CN1572968A - Fire retardant for fiber, fire-retardancy enduing method and fire retardation treated fiber - Google Patents
Fire retardant for fiber, fire-retardancy enduing method and fire retardation treated fiber Download PDFInfo
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- CN1572968A CN1572968A CN 200410060021 CN200410060021A CN1572968A CN 1572968 A CN1572968 A CN 1572968A CN 200410060021 CN200410060021 CN 200410060021 CN 200410060021 A CN200410060021 A CN 200410060021A CN 1572968 A CN1572968 A CN 1572968A
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Abstract
The invention relates to a treatment agent for fiber, the main component is the phosphonium salt (A) shown in the following formula (1), wherein, the R<1> independently represents the alkyl of 1 to 20 carbon atoms, the alkenyl of 2 to 20 carbon atoms, the naphthenic base of 5 to 6 carbon atoms, the aryl of 6 to 14carbon atoms, or the n-alkyl-aryl replaced by thealkylidene of 1 to 4 carbon atoms, a part hydrogen atoms of the alkyl can be replaced by hydroxyl, mercapto, alkoxy, carboxyl, amino or halogen atoms, a ring can formed between the R<1> by combining with each other, X represents anion.
Description
Technical field
The present invention relates to a kind of fiber fire retardant.The fire-retardant processing finishing agent that more specifically relates to the polyesters synthetic fiber.
Background technology
In the past as the fire-retardant processing of polyesters synthetic fiber with finishing agent known be hexabromo-Cyclododecane (spy opens clear 57-137377 communique)., the halogenation gas that has been produced when these have given the polyesters synthetic fiber of aforesaid halogen compounds in burning can bring harmful effect to environment, and this has problems halogen compound in the use, therefore the Fire-retardant processed goods that need provide non-halogen to be.
So the someone has proposed to replace halogen compound to make the method (open as, spy 2000-328445 communique, spy are opened the 2001-254268 communique, the spy opens 2002-88368 patent documentation 2) of fire-retardantization of polyesters synthetic fiber with phosphate compounds.
, because these compounds need a large amount of emulsifying agents to make fire retardant finish aqueous dispersion, and can't from the polyesters synthetic fiber after the processing, remove emulsion breaker fully, so above-claimed cpd do not have sufficient anti-flammability.In addition for the cationic dye capable of dyeing polyester, because of fiber can not suction the fire retardant of fire-retardantization aequum, so can't give anti-flammability.
In addition, proposed to become subdivision to contain the polyester (spy opens the 2000-154465 communique) of the dicarboxylic acids of forming by phosphinic acid derivatives as not halogen-containing fire retardant somebody as dicarboxylic acids.
, produce problems such as tenderly white streak because this molecular weight of polyesters height when handling polyesters synthetic fiber cloth and silk with this polyester, exists texture and becomes thick and stiff.
In addition, also proposed with condensation product the polyesters synthetic fiber to be carried out the method for fire-retardantization, described condensation product makes (I) alkyl phosphoric acid acid amides, (II) tetrahydroxy Jia Ji phosphonium salt or trihydroxy methyl phosphine oxide and (III) can prepare (spy opens clear 49-6299 communique, the spy opens clear 49-14797 communique) with the polyfunctional compound's of formalin reaction reactant aqueous solution.
But, when handling polyesters synthetic fiber cloth and silk, exist texture and become thick and stiff with this condensation product, produce problems such as tenderly white streak.
Summary of the invention
The purpose of this invention is to provide a kind of fire retardant, this fire retardant uses the not compound of halogen atom-containing, keeping good texture and do not producing under the situation of tenderly white streak, can be by back processing easily to the polyesters synthetic fiber, particularly give anti-flammability to the cation dyeable polyester class synthetic fiber that do not have to implement fire-retardantization in the past, make them not only in the early stage, and also have the anti-flammability that durability is arranged after the washing or after the dry-cleaning.
The inventor has carried out wholwe-hearted research for solving the problems of the technologies described above, thereby has finished the present invention.
The present invention is to be the fiber finishing agent of neccessary composition with the phosphonium salt (A) shown in the following general formula (1),
[in the formula, R
1Represent C respectively independently
1～C
20Alkyl, C
2～C
20Alkenyl, C
5～C
6Cycloalkyl, C
6～C
14Aryl or through C
1～C
4The aralkyl that alkylidene replaces, the part of hydrogen atom can be replaced by hydroxyl, sulfydryl, alkoxyl, carboxyl, amino or halogen atom in the above-mentioned alkyl; R in addition
1Between can also be incorporated into ring; X represents anion];
Give composition as anti-flammability and the fire retardant that contains Jiang Suo Shu phosphonium salt (A);
The application of finishing agent of described fiber as fire retardant;
Described fire retardant is applicable to the anti-flammability adding method of fiber;
Carry out fire-retardant processing resulting polyester class synthetic fiber with described fire retardant.
The specific embodiment
Among the present invention, the R in the described general formula (1)
1Represent C respectively independently
1～C
20Alkyl, C
2～C
20Alkenyl, C
5～C
6Cycloalkyl, C
6～C
14Aryl or through C
1～C
4The aralkyl that alkylidene replaces, the part of hydrogen atom can be replaced by hydroxyl, sulfydryl, alkoxyl, carboxyl, amino or halogen atom in the above-mentioned alkyl.Can also be incorporated into ring between the R1 in addition.
As substituent R
1Alkyl, can enumerate C
1～C
20The straight or branched alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, 3-methyl butyl, n-hexyl, 2-ethyl-butyl, n-heptyl, different heptyl, 2-ethylhexyl, different nonyl, positive decyl, isodecyl, dodecyl, n-hexadecyl, n-octadecane base, n-heptacosane base (icosyl), consider phosphorus content, preferred C wherein
1～C
6Alkyl.
Can enumerate C as alkenyl
2～C
20The alkenyl of straight or branched, for example vinyl, 1-propenyl, 2-propenyl, isopropenyl, 2-cyclobutenyl, 2-pentenyl, decene base, dodecenyl succinic, tridecylene base, hexadecene base, vaccenic acid base, eicosylene base, consider phosphorus content, preferred C wherein
2～C
6Alkenyl.
As cycloalkyl is cyclopentyl, cyclohexyl.
Can enumerate C as aryl
6～C
14Aryl, for example phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, cumenyl, octyl phenyl, xenyl, naphthyl, anthryl, phenanthryl, preferred phenyl, xenyl.
Can enumerate as aralkyl through C
1～C
4The aralkyl that alkylidene replaces, preferred benzyl, phenethyl.
In the above-mentioned alkyl, preferred C
1～C
4Alkyl, C
2～C
4Alkenyl, cyclopentyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl, more preferably methyl, ethyl, n-pro-pyl, normal-butyl, phenyl, benzyl.
In addition, substituent R
1The part of middle hydrogen atom can also be replaced by hydroxyl, sulfydryl, alkoxyl, carboxyl, amino, halogen atom.
As substituted R
1For example have: methylol, ethoxy, hydroxypropyl, hydroxy phenyl, mercapto methyl, mercaptoethyl, the sulfydryl propyl group, the sulfydryl phenyl, methoxy, methoxy ethyl, methoxy-propyl, methoxyphenyl, ethoxyl methyl, ethoxyethyl group, ethoxycarbonyl propyl, ethoxyl phenenyl, carboxymethyl, carboxyethyl, the carboxylic propyl group, carboxyl phenyl, amino methyl, amino-ethyl, aminopropyl, aminophenyl, methyl chloride, tonsilon, the chlorination propyl group, the chlorination phenyl, Diethylaminoethyl, the bromination ethyl, the bromination propyl group, bromination phenyl etc.Consider phosphorus content, preferred methylol, mercapto methyl, methoxy, carboxymethyl, amino methyl wherein, most preferably methylol.
X in the general formula (1) represents anion, does not have particular determination, specifically can be listed below:
(a) contain the anion of phosphorus atoms: phosphate ion, phosphorous acid ion, hypophosphorous acid ion, hexafluorophosphoric acid ester ion, D2EHDTPA ion, thiophosphorous acid ion, sulfo-hypophosphorous acid ion, carbophenothion acid ion, two sulphur phosphorous acid ions, two sulphur hypophosphorous acid ions; And the carboxylate ion (an alkyl phosphate ion, dialkyl group carbophenothion acid ion etc.) of they and aliphatic alcohol, aromatic series phenol
(b) contain many rings anion of nitrogen-atoms: benzotriazole salt (benzotriazalate), phthalimide-based etc.
(c) hydroxyl anion
(d) sulfate ion
(e) halogen atom anion: chlorion, bromide ion, iodide ion etc.
(f) contain the anion of boron atom: tetrafluoro boric acid ester ion, tetraphenyl borate ion etc.
(g) sulfurous acid ion
(h) nitrate ion
(i) nitrite ion
(j) carboxylic acid ion: formate ion, acetato-, propionic acid ion, oxalic ion, maleic acid ion
(k) carbonic acid ion
(l) hydrogen cyanide ion
(m) thiocyanate ion etc.
Wherein, consider preferred (a)～(f), more preferably (a)～(e) from anti-flammability and processability aspect.
Shang Shu De phosphonium salt can be opened flat 2-40389, spy according to the spy and open flat 3-74395, spy and open that disclosed known technology synthesizes in 2002-97182, the skill newspaper hall society " modern organic synthesis series 5 organic phosphorus compounds " etc.
For example, react, can obtain the tetrakis hydroxymethyl phosphonium phosphonium chloride by making phosphine, formaldehyde, hydrochloric acid according to the P105 of described skill newspaper hall society " modern organic synthesis series 5 organic phosphorus compounds ".In addition, the spy opens that disclosed method is among the 2002-97182: in the presence of alkali, commercially available phosphonium halide and benzotriazole are heated to 60～80 ℃ in water, make them carry out the salt exchange, De is Dao Phosphonium benzotriazole salt.
， Yi phosphonium salt (A) is that the adhesion amount of the fire retardant of neccessary composition is generally 0.1～10 quality % with respect to the polyesters synthetic fiber among the present invention.Consider from anti-flammability and light resistance aspect, more preferably 0.1～3 quality %.Adhesion amount effect when 0.1 quality % is above is better, and 10 quality % when following light resistance more abundant.For the polyesters synthetic fiber after the spinning are adhered to fire retardant, need modulate in the medium solution of dissolving or Fen San You phosphonium salt (A).As medium can be organic solvent or water, considers operation convenience, preferred water.
Fire retardant Yi phosphonium salt of the present invention (A) is a neccessary composition, can contain surfactant as required in addition.For example: phosphonium salt (A) is dissolved in water usually, and just can adopt following method when water insoluble, promptly, surfactant such as (A) and non-ionic surface active agent, anion surfactant and the organic solvent that cooperated are as required dissolved equably, slowly add water then their emulsification is disperseed.
For example have as non-ionic surface active agent: alkylene oxide add-on type non-ionic surface active agent, polyol-based non-ionic surfactant etc.
Can be listed below as alkylene oxide add-on type non-ionic surface active agent: (I) with C
2～C
4Alkylene oxide (ethylene oxide, expoxy propane, epoxy butane etc.; And their two or more combination, as follows) addition is at higher alcohol (C
8～C
18), higher fatty acids (C
12～C
24) or senior alkylamines (C
8～C
24) wait and the material (number-average molecular weight is 158～200,000) that obtains; (II) alkylene oxide is added be formed in the resultant ployalkylene glycol of glycol (Mw is 150～6,000) afterwards, again the material that reaction forms with higher fatty acids etc.; (III) higher fatty acids (C
12～C
24, as laurate, stearic acid) with multivalence (divalent～8 valencys or more than it) alcohol (C
8～C
60, as ethylene glycol, propylene glycol, glycerol, pentaerythrite, sorbitan) react and obtain after the carboxylate, again with the formed material of alkylene oxide addition (Mw is 250～30,000); (IV) with alkylene oxide addition resulting material (Mw is 200～30,000) on higher fatty acid amides; (V) with the alkylene oxide addition at the pure alkyl (C of multivalence (divalent～8 valencys or more than it)
8～C
60) resulting material (Mw is 120～30,000) etc. on the ether.
Can be listed below as polyol-based non-ionic surfactant: (I) divalent～8 valencys or its above polyalcohol (C
7～C
60) and aliphatic acid (C
8～C
60) ester that forms; (II) polyalcohol alkyl (C
7～C
60) ether; (III) aliphatic acid (C
8～C
60) alkanolamide etc.
Can be listed below as anion surfactant: (I) carboxylic acid (C
8～C
22Saturated or unrighted acid) or the salt (C of its salt (salt such as sodium, potassium, ammonium, chain hydramine), (II) carboxy methylation thing
8～C
16Aliphatic alcohol and/or its ethylene oxide (salt of carboxy methylation thing such as 1～10mol) addition product etc.), (III) sulfuric acid [higher alcohol sulfate salt (C
8～C
18The sulfuric acid of fatty acid alcohol etc.)] (IV) senior alkyl ether sulfuric acid [C,
8～C
18The ethylene oxide of fatty acid alcohol (sulfuric acid of 1～10mol) addition product], (V) sulfated oil (with the material after natural consaturated oil or the direct sulphation of unsaturated wax and the neutralization), (VI) sulfated fatty acid ester (with the low-carbon-ester sulphation of unrighted acid and the material after the neutralization), (VII) sulphation alkene is (with C
12～C
18Material after olefinic sulphur acidifying and the neutralization), (VIII) sulfonate [alkylbenzenesulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diesters type, alpha-olefin (C
12～C
18) sulfonate, N-oleoyl-methyl taurine sodium type etc.], (IX) phosphate ester salt [higher alcohol (C
8～C
60) phosphate ester salt, higher alcohol (C
8～C
60) ethylene oxide adduct phosphate ester salt, alkyl (C
8～C
60) phenol ethylene oxide adduct phosphate ester salt etc.] etc.
100 parts of the use level Xiang Dui Yu phosphonium salts (A) of above-mentioned surfactant are preferably 0.001～50 parts by mass, more preferably 0.05～35 parts by mass.
Use level is 0.001 parts by mass when above, and (A) dispersion stabilization in water is good, if below 50 parts by mass, fiber or fibre that the treatment fluid of being formed via (A) is handled still can have special excellent flame-retardant performance after washing and dry-cleaning.
Can be listed below as organic solvent: toluene, dimethylbenzene, Fluhyzon etc. are aromatic hydrocarbon based; Ketone such as acetone, MEK; Ethers such as diox, ethylene glycol monoethyl ether; Amide-types such as dimethyl formamide; Sulfoxide class and above-mentioned two or more mixtures such as dimethyl sulfoxide (DMSO).
100 parts of the use level Xiang Dui Yu phosphonium salts (A) of above-mentioned organic solvent are preferably 1～100 parts by mass, more preferably 10～90 parts by mass.Use level is 1 parts by mass when above, and (A) dispersion stabilization in water is good, if below 100 parts by mass, the anti-flammability of the fiber after handling through the treatment fluid of being made up of (A) is good.
Solid component concentration in the formed treatment fluid of Zhong You phosphonium salt of the present invention (A) is preferably 0.1～60 quality %, more preferably 0.1～40 quality %.
Use and modulate the formed treatment fluid of De You phosphonium salt (A) as described above, can handle the polyesters synthetic fiber according to known technology.
For example, when polyesters synthetic fiber or polyesters synthetic fiber cloth and silk being dyeed with liquid-flow dyeing machine, add this treatment fluid in dye bath, dipping polyesters synthetic fiber or polyesters synthetic fiber cloth and silk were handled several minutes～60 minutes under 80～130 ℃ temperature.As required with dehydrations such as centrifugal dehydrators, under 120～180 ℃ temperature, carry out several minutes heat treatment afterwards with the tentering device afterwards.
Handle with bathing by aforesaid dye bath, phosphonium salt (A) can effectively be adsorbed by cationic dye capable of dyeing polyesters synthetic fiber or cationic dye capable of dyeing polyesters synthetic fiber cloth and silk, shows high anti-flammability.
Do also can be listed below: polyesters synthetic fiber or polyesters synthetic fiber cloth and silk be impregnated in the treatment fluid of being made up of phosphonium salt (A), carry out the dry baking method of rolling then for other factures of phosphonium salt; This treatment fluid is sprayed on gunite on polyesters synthetic fiber or the polyesters synthetic fiber cloth and silk etc., considers that from the anti-flammability aspect of washing after back and the dry-cleaning preferred dye bath is with bathing facture.
The phosphonium salt of Ben Faming (A) can also also be used with other fire retardant.Can be listed below as this fire retardant: disclosed in the special permission 2969259 is the polyesters fire retardant (B) of copolymer composition with the phosphinic acid derivatives; The spy opens disclosed phosphoric acid ester fire retardant (C) among the 2000-328445; Have the spy and open the compound (D) of disclosed phospho hetero phenanthrene skeleton among the flat 2002-275473; The spy opens fire retardant (E) that is disclosed as phosphorus compound (II) of 2001-354821 etc.
Mass ratio Shi phosphonium salt (A)/other fire retardants=1/99～99/1 when Bing Yong phosphonium salt (A) and these fire retardants, You Xuan phosphonium salt (A)/other fire retardants=10/90～99/1.Phosphonium salt is 10 quality % when above, and better for the flame retardant effect of cationic dye capable of dyeing polyesters synthetic fiber, if be lower than 99 quality %, light resistance is good so.
As also being listed below: with method with the method that phosphonium salt (A) is handled with dye bath simultaneously; Behind dye bath Chu Li phosphonium salt (A), use the method for these fire retardants with the liquid flowing dyeing agent; Behind dye bath Chu Li phosphonium salt (A), handle the method etc. of these fire retardants by rolling baking.
In addition, fire retardant can also and be used with other fiber processing agents, stabilizing agent among the present invention.As described fiber processing agent, stabilizing agent can be listed below: softener (silicon class latex, change into industry system サ Off ア ノ-Le N-750 as Sanyo), suction processing agent (polyester resin latex, change into industry system パ-マ リ Application MR-100 as Sanyo), antistatic additive (phosphates surfactant, change into industry system サ Application ス Star ト KT-600 as Sanyo), hydrophobic oleophobic agent (paraffin, change into industry system ア ィ ソ ト-Le H as Sanyo), antilubricant (cataloid, change into industry system パ-マ リ Application SCC-A as Sanyo), cloth hard finishing agent, texture is adjusted agent, preservative agent, antioxidant, PH adjusts agent etc., as long as in not undermining scope of the present invention, bathe and to use with bath or he.
When using in bath or his bath, the use amount of described other fiber processing agents is preferably below the 50 quality % with respect to the quality of the phosphonium salt (A) of Ben Faming, more preferably below the 30 quality %.
Polyesters synthetic fiber applicatory are listed below among the present invention: by polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate (PBT), PEN, PBN, polyethylene terephthalate/isophthalic acid ester, polyethylene terephthalate/5-sodium is for sulfoisophthalate, polyethylene/poly-(2-hydroxybenzoyl) terephthalate, the formed cotton of polyester fibers such as polybutylene terephthalate (PBT)/isophthalic acid ester, yarn, short flax, wool top, the Guang line, braided fabric, nonwoven fabric etc.
Cationic dye capable of dyeing polyesters synthetic fiber particularly, because of its fiber itself inflammable, and fire retardant in the past is difficult to suction, even therefore also there is the problem that can not give enough anti-flammabilitys in the fire retardant that is suitable in the past, and fire retardant of the present invention fully is absorbed in cationic dye capable of dyeing polyesters synthetic fiber especially easily, thereby can bring into play sufficient anti-flammability.
Aforesaid cationic dye capable of dyeing polyesters synthetic fiber are meant polyethylene terephthalate/5-sodiosulfoisophthalic acid ester, are the part of terephthalic acid (TPA) in the common polyester fiber polyethylene terephthalate materials after by the displacement of 5-sodiosulfoisophthalic acid.
Can also list and the blending of blending, MIXED FABRIC or the described polyester fiber of the polyesters synthetic fiber of above-mentioned different compositions and other natural (cotton, fiber crops, wool etc.), semi-synthetic (artificial fibre, acetate etc.), synthetic (nylon, acrylic fiber etc.), inorganic (carbon, glass, pottery, asbestos, metal etc.) fiber, MIXED FABRIC etc.
The article of handling through fire retardant of the present invention can be used for following purposes: the vehicles such as automobile, railway, boats and ships, aircraft, communal facilitys such as cinema, hospital, hotel, or the seat cushion of family expenses, chair cover, curtain, volume curtain, wall curtain, smallpox paperboard, window paper, carpet, thick curtain, maintenance cloth for building, protection are with fiber or fibres such as net, canvas, tents.
Embodiment
Further specify the present invention with following embodiment, but the present invention is not subjected to the qualification of embodiment.Part expression parts by mass among the embodiment, % represents quality %, than the expression mass ratio, evaluating characteristics carries out in accordance with the following methods.
(1) anti-flammability
Estimate according to JIS L 1091D method (connecing scorching test).
(2) washing methods
Carry out according to JIS L 1042 methods.
(3) dry cleaning process
Carry out according to JIS L 1018 methods.
(4) tenderly white streak
Scrape the wiper surface with the paper tape cutter, with the naked eye judge to have or not tenderly white streak to produce.Do not have the usefulness zero of tenderly white streak generation and represent the usefulness * expression of generation.
(5) texture (bending stiffness)
Under 20 ℃ of temperature, humidity 65% condition, adjust test portion (processing cloth) after 24 hours, measure bending stiffness with pure bending testing machine [カ ト-テ Star Network society system, KES-FB-2].
Synthesis example 1 (employed polyesters fire retardant in embodiment 2, comparative example 1)
Mix following material: 125 parts of phosphinic acid derivatives shown in 65 parts of dimethyl terephthalate (DMT)s, 290 parts of ethylene glycol and the general formula (2), be 0.1% manganese acetate, 0.5% lithium acetate and 0.03% antimony trioxide with respect to dimethyl terephthalate (DMT) and phosphinic acid derivatives as catalyst.Carried out ester exchange reaction in 3 hours at normal pressure and 160～220 ℃ of following heating afterwards, distillating the roughly methyl alcohol of theoretical amount, is the adjustment of system 250 ℃ then, slowly reduces pressure below the 1Torr, react obtain after 6 hours that weight average molecular weight is 9,000, phosphorus content is 5.5% polyester.
With 50 parts of 150 parts of this polyester, 100 parts of dimethyl formamides, laruyl alcohol ethylene oxide 15mol addition product 80 ℃ of dissolvings equably, slowly add hot water (80 ℃) 700 parts and carry out particlized, after being cooled to normal temperature, pulverized continuously 30 minutes with Viscomill (ア ィ メ Star Network ス system horizontal wet micro mist dispersion machine), obtain 1000 parts of polyesters fire retardants (B).(B) be milky dispersion liquid, viscosity is 350cp (25 ℃), and average grain diameter is 0.3 μ m, and PH is 6.5.
Synthesis example 2 (employed phosphoric acid ester fire retardant in embodiment, comparative example 2)
100 parts of 500 parts of the two diphenyl phosphoesters of resorcinol, triphenylethylene phenol poly(ethylene oxide) 20mol addition product are mixed at 60 ℃, and make it emulsification for 400 parts, obtain 1000 parts of phosphoric acid ester fire retardants (C) to wherein slowly adding entry.
Embodiment 1～7, comparative example 1,2
Make to be the phosphonium salt of Ben Faming (A), use Si Zheng Ding Ji Phosphonium benzotriazole salt (the system ヒ シ コ of Nippon Chemical Ind-リ Application PX-4BT) 30% aqueous solution (A-1), 4-phenyl phosphonium bromide (the system TPP-PB of Hokko Chemical Industry Co., Ltd.) 30% aqueous solution (A-2), four positive fourth base Phosphonium hydroxide (the system TBPH of Hokko Chemical Industry Co., Ltd.), 30% aqueous solution (A-3) adopts the fire retardant dispersion liquid (B) that is prepared by synthesis example 1 as the polyesters fire retardant that with the phosphinic acid derivatives is copolymer composition, use the fire retardant (C) for preparing by synthesis example 2 as the phosphoric acid ester fire retardant.
According to the above-mentioned fire retardant of the mixed shown in the table 1, obtain each fire-retardant processed and bathe.
Table 1
| Phosphonium salt (A) | Polyesters fire retardant (B) | Phosphoric acid ester fire retardant (C) | |||
| ????A-1 | ????A-2 | ????A-3 | |||
| Embodiment 1 | ????100 | ||||
| Embodiment 2 | ????50 | ????50 | |||
| Embodiment 3 | ????50 | ????50 | |||
| Embodiment 4 | ????100 | ||||
| Embodiment 5 | ????50 | ????50 | |||
| Embodiment 6 | ????50 | ????50 | |||
| Embodiment 7 | ????50 | ????50 | |||
| Comparative example 1 | ????100 | ||||
| Comparative example 2 | ????100 | ||||
Numeral in the table is quality %
In the fire-retardant processed, the polyesters synthetic fiber cloth with respect to the rate that interweaves shown in the table 2 makes bath raio reach 1: 20, and the purity of each fire retardant reaches 5%o.w.f., handles 60 minutes at 130 ℃.In addition, the composition of cationic dye capable of dyeing PET is polyethylene terephthalate/5-sodiosulfoisophthalic acid ester.
In embodiment 3,6,7 and the comparative example 2, bath raio is carried out with dithionite 1g/L, soda lime 2g/L, washing agent (Sanyo changes into industry system グ ラ Application ア Star プ US-30) 2g/L in this processing back, and 1: 20,80 ℃ * 30 minutes reduction is washed.
Table 2
| Common PET | Cationic dye capable of dyeing PET | |
| Cloth 1 | ????100 | ????0 |
| Cloth 2 | ????90 | ????10 |
| Cloth 3 | ????50 | ????50 |
Numeral in the table is quality %
It is 250g/m that the order of each cloth is paid (basis weight)
2
Afterwards, drying is respectively processed cloth (100 ℃ * 5 minutes) and is carried out dry heat treatment (180 ℃ * 1 minute), and it is as shown in table 3 that each processes the measurement result of cloth characteristic.
Table 3.
| Cloth 1 | Cloth 2 | Cloth 3 | |||||||||||||
| Anti-flammability | Tenderly white streak | Bending stiffness gcm | Anti-flammability | Tenderly white streak | Bending stiffness gcm | Anti-flammability | Tenderly white streak | Bending stiffness gcm | |||||||
| Initial stage | After the washing | After the dry-cleaning | Initial stage | After the washing | After the dry-cleaning | Initial stage | After the washing | After the dry-cleaning | |||||||
| Embodiment 1 | ?3.4 | ??3.2 | ??3.2 | ?○ | ??0.15 | ??3.6 | ??3.4 | ??3.4 | ?○ | ??0.18 | ??4.0 | ??3.8 | ??4.0 | ??○ | ??0.20 |
| Embodiment 2 | ?4.2 | ??4.2 | ??4.4 | ?○ | ??0.19 | ??4.6 | ??4.4 | ??4.6 | ?○ | ??0.21 | ??4.4 | ??4.2 | ??4.4 | ??○ | ??0.24 |
| Embodiment 3 | ?4.2 | ??4.0 | ??3.8 | ?○ | ??0.16 | ??4.5 | ??4.5 | ??4.5 | ?○ | ??0.17 | ??4.2 | ??4.2 | ??4.2 | ??○ | ??0.19 |
| Embodiment 4 | ?3.2 | ??3.4 | ??3.2 | ?○ | ??0.16 | ??3.2 | ??3.0 | ??3.2 | ?○ | ??0.19 | ??4.0 | ??4.0 | ??4.0 | ??○ | ??0.19 |
| Embodiment 5 | ?4.0 | ??4.2 | ??4.2 | ?○ | ??0.19 | ??4.8 | ??4.6 | ??4.8 | ?○ | ??0.20 | ??4.5 | ??4.4 | ??4.5 | ??○ | ??0.25 |
| Embodiment 6 | ?4.2 | ??4.0 | ??3.8 | ?○ | ??0.16 | ??4.5 | ??4.5 | ??4.5 | ?○ | ??0.18 | ??4.3 | ??4.3 | ??4.3 | ??○ | ??0.19 |
| Embodiment 7 | ?4.2 | ??4.0 | ??3.8 | ?○ | ??0.16 | ??4.7 | ??4.7 | ??4.7 | ?○ | ??0.18 | ??4.4 | ??4.4 | ??4.4 | ??○ | ??0.19 |
| Comparative example 1 | ?4.0 | ??4.2 | ??4.2 | ?× | ??0.45 | ??4.0 | ??4.2 | ??4.0 | ?× | ??0.51 | ??3.2 | ??3.4 | ??3.4 | ??× | ??0.55 |
| Comparative example 2 | ?4.2 | ??4.0 | ??3.8 | ?○ | ??0.16 | ??3.4 | ??2.8 | ??2.8 | ?○ | ??0.17 | ??2.2 | ??2.2 | ??2.0 | ??○ | ??0.19 |
| Blank (blank) | ?2.4 | ??2.4 | ??2.4 | ?○ | ??0.16 | ??1.8 | ??1.6 | ??1.8 | ?○ | ??0.18 | ??1.2 | ??1.2 | ??1.0 | ??○ | ??0.19 |
Fire-retardant processed goods of the present invention passes through polyesters synthetic fiber goods, particularly cationic dye capable of dyeing polyesters synthetic fiber cloth and silk carries out back processing, handle with this, compare with conventional art, tenderly white streak can not occur, and can give the durability excellent flame-retardant performance by carry out back processing with not halogen-containing compound.Therefore extremely useful as the polyesters synthetic fiber with back processing fire retardant.
Claims (11)
1. a fiber finishing agent is a neccessary composition with the phosphonium salt (A) shown in the following general formula (1),
In the formula, R
1Represent independently that respectively carbon number is that 1～20 alkyl, carbon number are that 2～20 alkenyl, carbon number are that 5～6 cycloalkyl, carbon number are 6～14 aryl or are the aryl alkyl that 1～4 alkylidene replaces through carbon number, the part of hydrogen atom can be replaced R in the above-mentioned alkyl by hydroxyl, sulfydryl, alkoxyl, carboxyl, amino or halogen atom
1Between can also be incorporated into ring, X represents anion.
2. fiber finishing agent as claimed in claim 1, wherein said X are to be selected from the anion that contains phosphorus atoms, the heterocycle anion that contains nitrogen-atoms, hydroxyl anion, sulfate anion, halogen atom anion and to contain a kind of anion in the anion of boron atom.
3. fiber finishing agent as claimed in claim 2, wherein said X are the heterocycle anion that contains nitrogen-atoms.
4. as each the described fiber finishing agent in the claim 1～3, it makes phosphonium salt be dispersed or dissolved in water or/and in the organic solvent and form.
5. fiber finishing agent as claimed in claim 4, it is phosphonium salt emulsification is dispersed in the water that has cooperated surfactant and organic solvent and forms.
6. a fire retardant is characterized in that, gives composition as anti-flammability and contains each described fiber finishing agent in the claim 1～5.
7. fire retardant as claimed in claim 6, wherein, also containing with the phosphinic acid derivatives is the polyesters fire retardant or the phosphoric acid ester fire retardant of copolymer composition.
8. the described fiber of each in the claim 1～5 application of finishing agent as fire retardant.
9. anti-flammability adding method, it is characterized in that, by: to the polyesters synthetic fiber provide in operation (I), drying process (II) and the heat treatment step (III) of claim 6 or 7 described fire retardants (I) and (II) or/and (III) constitute.
10. anti-flammability adding method as claimed in claim 9, wherein, the solid component concentration of fire retardant is 0.1～60 weight % in the treatment fluid.
11. polyesters synthetic fiber is characterized in that, handle and obtain with claim 9 or 10 described anti-flammability adding methods.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003175942 | 2003-06-20 | ||
| JP2003175942A JP3948620B2 (en) | 2003-06-20 | 2003-06-20 | Flame retardant for polyester synthetic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1572968A true CN1572968A (en) | 2005-02-02 |
Family
ID=34098947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410060021 Pending CN1572968A (en) | 2003-06-20 | 2004-06-21 | Fire retardant for fiber, fire-retardancy enduing method and fire retardation treated fiber |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3948620B2 (en) |
| CN (1) | CN1572968A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101631910B (en) * | 2007-02-28 | 2013-05-22 | 松本油脂制药株式会社 | Flameproofing agent, flame-retardant fiber and method for producing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6375181A (en) * | 1986-09-10 | 1988-04-05 | 株式会社 新洋インテリア | Flameproof processing of polyester/cellulose fiber mixed cloth |
| JPH02500454A (en) * | 1986-09-26 | 1990-02-15 | バーリングトン・インダストリイズ・インコーポレイテッド | Heat resistant cotton blend fiber |
| GB9412484D0 (en) * | 1994-06-22 | 1994-08-10 | Albright & Wilson | Flame-retardant treatment of fabrics |
| JP2001131872A (en) * | 1999-10-25 | 2001-05-15 | Koizumi Kagaku Kk | Treating agent and treating bath for cellulose fiber material, and method for treating the same |
| JP4550247B2 (en) * | 2000-09-20 | 2010-09-22 | 日本化学工業株式会社 | Phosphonium compound, production method thereof, and composition thereof |
-
2003
- 2003-06-20 JP JP2003175942A patent/JP3948620B2/en not_active Expired - Fee Related
-
2004
- 2004-06-21 CN CN 200410060021 patent/CN1572968A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101631910B (en) * | 2007-02-28 | 2013-05-22 | 松本油脂制药株式会社 | Flameproofing agent, flame-retardant fiber and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005009041A (en) | 2005-01-13 |
| JP3948620B2 (en) | 2007-07-25 |
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