the present invention prevent fires processing cloth all be 100%, for the average afterflame time of estimating B, with the prevent fires cloth of processing of aqueous liquid dispersion of the present invention is 0.7～0.9, in addition, is 3.6～4.6 for the average burning area of estimating C, compare with the result of the cloth that is untreated, all demonstrate the premium properties of fireproofing agent of the present invention.
As mentioned above, use the test-results of aqueous liquid dispersion of the present invention all to demonstrate good fire resistance of the present invention.In addition,, also keep above-mentioned performance, illustrate that the weather resistance aspect is also very good although fireproofing agent of the present invention has carried out 5 round-robin washings etc. repeatedly.
Industrial applicability
According to the present invention, can provide can mixing fiber, particularly CDP and other polyester Spin fiber and give the aqueous liquid dispersion of the Halogen fireproof agent of the good fire protecting performance with durability.
Claims (19)
1. aqueous liquid dispersion wherein, contains a kind～3 kinds phosphorus compounds and the tensio-active agent that are selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes,
In the general formula (1), R
11, R
12And R
13Expression (C1-C8) alkyl or can be independently respectively by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group,
In the general formula (2), R
21, R
22And R
23Respectively expression can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group independently,
In the general formula (3), R
31, R
32And R
33Respectively expression can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group independently.
2. the described aqueous liquid dispersion of claim 1 wherein, contains the a kind of phosphorus compound that is selected from by in the group of the phosphine oxide of general formula (1) expression, the phosphine of general formula (2) expression and the phosphorous acid ester formation that general formula (3) is represented.
3. claim 1 or 2 described aqueous liquid dispersions, wherein, the phosphoric acid ester that also contains general formula (4) expression is as phosphorus compound,
In the general formula (4), R
41, R
42And R
43Respectively expression can be by hydroxyl, amino, cyano group, carboxyl, urea groups, (C1-C4) alkyl, two (C1-C4) alkylamino, diphenylamino, aryl, phenoxy group or (C1-C4) aryl that replaces of alkoxyl group independently.
4. each described aqueous liquid dispersion in the claim 1～3, wherein, contain the a kind of phosphorus compound being selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of general formula (1) expression, general formula (2) expression and general formula (3) expression constitutes and the phosphoric acid ester of general formula (4) expression.
5. each described aqueous liquid dispersion in the claim 1～4 wherein, also contains UV light absorber.
6. each described aqueous liquid dispersion in the claim 1～5, wherein, containing total amount in aqueous liquid dispersion is being selected from by the phosphorus compound in the group of the phosphine oxide of general formula (1) expression, the phosphine of general formula (2) expression, the phosphorous acid ester of general formula (3) expression and the phosphoric acid ester formation that general formula (4) is represented of 1～90 weight %.
7. the described aqueous dispersions of claim 6 wherein, contains 0.1～89.9 weight % and is selected from by a kind of phosphorus compound in the group of the phosphine oxide of general formula (1) expression, the phosphine of general formula (2) expression and the phosphorous acid ester formation that general formula (3) is represented in aqueous liquid dispersion.
8. the described aqueous liquid dispersion of claim 7 wherein, also contains the phosphoric acid ester of 0.1～89.9 weight % general formula (4) expression in aqueous liquid dispersion.
9. each described aqueous liquid dispersion in the claim 1～8, wherein, tensio-active agent is nonionic surface active agent and/or aniorfic surfactant.
10. each described aqueous liquid dispersion in the claim 1～9 wherein, contains 0.1～10 weight % UV light absorber in aqueous liquid dispersion.
11. each described aqueous liquid dispersion in the claim 1～10 wherein, when the amount with respect to phosphorus compound contains UV light absorber, contains 5～200 weight % tensio-active agents with respect to the total amount of phosphorus compound and UV light absorber.
12. a composition wherein, contains a kind～3 kinds phosphorus compounds and the tensio-active agent that are selected from the group that the phosphorous acid ester by the phosphine of the phosphine oxide of the general formula described in the claim 1 (1) expression, general formula (2) expression and general formula (3) expression constitutes.
13. the described composition of claim 12 wherein, also contains the phosphoric acid ester of the general formula described in the claim 2 (4) expression.
14. a fireproofing agent, it has used each described aqueous liquid dispersion in the claim 1～11.
15. the described fireproofing agent of claim 14, it is used for fiber.
16. the described fireproofing agent of claim 15, wherein, fiber is a trevira.
17. the described fireproofing agent of claim 16, wherein, trevira is cationic dye capable of dyeing type trevira or the mixed fibre that contains cationic dye capable of dyeing type trevira.
18. a fiber fire prevention working method is characterized in that, handles trevira with each described aqueous liquid dispersion in the claim 1～11.
19. fiber that has carried out fire prevention processing by the described method of claim 18.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP285859/2006 | 2006-10-20 | ||
| JP2006285859 | 2006-10-20 | ||
| JP290421/2006 | 2006-10-25 |
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| Publication Number | Publication Date |
|---|---|
| CN101528893A true CN101528893A (en) | 2009-09-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800390797A Pending CN101528893A (en) | 2006-10-20 | 2007-10-19 | Halogen-free flameproofing agent and method for flameproofing fiber by using the same |
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|---|---|
| CN (1) | CN101528893A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649408A (en) * | 2011-08-10 | 2014-03-19 | 松本油脂制药株式会社 | Flameproofing agent for fibers, method for producing flame-retardant fiber, and flame-retardant fiber |
| CN105073951A (en) * | 2013-04-01 | 2015-11-18 | 株式会社Adeka | Flame-retardant agent composition, flame-retardant fiber treated with flame-retardant agent composition, and method for increasing amount of flame-retardant component adhered onto fibers using said composition |
-
2007
- 2007-10-19 CN CNA2007800390797A patent/CN101528893A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103649408A (en) * | 2011-08-10 | 2014-03-19 | 松本油脂制药株式会社 | Flameproofing agent for fibers, method for producing flame-retardant fiber, and flame-retardant fiber |
| CN105073951A (en) * | 2013-04-01 | 2015-11-18 | 株式会社Adeka | Flame-retardant agent composition, flame-retardant fiber treated with flame-retardant agent composition, and method for increasing amount of flame-retardant component adhered onto fibers using said composition |
| CN105073951B (en) * | 2013-04-01 | 2017-08-15 | 株式会社Adeka | The method of fire retardant combination, the flame retardant fiber handled with fire retardant combination and the adhesion amount using said composition increase flame-retardant composition in the fibre |
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