CN1259324C - Cation, reactnig silicone coloring fixing agent and preparing method thereof - Google Patents
Cation, reactnig silicone coloring fixing agent and preparing method thereof Download PDFInfo
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- CN1259324C CN1259324C CN 200410025014 CN200410025014A CN1259324C CN 1259324 C CN1259324 C CN 1259324C CN 200410025014 CN200410025014 CN 200410025014 CN 200410025014 A CN200410025014 A CN 200410025014A CN 1259324 C CN1259324 C CN 1259324C
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Abstract
The present invention discloses a positive-ion reaction type organosilicon color fixing agent which is formed by the reaction of hydroxy silicone oil, dimethyl dichlorosilane, amine, siloxane and a quaternary ammonium reagent. The fixing agent disclosed by the present invention a green environmental protection permanent fixing agent without formaldehyde, which improves the color fixation effect of active dye and solves the problems that the active dye is difficult to fix color and the water washing degree is poor. In addition, the fixing agent of the present invention integrates color fixation and softness into a whole, has the sterilization effect, is used for the color fixation of direct dye and acid dye, improves the wet fastness of fabrics, improves friction fastness and light fastness, has little influence to fabric color, and even has the function of color lighting to dark color.
Description
Technical field
The present invention relates to laking agent and preparation method thereof, particularly a kind of positively charged ion, response type laking agent and preparation method thereof.
Background technology
Along with expanding economy, variation with rapid changepl. never-ending changes and improvements is taking place to the demand of clothing, food, lodging and transportion--basic necessities of life in people.At present, people except attractive in appearance, more pay attention to comfortable to the pursuit of dress material.Cotton fibre becomes the main material that people wear the clothes gradually with its comfortable characteristics attractive in appearance, and therefore, the cotton fibre material of high-quality printing and dyeing is subjected to people's favor day by day.
Anionic water-soluble such as substantive dyestuff and matching stain dyestuff chromatogram is complete, coloured light is more bright-coloured, but owing to only depend on Van der Waals force, hydrogen bond to combine with fiber, and have the solubility group on the most dyestuff, make fastness to wet rubbing not good, promptly fade, the staining phenomenon is serious.Only theoretically, reactive dyestuffs and fibroplastic covalent linkage are quite firm, as there not being the dyefastness problem.But in fact, dyestuff unreacted reactant and hydrolyzate can not be washed to the greatest extent from dying thing, and this part dyestuff will fade, in dying, especially serious when dark.In addition, the covalent linkage on the DYED FABRICS also can be because of scission of link takes place in hydrolysis, thereby causes fading.In view of this, in dyeing, use laking agent to carry out fixation treatment at present and become the important means that solves the wet fastness of DYED FABRICS.
The substantive dyestuff, matching stain and the reactive dyestuffs that contain hydrophilic radical (sulfonic acid or carboxylate salt), water-soluble after, dyestuff all can be dissociated into the positively charged ion of sodium and the negatively charged ion of dyestuff.The cationic laking agent that adopts has bigger reactivity to the dyestuff negatively charged ion at present, and the dye molecule on product dyed thereby is increased, and hydrophilic radical is closed in and forms insoluble dyes salt precipitation on the fabric:
Water-soluble dye ammonium salt laking agent insoluble salt
Like this, can prevent that dyestuff from coming off and hydrolysis from fabric because of ionization, thereby improve colour fastness.But this type of laking agent is to the DeGrain of " wet friction " of raising product dyed thereby, promptly when washing, soaping, have acid-basicity or sweat stain is arranged, dye molecule and the strong fracture easily of combining of fiber, and split away off from fiber, enter in the aqueous solution, cause fading and staining, it is poor also can be interpreted as wet colour fastness.
Since World War II, invented and used multiple laking agent, mainly contain four kinds in cats product class laking agent, no surface-active quaternary laking agent, resin type laking agent, response type laking agent etc.Simultaneously, the application conditions and the effect of various laking agent have also been carried out a series of research; Wherein, cats product class laking agent has colour fixation preferably as a rule, but not anti-soaping, and tend to reduce the original light fastness of dyestuff; Do not have surface-active quaternary laking agent and can improve dyefastness, especially fastness to washing is also less to dying the influence of looking for pool, light fastness, but fabric intensity is had certain influence, and soaping fastness is improved little; The resin type laking agent is to be applied to a kind of comparatively widely laking agent of substantive dyestuff, but all there is certain shortcoming, influential and contain formaldehyde to the coloured light of fabric after use such as color fixing agent Y, color fixing agent M need add the decline that mantoquita prevents light fastness when using, but the coloured light to fabric has produced considerable influence, when especially running into iron ion, also have some resin type laking agent to exist to shortcomings such as hot water fastness differences; The response type laking agent be development recently novel laking agent (Wenshui is flat, dyeing and printing auxiliary, 2000, Vol 17, No6,32-33; Zhu Guohua, Guan Yonghua, Nantong Polytechnic College journal, 16 (2), 2000,06,28-32), has colour fixation preferably, this type of laking agent biggest advantage is to improve the wet colour fastness of dyestuff, and less to the color and luster influence, and there is shortcoming in the laking agent that also has certainly, just easily cause the defect that look becomes as laking agent NF1, the development of this laking agent at present still is in the further exploration.
Summary of the invention
One of the object of the invention is, discloses a kind of formaldehydeless positively charged ion that has good colour fixation and do not influence fabric color and light fastness, response type organosilicon color fixing agent, overcomes the deficiency that existing cationic laking agent exists;
Two of the object of the invention is: the preparation method that a kind of above-mentioned cationic laking agent is provided.
The present invention's general introduction:
Positively charged ion disclosed by the invention, response type organosilicon color fixing agent contain organosilicon radical (being siloxanes), and it can react with the hydroxyl on the fiber:
Fiber generates covalent linkage after the organosilicon color fixing agent fiber fixation, thereby make firm being connected on the fiber of dyestuff, can not be subjected to the influence of soda acid, improve wet treatment degree, light fastness and crock fastness greatly, not staining is not faded, and reaches the effect of permanent fixation.
In addition, this laking agent is the quaternary ammonium compound of long-chain, has soft effect preferably, can be antistatic, can improve the tearing brute force of fabric; Simultaneously, it is again the organosilicon quaternary ammonium salt series bactericidal agent, attracts electronegative bacteria cell wall, and the opposite side of long-chain contact bacteria cell wall is subjected to the negative charge that positively charged ion attracts and reduces, cell wall rupture then, and Dissolve things inside oozes out and dead.
Technical scheme:
The said positively charged ion of the present invention, response type organosilicon color fixing agent, its compound for having structure shown in the formula (1):
In the formula: n=0～20, m=1～12; R is :-(CH
2) aSi (R
1)
3-CH
2CH=CH
2-CH
2R
2Ar; C
kH
2k+1Cl or-CH
2R
3N
+(CH
3)
3Cl
-
Wherein: a=1～15; K=8～18; R
1Be C
1～C
8Alkyl or alkoxyl group, preferred C
1～C
4Alkyl or alkoxyl group, the best is CH
3OCH
3C
2H
5Or OC
2H
5R
2Be (CH
2)
bAlkyl chain, b=0～10, preferred b=0; R
3Be (CH
2)
dAlkyl chain, d=7～17.
Prepare the method for the said cationic laking agent of the present invention, it comprises the steps:
The preparation feedback equation is as follows:
The implication of n, m and R is described identical with preamble in the equation.
(1) hydroxy silicon oil [compound (2)] and dimethyldichlorosilane(DMCS) [compound (3)] are added in the reactor with 1: 2 ratio (mol ratio), heating 40 ℃～150 ℃ reacted 10～90 minutes down, make compound (4), wherein optimal reaction temperature is 60 ℃～100 ℃, and optimum reacting time is 20～60 minutes;
(2) with compound (4) and organic amine [NH
2((CH
2)
2NH)
mH] join in the reactor with 1: 4 ratio (mol ratio), in 20～80 ℃, be advisable with 30～60 ℃, react to white smoke and disappear, heat the HCl that will generate then and dissociate and take out, Heating temperature is dissociated with HCl and is as the criterion, reaction times dissociates fully with HCl and is as the criterion, and makes compound (5);
(3) with compound (5) and quaternizing agent (haloalkane, preferred alkyl chloride) be 1: 0.5～1.5 to join in the reactor with mol ratio, preferred mol ratio is 1: 1～1.2, makes target compound (1) in 80 ℃～150 ℃ reactions, and the temperature of reaction of recommendation is 80 ℃～120 ℃.
Innovation part of the present invention is the organosilicon quaternary ammonium salt positively charged ion is used for the fixation of anionic dyestuff, has the characteristics of permanent fixation more again with other laking agent products, simultaneously softness and sterilization is integrated in one; And be easy to get cheapness, synthesis technique of raw material is simple, the reaction conditions gentleness, and simple, yield is higher, is easy to suitability for industrialized production.Product is formaldehydeless environmental protection laking agent, anionic dyestuff (substantive dyestuff, matching stain and reactive dyestuffs) is all had good colour fixation, improve its wet colour fastness, friction fastness, light fastness, perspiration fastness and acid-fast alkali-proof and do not influence the color and luster of fabric.
The using method of the said laking agent of the present invention is compared with the using method of existing laking agent: except that the laking agent consumption is different (few 30～50 (weight) % of the existing laking agent of the amount ratio of the said laking agent of the present invention can reach the colour fixation of existing laking agent), all the other are all identical.
Embodiment:
The present invention is further illustrated below by embodiment, and purpose is better to understand content of the present invention.Therefore, the cited case does not limit protection scope of the present invention:
Embodiment 1
Synthetic laking agent structure is:
R is-CH in the formula
2CH
2CH
2Si (OCH
3)
3
1, chloride silicone oil is synthetic:
The hydroxy silicon oil (n=4) that in there-necked flask, adds 0.10mol, the dimethyldichlorosilane(DMCS) that in dropping funnel, adds 0.20mol, stir down at 40 ℃, dimethyldichlorosilane(DMCS) slowly progressively increases, can be observed that liquid can emit bubble in the there-necked flask this moment, produce with a large amount of HCl white gas in the reaction, take out the body that degass, make colourless or light yellow liquid.
2, the reaction of chlorine silicone oil and amine:
The triethylene tetramine (m=2) that in there-necked flask, adds 0.04mol, at room temperature stir, drip the chloride silicone oil (n=4) of 0.01mol with dropping funnel, produce white fog in the bottle this moment, and with a large amount of white salt generations, after for some time, white fog dies down, and this is because the excessive amine and the cause of HCl effect, heating then, the salt elder generation fusion of white, i.e. back HCl disassociation, decompression is bled and is no longer included in bottle till the white smoke, leaves standstill the back system layering, the transparent weak yellow liquid on upper strata is the organosilicon aminated compounds, airtight preservation.
3, laking agent is synthetic:
In there-necked flask, add 100ml methyl alcohol and 0.01mol organosilicon aminated compounds, stir under the room temperature, slowly drip 0.18mol siloxanes (a=3) with dropping funnel, 80 ℃ of reacting by heating after finishing, afterreaction was complete in 5 hours, and the product that obtains is a laking agent.
IR(KBr)：ν-Si-O-＝1064.5cm
-1(S)，ν-Si-C-＝829.8cm
-1(S)。
Embodiment 2
Synthetic laking agent structure is:
In the formula: R is-CH
2CH
2CH
2CH
2CH
2Si (CH
3)
3
1, chloride silicone oil is synthetic:
The hydroxy silicon oil (n=6) that in there-necked flask, adds 0.10mol, the dimethyldichlorosilane(DMCS) that in dropping funnel, adds 0.20mol, stir down at 150 ℃, dimethyldichlorosilane(DMCS) slowly progressively increases, can be observed that liquid can emit bubble in the there-necked flask this moment, produce with a large amount of HCl white gas in the reaction, take out the body that degass, make colourless or light yellow liquid.
2, chlorine silicone oil is with the reaction of amine
The triethylene tetramine (m=3) that in there-necked flask, adds 0.04mol, at room temperature stir, drip the chloride silicone oil of 0.01mol with dropping funnel, produce white fog in the bottle this moment, and with a large amount of white salt generations, after for some time, white fog dies down, and this is because the excessive amine and the cause of HCl effect, heating then, the salt elder generation fusion of white, i.e. back HCl disassociation, decompression is bled and is no longer included in bottle till the white smoke, leaves standstill the back system layering, the transparent light yellow liquid on upper strata is the organosilicon aminated compounds, airtight preservation.
3, laking agent is synthetic
Add 100ml ethanol and 0.01mol organosilicon aminated compounds in there-necked flask, stir under the room temperature, slowly drip 0.14mol silane (a=5) with dropping funnel, in 150 ℃ of reacting by heating, afterreaction was complete in 5 hours after finishing, and the product that obtains is a laking agent.
IR(KBr)：ν-Si-O-＝1058.5cm
-1(S)，ν-Si-C-＝825.8cm
-1(S)，ν-Si(CH
3)
3-＝840.5cm
-1、756.0cm
-1(S)。
Embodiment 3
Synthetic laking agent structure is:
In the formula: R is-CH
2CH
2CH
2Si (OC
2H
5)
3
1, chloride silicone oil is synthetic:
In there-necked flask, add 30ml ethanol, 0.10mol hydroxy silicon oil (n=8), the dimethyldichlorosilane(DMCS) that in dropping funnel, adds 0.20mol, stir down at 80 ℃, dimethyldichlorosilane(DMCS) slowly progressively increases, produce with a large amount of HCl white gas in the reaction, take out the body that degass, make colourless or light yellow thick liquid.
2, chlorine silicone oil is with the reaction of amine
In there-necked flask, add 50ml ethanol, at room temperature stir, feed ammonia (m=0), drip the chloride silicone oil of 0.01mol simultaneously with dropping funnel, produce white fog in the bottle this moment, and with a small amount of white salt generation, after for some time, white fog dies down, this is because the excessive amine and the cause of HCl effect, heating then, the salt elder generation fusion of white, i.e. back HCl disassociation, decompression is bled and is no longer included till the white smoke in bottle, leave standstill the back system layering, the transparent yellow liquid on upper strata is the organosilicon aminated compounds, airtight preservation.
3, laking agent is synthetic:
In there-necked flask, add 100ml Virahol and 0.01mol organosilicon aminated compounds, stir under the room temperature, slowly drip 0.06mol siloxanes (a=3) with dropping funnel, 100 ℃ of reacting by heating after finishing, afterreaction was complete in 5 hours, and the product that obtains is a laking agent.
IR(KBr)：ν-Si-O＝1070.0cm
-1(S)，ν-Si-C-＝836.5cm
-1(S)。
Embodiment 4
R:-CH in the formula
2CH=CH
2
1, chloride silicone oil is synthetic:
The hydroxy silicon oil (n=4) that in there-necked flask, adds 0.10mol, the dimethyldichlorosilane(DMCS) that in dropping funnel, adds 0.20mol, stir down at 40 ℃, dimethyldichlorosilane(DMCS) slowly progressively increases, can be observed that liquid can emit bubble in the there-necked flask this moment, produce with a large amount of HCl white gas in the reaction, take out the body that degass, make colourless or light yellow liquid.
2, the reaction of chlorine silicone oil and amine:
The triethylene tetramine (m=2) that in there-necked flask, adds 0.04mol, at room temperature stir, drip the chloride silicone oil (n=4) of 0.01mol with dropping funnel, produce white fog in the bottle this moment, and with a large amount of white salt generations, after for some time, white fog dies down, and this is because the excessive amine and the cause of HCl effect, heating then, the salt elder generation fusion of white, i.e. back HCl disassociation, decompression is bled and is no longer included in bottle till the white smoke, leaves standstill the back system layering, the transparent weak yellow liquid on upper strata is the organosilicon aminated compounds, airtight preservation.
3, laking agent is synthetic:
In there-necked flask, add 100ml methyl alcohol and 0.01mol organosilicon aminated compounds, stir under the room temperature, slowly drip the 0.18mol chlorallylene with dropping funnel, 80 ℃ of reacting by heating after finishing, afterreaction was complete in 5 hours, and the product that obtains is a laking agent.
IR(KBr)：ν-Si-O-＝1060.5cm
-1(S)，ν-Si-C-＝832.8cm
-1(S)。
Embodiment 5
Synthetic laking agent structure is:
In the formula: R-CH
2Ar
1, chloride silicone oil is synthetic:
The hydroxy silicon oil (n=6) that in there-necked flask, adds 0.10mol, the dimethyldichlorosilane(DMCS) that in dropping funnel, adds 0.20mol, stir down at 150 ℃, dimethyldichlorosilane(DMCS) slowly progressively increases, can be observed that liquid can emit bubble in the there-necked flask this moment, produce with a large amount of HCl white gas in the reaction, take out the body that degass, make colourless or light yellow liquid.
3, chlorine silicone oil is with the reaction of amine
The triethylene tetramine (m=3) that in there-necked flask, adds 0.04mol, at room temperature stir, drip the chloride silicone oil of 0.01mol with dropping funnel, produce white fog in the bottle this moment, and with a large amount of white salt generations, after for some time, white fog dies down, and this is because the excessive amine and the cause of HCl effect, heating then, the salt elder generation fusion of white, i.e. back HCl disassociation, decompression is bled and is no longer included in bottle till the white smoke, leaves standstill the back system layering, the transparent light yellow liquid on upper strata is the organosilicon aminated compounds, airtight preservation.
3, laking agent is synthetic
Add 100ml ethanol and 0.01mol organosilicon aminated compounds in there-necked flask, stir under the room temperature, slowly drip the 0.14mol Benzyl Chloride with dropping funnel, in 120 ℃ of reacting by heating, afterreaction was complete in 5 hours after finishing, and the product that obtains is a laking agent.
IR(KBr)：ν-Si-O-＝1068.5cm
-1(S)，ν-Si-C-＝835.8cm
-1(S)。
Embodiment 6
Synthetic laking agent structure is:
In the formula: R is-C
12H
25N
+(CH
3)
3Cl
-
1, chloride silicone oil is synthetic:
In there-necked flask, add 30ml ethanol, 0.10mol hydroxy silicon oil (n=8), the dimethyldichlorosilane(DMCS) that in dropping funnel, adds 0.20mol, stir down at 80 ℃, dimethyldichlorosilane(DMCS) slowly progressively increases, produce with a large amount of HCl white gas in the reaction, take out the body that degass, make colourless or light yellow thick liquid.
4, chlorine silicone oil is with the reaction of amine
In there-necked flask, add 50ml ethanol, at room temperature stir, feed ammonia (m=0), drip the chloride silicone oil of 0.01mol simultaneously with dropping funnel, produce white fog in the bottle this moment, and with a small amount of white salt generation, after for some time, white fog dies down, this is because the excessive amine and the cause of HCl effect, heating then, the salt elder generation fusion of white, i.e. back HCl disassociation, decompression is bled and is no longer included till the white smoke in bottle, leave standstill the back system layering, the transparent yellow liquid on upper strata is the organosilicon aminated compounds, airtight preservation.
5, laking agent is synthetic:
In there-necked flask, add 100ml Virahol and 0.01mol organosilicon aminated compounds, stir under the room temperature, 0.06mol end group chlorinated dodecane based quaternary ammonium salt is dissolved with the 20ml Virahol, slowly drip with dropping funnel, 130 ℃ of reacting by heating after finishing, afterreaction was complete in 5 hours, and the product that obtains is a laking agent.
IR(KBr)：ν-Si-O-＝1066.0cm
-1(S)，ν-Si-C-＝830.5cm
-1(S)。
Embodiment 7
Said laking agent of the present invention and existing laking agent are used the contrast experiment:
Color fixing condition: temperature: 30～80 ℃; Bath raio: 1: 15～50; The fixation time: 15～60 minutes, its experiment the results are shown in following table:
| Laking agent | Outward appearance | Non-volatile matter is water-soluble | Stability | The fixation experiment | |||||
| Soaping fastness | Crock fastness | Perspiration fastness | |||||||
| Fade (level) | Wet rub (level) | Staining (level) | Fade (level) | Staining (level) | Unlubricated friction (level) | ||||
| The product of example 1 | Weak yellow liquid | Well | Better | 4-5 | 3-5 | 3-5 | 3-5 | 3-5 | 4-5 |
| The product of example 2 | Light yellow liquid | Well | Better | 4-5 | 3-4 | 3-5 | 3-4 | 3-5 | 4-5 |
| The product of example 3 | Yellow liquid | Well | Better | 4-5 | 3-5 | 4 | 3-5 | 2-3 | 3-4 |
| The product of example 4 | Light yellow liquid | Well | Better | 4-5 | 3-5 | 4 | 4 | 3-5 | 3-5 |
| The product of example 5 | Yellow liquid | Well | Better | 4-5 | 4-5 | 4-5 | 3-5 | 3-4 | 4 |
| The product of example 6 | Yellow liquid | Well | Better | 4-5 | 3-5 | 3-5 | 4 | 3 | 3-5 |
| 1631 | The white dope | Better | Well | 1-3 | 1-3 | 3 | 2 | 1-3 | 1-3 |
| Color fixing agent Y (polymkeric substance of Dyhard RU 100 and formaldehyde) | Colourless transparent liquid | Well | Well | 2-3 | 2-4 | 2 | 2-3 | 2-3 | 2-3 |
| Organosilicon quaternary ammonium salt | White liquid | Relatively poor | Better | 2-3 | 2-4 | 2-3 | 2-3 | 2 | 3-4 |
| Laking agent ED-Z (resin reaction type laking agent) | Brown liquid | Relatively poor | Well | 2-3 | 3 | 2-3 | 2-3 | 3-4 | 2-3 |
| Laking agent GS501 (polymkeric substance that contains quaternary ammonium salt) | Brown liquid | Better | Well | 2-4 | 2-4 | 3-4 | 3 | 2-3 | 2-3 |
Claims (10)
1, a kind of positively charged ion, response type organosilicon color fixing agent, its compound for having structure shown in the formula (1):
In the formula: n=0～20, m=1～12; R is :-(CH
2) aSi (R
1)
3-CH
2CH=CH
2-CH
2R
2Ar; C
kH
2k+1Cl or-CH
2R
3N
+(CH
3)
3Cl
-
Wherein: a=1～15; K=8～18, R
1Be C
1～C
8Alkyl or alkoxyl group, R
2Be (CH
2)
bAlkyl chain, b=0～10, R
3Be (CH
2)
dAlkyl chain, d=7～17.
2, as the said laking agent of claim 1, it is characterized in that, wherein R
1Be C
1～C
4Alkyl or alkoxyl group.
3, as the said laking agent of claim 2, it is characterized in that, wherein R
1Be CH
3OCH
3C
2H
5Or OC
2H
5
As the said laking agent of claim 1, it is characterized in that 4, wherein R is-CH
2Ar.
As the preparation method of said any one laking agent of claim 1～4, it is characterized in that 5, said preparation method comprises the steps:
(1) compound (2) and compound (3) are added in the reactor with 1: 2 ratio of mol ratio, reacted 10～90 minutes down, make compound (4) in 40 ℃～150 ℃;
(2) with compound (4) and organic amine [NH
2((CH
2)
2NH)
mH] join in the reactor with 1: 4 ratio of mol ratio, in 20～80 ℃, react to white smoke and disappear, heat the HCl that will generate then and dissociate and take out, Heating temperature is dissociated with HCl and is as the criterion, and the reaction times dissociates fully with HCl and is as the criterion, and makes compound (5);
(3) be 1: 0.5～1.5 to join in the reactor compound (5) and quaternizing agent with mol ratio, make target compound (1) in 80 ℃～150 ℃ reactions;
The preparation feedback equation is as follows:
The implication of n, m and R identical with described in the claim 1 in the preparation feedback equation.
As the said preparation method of claim 5, it is characterized in that 6, wherein the temperature of reaction in the step (1) is 60 ℃～100 ℃, the reaction times is 20～60 minutes.
7, as the said preparation method of claim 5, it is characterized in that, wherein compound (4) and organic amine [NH
2((CH
2)
2NH)
mH] reaction temperature be 30～60 ℃.
As the said preparation method of claim 5, it is characterized in that 8, wherein compound (5) is 1: 1～1.2 with the mol ratio of quaternizing agent, and its temperature of reaction is 80 ℃～120 ℃.
9, as the said preparation method of claim 6, it is characterized in that, wherein compound (4) and organic amine [NH
2((CH
2)
2NH)
mH] reaction temperature be 30～60 ℃.
As the said preparation method of claim 9, it is characterized in that 10, wherein compound (5) is 1: 1～1.2 with the mol ratio of quaternizing agent, and its temperature of reaction is 80 ℃～120 ℃.
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|---|---|---|---|
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| CN101302268B (en) * | 2008-07-03 | 2010-12-08 | 华东理工大学 | Non-formaldehyde organosilicon color fixing agent |
| CN104744641B (en) * | 2015-03-09 | 2018-04-17 | 浙江工业职业技术学院 | A kind of cation formaldehyde-free color fixing agent lotion |
| CN104744642B (en) * | 2015-03-09 | 2018-04-03 | 浙江工业职业技术学院 | The preparation method of nano-titanium dioxide modified color-fixing agent emulsion |
| CN104927064B (en) * | 2015-05-28 | 2017-06-23 | 齐鲁工业大学 | A kind of preparation method of the high molecular dye based on hyperbranched polyurethane |
| CN105622944B (en) * | 2016-03-30 | 2018-08-07 | 科凯精细化工（上海）有限公司 | A kind of quaternized organic silicone oil and preparation method thereof |
| CN105622945B (en) * | 2016-03-30 | 2018-09-14 | 科凯精细化工（上海）有限公司 | Deep finishing agent of a kind of increasing and preparation method thereof |
| CN108660813A (en) * | 2018-07-07 | 2018-10-16 | 曾文华 | A kind of formaldehyde-free color fixing agent and preparation method thereof |
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