CN102493186B - Low-temperature scouring and bleaching aid for textiles as well as preparation method and application of low-temperature scouring and bleaching aid - Google Patents

Low-temperature scouring and bleaching aid for textiles as well as preparation method and application of low-temperature scouring and bleaching aid Download PDF

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CN102493186B
CN102493186B CN2011103794080A CN201110379408A CN102493186B CN 102493186 B CN102493186 B CN 102493186B CN 2011103794080 A CN2011103794080 A CN 2011103794080A CN 201110379408 A CN201110379408 A CN 201110379408A CN 102493186 B CN102493186 B CN 102493186B
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bleaching
scouring
low
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metal complex
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CN102493186A (en
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毛志平
尹冲
张琳萍
徐红
钟毅
宋敏
鲁玉洁
秦新波
单宋玉
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Donghua University
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Abstract

The invention relates to a low-temperature scouring and bleaching aid for textiles as well as a preparation method and application of the low-temperature scouring and bleaching aid. The low-temperature scouring and bleaching aid comprises the following components of a metal complex and a scouring and bleaching agent, wherein the addition amount of the metal complex accounts for 0.01-99.9 percent of the total weight. The preparation method comprises the following steps of: adding the metal complex into the scouring and bleaching aid according to the proportion that the metal complex accounts for 0.01-99.9 percent of the total weight of reactant, and stirring for 15-30min to obtain the low-temperature scouring and bleaching aid. According to the invention, the metal complex is added into the conventional scouring and bleaching aid for textiles, so that the efficiency of the aid can be increased; when the low-temperature scouring and bleaching aid is used for a pretreatment process in which hydrogen peroxide is used as a bleaching agent, the scouring and bleaching temperature can be reduced, and the scouring and bleaching temperature of the textiles can be reduced to 60-85 DEG C from 95-100 DEG C or even below, therefore the production energy consumption is greatly reduced. The low-temperature scouring and bleaching aid has favorable application prospect.

Description

A kind of textiles low-temperature scouring and bleaching assistant and its preparation method and application
Technical field
The invention belongs to Pretreatment of textile auxiliary agent and its preparation method and application field, particularly a kind of textiles low-temperature scouring and bleaching assistant and its preparation method and application.
Background technology
In recent years, abroad had metallic compound has been added on the precedent that increases bleaching effect in auxiliary agent, company number is the Activation of Hydrogen Peroxide Solution agent of OSBON such as Japanese Diaod synthetic chemical industry, it is used for cold rolling heap Scouring and bleaching process, can solve the uneven bleaching problem that causes because of the extraneous temperature difference and the asynchronism(-nization) of banking up.But this activator activation efficiency is not high, can not take full advantage of hydrogen peroxide, if will improve reaction efficiency, also needs to add the transition elements complex compound in activator, as manganese, copper, iron, nickel, the isoionic huge legendary turtle compound of cobalt.In solution, these complex compounds can dissociate a certain amount of metal ion, thereby play catalytic action, the decomposition rate of hydrogen peroxide is accelerated, reduce the required time of bleaching, but the metal ion that dissociates can cause on the intensity of fabric very large impact, so this activator and fail to obtain very large popularization.
Patent CN200910046259.9 discloses a kind of composition, and this composition has added manganese, zinc, the isoionic salt of aluminium, and has added the chelating agent of these metals of energy chelating, as hydrogen peroxide catalyst hydrogen peroxide bleaching.
Patent CN200810027264.0 discloses a kind of cleaning compositions that contains the metal catalytic bleach system, a kind of the have manganese of polynary ring structure or metal complex of iron, its main application is clothes washing, main component comprises: transition metal complex, peroxide, water softener, essence, surfactant, enzyme, fluorescent whitening agent etc., the effectively spot on the clothing of place to go.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of textiles low-temperature scouring and bleaching assistant and its preparation method and application, and this scouring and bleaching assistant has added metal complex, can reduce the temperature of scouringing and bleaching, and greatly reduces energy consumption, has a good application prospect.
A kind of textiles low-temperature scouring and bleaching assistant of the present invention, described low-temperature scouring and bleaching assistant comprises metal complex and scouring and bleaching assistant, the addition of metal complex is the 0.01-99.9% of gross weight.
The addition of described metal complex is the 0.01-5.0% of gross weight.
Described textiles is for containing cotton fabrics grey cloth, knit grey cloth or base yarn.
Described metal complex is N, N ', N "-three [salicylidene amino-ethyl] amine) metal complex, benzo four acid amides Macrocyclic metal complexes, terpyridyl metal complex, tetraazacyclododecane hexadecane metal complex, two pyridine pyrimidine metal complex, four nitrogen dicyclo tetradecane metal complexs, four pyridine radicals five nitrogen metal complexs, Macrocyclic polyamine bridging metal complex, three pyridine radicals four nitrogen metal complexs, 1-10 phenanthroline metal complex, bipyridyl four nitrogen metal complexs or three pyridine radicals five nitrogen metal complexs.
Described scouring and bleaching assistant is bleaching assistant, boil and float auxiliary agent, move back to boil and float auxiliary agent, scouring agent, bleeding agent or stabilizing agent.
Described scouring and bleaching assistant is scouring agent 88-ECO, scouring enzyme DR-510, scouring agent HA-SSA, concise bleeding agent FB-18, KDN easily cotton clear, scouring agent ST-1 or stabilizing agent KDN-T.
The preparation method of a kind of textiles low-temperature scouring and bleaching assistant of the present invention comprises:
The 0.01-99.9% of metal complex by the reactant gross weight added in scouring and bleaching assistant, stir 15~30min, and get final product.
The application of a kind of textiles low-temperature scouring and bleaching assistant of the present invention, described scouring and bleaching assistant is scouringed and bleaching for the low temperature that contains cotton fabrics grey cloth, knit grey cloth or base yarn.
Beneficial effect
The metal complex that the present invention relates to adds in the conventional scouring and bleaching assistant of textiles, can increase the efficient of auxiliary agent, be used for using hydrogen peroxide as the pre-treatment process of bleaching agent, can reduce the temperature of scouringing and bleaching, the fabric temperature of scouringing and bleaching is down to 60-85 ℃ from 95-100 ℃, even can be down to lower temperature, greatly reduce energy consumption, have a good application prospect.
Description of drawings
Fig. 1 is N, N ', N "-three [salicylidene amino-ethyl] amine) structural representation of metal complex; Wherein, M represents different metal ions, is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II);
Fig. 2 is the structural representation of benzo four acid amides Macrocyclic metal complexes; Wherein, R=Me or F; X=H, Cl, NO 2, MeOOC, CH 3M represents different metal ions, is selected from a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Cu (I)-(II), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Co (I)-(II)-(III);
Fig. 3 is the structural representation of terpyridyl metal complex; Wherein, R 1, R 2, R 3Be independently hydrogen, C separately 1-18Alkyl, aryl, cyano group, nitro, halogen etc.; M represents different metal ions, is selected from a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Cu (I)-(II), Co (I)-(II)-(III);
Fig. 4 is 5,5,7,12,12,14-hexamethyl, Isosorbide-5-Nitrae, the structural representation of 8,11-tetraazacyclododecane hexadecane metal complex; Wherein, M represents different metal ions, is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II);
Fig. 5 is the structural representation of two pyridine pyrimidine metal complexs; Wherein, R 1, R 2, R 3Be independently hydrogen separately, the C of replacement 1-18Alkyl or aryl, cyano group, nitro, halogen; M represents different metal ions, is selected from a kind of in Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Cr (I)-(II), Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III), Ni (II)-(III), Cu (I)-(II), Zn (I)-(II);
Fig. 6 is the structural representation of two pyridine pyrimidine metal complexs; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III);
Fig. 7 is the structural representation of four pyridine radicals five nitrogen metal complexs; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III);
Fig. 8 is the structural representation of bridging Macrocyclic polyamine metal complexes; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III);
Fig. 9 is the structural representation of three pyridine radicals four nitrogen metal complexs; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III);
Figure 10 is the structural representation of 1-10 phenanthroline metal complex; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III); R 1, R 2, R 3, R 4Be independently hydrogen separately, the C of replacement 1-18Alkyl or aryl, cyano group, nitro, halogen etc.;
Figure 11 is the structural representation of bipyridyl four nitrogen metal complexs; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III); R1 is methyl, ethyl; R2 is methyl, ethyl, pyridine radicals, trimethylamine groups;
Figure 12 is the structural representation of three pyridine radicals five nitrogen metal complexs; Wherein, M represents different metal ions, a kind of in Mn (II)-(III)-(IV)-(V), Fe (II)-(III), Co (I)-(II)-(III); R1, R2, R4 is selected from methyl, ethyl; R3 is selected from methyl, ethyl, hydroxyethyl, methoxy ethyl.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Take the scouring agent 88-ECO of the triumphant Chemical Manufacture of 99.8kg section, evenly add 0.2kg (mass fraction) N, N '; N under stirring at normal temperature "-three [salicylidene amino-ethyl] amine) manganese complex, add completely, continue to stir 15min, this scouring agent is used in the knitted fabric process of scouringing and bleaching.
The Scouring and bleaching process experiment: do two check experiments, 1# technique is conventional needle fabric Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: 20s cotton combing knitting single jersey, 180g/m 2
1# tradition bleaching process
Figure BDA0000111919480000031
Bath raio 1: 20,95 ℃, 60min
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000041
Bath raio 1: 20,70 ℃, 60min
Table 1 result of scouringing and bleaching
Figure BDA0000111919480000042
Embodiment 2
Take the efficient scouring enzyme DR-510 of the flourish Chemical Manufacture of 99.9kg Wuxi moral, evenly add 0.1kg (mass fraction) the benzo four large ring iron complexes of acid amides under stirring at normal temperature, adds completely, continue stirring 15min, obtain new auxiliary.
This example is done two check experiments, and 1# technique is traditional woven thing Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: polyester-cotton blend woven fabric T/C40 * 40*120 * 80
1# tradition polyester-cotton blend woven fabric bleaching process
Figure BDA0000111919480000043
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000044
100% pick-up soaks one more and rolls, 80 ℃ of decatizes 45 minutes.
Table 2 result of scouringing and bleaching
Figure BDA0000111919480000051
Embodiment 3
Take the multi-functional concise dose of HA-SSA that Hai'an, 49.9kg Jiangsu petrochemical plant is produced, evenly add 0.1kg (mass fraction) terpyridyl manganese complex under stirring at normal temperature, adds completely, continue stirring 15min, obtain new auxiliary.This multi-functional concise dose is used in during cheese scourings and bleaching.
This example is done two check experiments, and 1# technique is traditional cheese Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: textile cheese (C70S/2)
1# traditional cotton cheese Scouring and bleaching process
Figure BDA0000111919480000052
Bath raio 1: 10,95 ℃, 60min
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000053
Bath raio 1: 10,70 ℃, 60min
Table 3 result of scouringing and bleaching
Figure BDA0000111919480000054
Take the efficient concise bleeding agent FB-18 that 49.95kg sea hugeization weaving chemical science and technology research institute produces, evenly add 0.05kg (mass fraction) 5,5 under stirring at normal temperature, 7,12,12,14-vegolysen, 4,8,11-tetraazacyclododecane iron complex adds complete, continue to stir 15min, obtain new auxiliary.This infiltration scouring agent is applied in during cotton fabrics scourings and bleaching.
This example is done two check experiments, and 1# technique is traditional cotton knitted fabric Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: 20s cotton combing single jersey, 180g/m 2
1# traditional cotton knitted fabric bleaching process
Figure BDA0000111919480000061
Bath raio 1: 20,95 ℃, 60min
2# low temperature is scouringed and bleaching
Hydrogen peroxide (30%) 6g/L
Caustic soda 2g/L
The concise bleeding agent FB-18 2g/L that adds 0.1% catalyst
Bath raio 1: 20,70 ℃, 60min
Table 4 result of scouringing and bleaching
Embodiment 5
Take the KDN that the upper Haikang of 99.9kg ground grace biotechnology company produces easily cotton clear, evenly add the two pyridine pyrimidine radicals of 0.1kg (mass fraction) manganese complex under stirring at normal temperature, adds completely, continue stirring 15min, obtain new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technique is traditional cheese Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000071
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
100% pick-up soaks one more and rolls, 80 ℃ of decatizes 45 minutes.
Table 5 result of scouringing and bleaching
Embodiment 6
Take the homemade scouring agent ST-1 of 99.9kg, add 0.1kg (mass fraction) four nitrogen dicyclo tetradecane iron complexes, adds completely, continue stirring 15min, obtain new auxiliary.This scouring agent is used for pure cotton knitted fabric scourings and bleaching.
Table 6 self-control scouring agent ST-1 formula
Figure BDA0000111919480000074
This example is done two check experiments, and 1# technique is conventional needle fabric Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts, and 3# technique is not for adding the low temperature Scouring and bleaching process of metal complex.
Process fabric: 20s cotton combing single jersey, 180g/m 2
1# traditional cotton knitted fabric bleaching process
Figure BDA0000111919480000075
Figure BDA0000111919480000081
Bath raio 1: 20,95 ℃, 60min
2# low temperature is scouringed and bleaching
Bath raio 1: 20,70 ℃, 60min.
3# low temperature is scouringed and bleaching
Figure BDA0000111919480000083
Bath raio 1: 20,70 ℃, 60min.
Table 7 result of scouringing and bleaching
Embodiment 7
Take in the stabilizing agent KDN-T that on 49.94kg, ground, Haikang grace biotechnology company produces, add 0.06kg (mass fraction) four pyridine radicals five nitrogen manganese complexes, this stabilizing agent is applied in the cotton fabrics Scouring and bleaching process.
This example is done two check experiments, and 1# technique is traditional woven thing Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000085
Figure BDA0000111919480000091
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000092
100% pick-up soaks one more and rolls, and 80 ℃, decatize 45 minutes.
Table 8 result of scouringing and bleaching
Embodiment 8
Take the homemade scouring agent ST-1 of 99.9kg, add 0.1kg (mass fraction) Macrocyclic polyamine bridging manganese complex, adds complete after, continue to stir 15min, obtain new auxiliary, this scouring agent is scouringed and bleaching for pure cotton knitted fabric.
This example is done two check experiments, and 1# technique is traditional woven thing Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000094
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000095
100% pick-up soaks one more and rolls, and 80 ℃, decatize 45 minutes.
Table 9 result of scouringing and bleaching
Figure BDA0000111919480000102
Embodiment 9
Take the KDN that the upper Haikang of 99.9kg ground grace biotechnology company produces easily cotton clear, evenly add 0.1kg (mass fraction) three pyridine radicals four nitrogen manganese complexes under stirring at normal temperature, adds completely, continue stirring 18min, obtain new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technique is traditional cheese Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000103
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
100% pick-up soaks one more and rolls, 80 ℃ of decatizes 45 minutes.
Table 10 result of scouringing and bleaching
Figure BDA0000111919480000111
Embodiment 10
Take the KDN that the upper Haikang of 99.9kg ground grace biotechnology company produces easily cotton clear, evenly add 0.1kg (mass fraction) 1-10 phenanthroline manganese complex under stirring at normal temperature, adds completely, continue stirring 20min, obtain new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technique is traditional cheese Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000112
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
100% pick-up soaks one more and rolls, 80 ℃ of decatizes 45 minutes.
Table 11 result of scouringing and bleaching
Figure BDA0000111919480000114
Embodiment 11
Take the KDN that the upper Haikang of 99.92kg ground grace biotechnology company produces easily cotton clear, evenly add 0.08kg (mass fraction) two pyridine four nitrogen manganese complexes under stirring at normal temperature, adds completely, continue stirring 15min, obtain new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technique is traditional cheese Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000121
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000122
100% pick-up soaks one more and rolls, 80 ℃ of decatizes 45 minutes.
Table 12 result of scouringing and bleaching
Embodiment 12
Take the KDN that the upper Haikang of 99.9kg ground grace biotechnology company produces easily cotton clear, evenly add 0.1kg (mass fraction) three pyridine five nitrogen manganese complexes under stirring at normal temperature, adds completely, continue stirring 15min, obtain new auxiliary.This digesting agent is applied in the woven fabric cold bleaching.
This example is done two check experiments, and 1# technique is traditional cheese Scouring and bleaching process, and 2# technique is for adding the low temperature Scouring and bleaching process of metal complex catalysts.
Process fabric: cotton fabrics C40 * 40*173 * 120
1# traditional cotton woven fabric bleaching process
Figure BDA0000111919480000131
100% pick-up soaks one more and rolls, 95 ℃ of decatizes 45 minutes.
2# low temperature is scouringed and bleaching
Figure BDA0000111919480000132
100% pick-up soaks one more and rolls, 80 ℃ of decatizes 45 minutes.
Table 13 result of scouringing and bleaching
Figure BDA0000111919480000133

Claims (2)

1. the application of a textiles low-temperature scouring and bleaching assistant is characterized in that: described low-temperature scouring and bleaching assistant is scouringed and bleaching for the low temperature that contains cotton fabrics grey cloth, knit grey cloth or base yarn; Low-temperature scouring and bleaching assistant comprises metal complex and scouring and bleaching assistant, and described metal complex is 1,10-ferrosin metal complex, and its structure is:
Figure FDA00003064902100011
In formula, M is metal ion, is selected from a kind of in Mn (II)-(III); R 1, R 2, R 3, R 4Be independently hydrogen separately, the C of replacement 1-18Alkyl or aryl, cyano group, nitro, halogen; Described scouring and bleaching assistant is refining agent, bleeding agent or stabilizing agent; The addition of described metal complex is the 0.01-99.9% of low-temperature scouring and bleaching assistant gross weight.
2. the application of a kind of textiles low-temperature scouring and bleaching assistant according to claim 1 is characterized in that: the addition of described metal complex is the 0.01-5% of low-temperature scouring and bleaching assistant gross weight.
CN2011103794080A 2011-11-24 2011-11-24 Low-temperature scouring and bleaching aid for textiles as well as preparation method and application of low-temperature scouring and bleaching aid Active CN102493186B (en)

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Related Child Applications (11)

Application Number Title Priority Date Filing Date
CN2013101278503A Division CN103174008A (en) 2011-11-24 2011-11-24 Application of bipyridyl tetranitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101281968A Division CN103174011A (en) 2011-11-24 2011-11-24 Application of tetranitrogen bicyclotetradecane metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN201310127812.8A Division CN103174007B (en) 2011-11-24 2011-11-24 Application of tripyridyl tetranitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101282138A Division CN103194897A (en) 2011-11-24 2011-11-24 Application of benzo-tetraamido macrocyclic metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101281991A Division CN103194895A (en) 2011-11-24 2011-11-24 Application of tetraazacyclohexadecane metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101278113A Division CN103174006A (en) 2011-11-24 2011-11-24 Application of bipyridyl pyrimidine metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101278607A Division CN103174010A (en) 2011-11-24 2011-11-24 Application of macrocyclic polyamine bridged metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101281949A Division CN103194894A (en) 2011-11-24 2011-11-24 Application of tetrapyridyl pentanitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN2013101282000A Division CN103194896A (en) 2011-11-24 2011-11-24 Application of terpyridyl metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN201310127858XA Division CN103174009A (en) 2011-11-24 2011-11-24 Application of tripyridyl pentanitrogen metal complex to low-temperature scouring and bleaching auxiliary for textiles
CN201310134885XA Division CN103225206A (en) 2011-11-24 2011-11-24 Application of N,N',N"-tri[salicylideneaminoalcohol ethyl]amine) metal complex in low-temperature scouring and bleaching auxiliary agent of textile

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