CN1195004A - Modified inorganic pigment composition for dyeing and its use - Google Patents
Modified inorganic pigment composition for dyeing and its use Download PDFInfo
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- CN1195004A CN1195004A CN 97107422 CN97107422A CN1195004A CN 1195004 A CN1195004 A CN 1195004A CN 97107422 CN97107422 CN 97107422 CN 97107422 A CN97107422 A CN 97107422A CN 1195004 A CN1195004 A CN 1195004A
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Abstract
A modified inorganic pigment composition used for dyeing leather, natural fibre and its fabrics, and chemical fibre and its fabrics contains modified inorganic pigment particles (less than 1 micron) (5-35 Wt.%), surfactant (0.05-5 Wt.%) and solvent (rest). On the surface of modified inorganic pigment particle, there are active radicals such as carboxyl and/or sulfo, or amino and/or amido. Said pigment composition does not have cancerogenic danger.
Description
The present invention relates to can be used for painted modified inorganic color compositions and uses thereof, more particularly, the present invention relates to replace the composition of the modified inorganic pigment aromatics organic dye dyeing, that have active group, and this composition is used for the purposes of leather, natural fiber and fabric thereof, man-made fiber and textile dyeing thereof.
Leather, natural fiber and fabric thereof, man-made fiber and coloration of textile materials thereof, usually use the aromatics organic dye, such dyestuff is complicated process of preparation not only, there is serious environmental to pollute in production and the use, and there is a carcinogenic danger, therefore increasing aromatics organic dye is under an embargo and produces and use, Yang Xin's latitude has been reported the regulation that bans use of 20 kinds of aromatic amines that German Government was issued in 1994 in " Chinese leather information newspaper " February 18 nineteen ninety-five, wherein relates to aromatics organic dye kind more than 100 commonly used.
Mineral dye, as carbon black, titanium white, iron oxide red, iron orchid, chrome green etc., be widely used in coating, painted, but owing to do not have the mortise ability, must or be embedded in the pollutant by tackiness agent and fix, Sun Yan etc. are at " printing and dyeing " Vol19 (3) P19, report the multiple tackiness agent that uses in the pigment dyeing in 1993, and be referred to as the key assistant of pigment dyeing.In leather industry, pigment is mainly used in the surface daub on a wall of leather.In finishing agent, pigment is only as the colouration material, and with protein or fluoropolymer resin as tackiness agent, see " leather handbook P199,1979 years Beijing, Light Industry Press.
About modified inorganic pigment, report is all arranged both at home and abroad, Chinese patent CN1121944A has introduced a kind of preparation method of oxide compound mononitride base tinting pigment, it is characterized in that adjusting form and aspect, increases the brightness of color.The NorioTsubokawa of Japan etc. are at Polymer Journal Vol.24, No 8, P809-816, and 1992 have reported the method for superfine powders such as silicon, titanium oxide, iron powder being carried out surface graft modification, its objective is and improve the dispersiveness of these materials in solvent, overcome flocculation.The weak point of above modified pigment is that above-mentioned modified pigment does not still have the ability with pollutant body mortise, thereby can not be directly used in dyeing.
The objective of the invention is provides a kind of painted modified inorganic color compositions that can be used at the deficiencies in the prior art.Another object of the present invention provides the purposes of this color compositions.
As everyone knows, there is great amount of hydroxy group in the surface of inorganic pigment microparticles, Shen Zhong: solid surface modification and application thereof " chemical industry progress " 1993, the 2-4 phase, principle of the present invention be by with the reaction of these hydroxyls, introduce carboxyl on the pigment particle surface, sulfonic group, amino, amide group isoreactivity group, the introducing of these active groups, can make mortise between modified inorganic pigment and the pollutant and realize dyeing.
Provided by the inventionly can be used for painted modified inorganic color compositions, said composition contains inorganic pigment microparticles, tensio-active agent and solvent, the particle diameter that it is characterized in that the modified inorganic pigment particle is less than 1 micron, preferably less than 0.1 micron, most preferably be 0.02～0.05 micron, inorganic pigment microparticles surface through modification has carboxyl and/or sulfonic group, the perhaps such active group of amino and/or amide group, gross weight based on said composition, the weight percent of each component is: the modified inorganic pigment particle is 5～35, and tensio-active agent is 0.05～5, the solvent surplus.
The inventor finds, when the particle diameter of modified inorganic pigment particle during greater than 1 micron, can influence its dyeing course perviousness and in conjunction with fastness and make its shelf stability reduction, when pigment in the composition weigh less than 5% the time, it still has Color, but, be rational inadequately from economy; Otherwise when its weight greater than 35% the time, then can increase the difficulty of preparation process; When dosage of surfactant is lower than 0.05%, can influences the dispersiveness of pigment particle and use stability; When being higher than 5%, can influence painted fastness.
Being used for the pigment of modification in the composition of the present invention is mineral dye, wherein preferred carbon black, ferric oxide, titanium oxide, zinc oxide, chromic oxide, at least a in the molybdenum oxide.
Tensio-active agent in the present composition is a negatively charged ion commonly known in the art, at least a in positively charged ion or the nonionic surface active agent.With having the cloudy tensio-active agent that is used from the active group modified pigment is negatively charged ion and/or non-ionic type, with having the tensio-active agent that the group modified pigment of cation activity is used is positively charged ion and/or non-ionic type, and these all are the known knowledge of these those skilled in the art.
The solvent of the present composition be water and/or can with other solvents of water arbitrary proportion blended, for example alcohol, ketone etc. are for the consideration of economy and environment aspect, the most preferred with water.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The preparation method who can be used for painted modified inorganic color compositions:
1. the activation of mineral dye
1.1 haloalkylene oxide activated inorganic pigment
With 100 parts of mineral dyes, 100～300 parts of haloalkylene oxide, 0.5～5 part in water-soluble metal oxyhydroxide, add and have agitator, in the reactor of thermometer and reflux exchanger, in 100～180 ℃ of reactions of temperature 60～300 minutes, liquid is removed in distillation, obtains oxirane activated inorganic pigment.
1.2 aldehyde activated inorganic pigment
With 100 parts of mineral dyes, 2～20 parts of aldehyde compounds, 100～300 parts of deionized waters add and have agitator, in the reactor of thermometer and condenser, in 25～60 ℃ of reactions of temperature 20～120 minutes, remove by filter liquid, obtain aldehyde activated inorganic pigment.
2. the introducing of active group and preparation of compositions
2.1 carboxy-modified mineral dye
With live 100 parts of mineral dyes of oxirane activated inorganic pigment or aldehyde, lactic acid, citric acid, alcohol acid or amino acid/11～5 part, 200～300 parts of deionized waters, add and have agitator, in the reactor of thermometer and condenser, regulate pH value to 6～9 with sodium hydroxide, in 95～120 ℃ of reactions of temperature 60～300 minutes, obtain carboxy-modified mineral dye.
2.2 band carboxyl polymer modified inorganic pigment
With 100 parts of oxirane activated inorganic pigment or aldehyde activated inorganic pigment, 2～6 parts of vinylformic acid or acrylate, 1～3 part of vinyl monomer, 0.5～3 part of persulphate, 2～5 parts of anionic surfactants, 200～300 parts of deionized waters, add and have agitator, in the reactor of thermometer and condenser, regulate pH value to 6～9 with sodium hydroxide, in 70～90 ℃ of reactions of temperature 200～480 minutes, obtain band carboxyl polymer modified inorganic pigment.
2.3 sulfonic group modified mineral dye
With 100 parts of oxirane activated inorganic pigment or aldehyde activated inorganic pigment, 1～5 part of water soluble hydroxy sulfonate or cysteic acid salt, 200～300 parts of deionized waters, add and have agitator, in the reactor of thermometer and condenser, regulate pH value to 6～9 with sodium hydroxide,, obtain sulfonic group modified mineral dye in 70～95 ℃ of reactions of temperature 60～300 minutes.
2.4 band sulfonic group polymkeric substance thing modified inorganic pigment
With 100 parts of oxirane activated inorganic pigment or aldehyde activated inorganic pigment, 1～5 part in propene sulfonic acid salt or methacrylic sulfonate, 0.3～3 part of persulphate, anionic surfactant 2-5 part, 200～300 parts of deionized waters add and have agitator, in the reactor of thermometer and condenser, regulate pH value to 6～9 with sodium hydroxide,, obtain band sulfonic group polymer modification mineral dye in 70～90 ℃ of reactions of temperature 120～480 minutes.
2.5 amino modified mineral dye
With 100 parts of oxirane activated inorganic pigment or aldehyde activated inorganic pigment, 1～5 part of 1～6 carbocyclic aliphatic family diamines, 0.5～3 part of cats product, 200～300 parts of deionized waters add and have agitator, in the reactor of thermometer and condenser, in 70～90 ℃ of reactions of temperature 120～480 minutes, be cooled to 30～40 ℃ then,, obtain amino modified mineral dye with salt acid for adjusting pH value 6.5～7.5.
2.6 band amido polymer modified inorganic pigment
With 100 parts of oxirane activated inorganic pigment or aldehyde activated inorganic pigment, 1～5 part of acrylamide, 0.5～3 part of persulphate, 2～5 parts of cats products, 200～300 parts of deionized waters add and have agitator, in the reactor of thermometer and condenser, in 70～90 ℃ of reactions of temperature 120～480 minutes, obtain band amido polymer modified inorganic pigment.
The purposes that can be used for painted modified inorganic color compositions of above-mentioned either party's method preparation is to be used for leather, natural fiber and fabric thereof, man-made fiber and coloration of textile materials thereof.
Color compositions of the present invention can with known additive such as levelling agent in this field, diffusant, laking agent, antioxidant, sanitas spices etc. are common to be used, and its precondition is that these additives are realized purpose of the present invention and obtaining of excellent results of the present invention do not have a negative impact.
Color compositions of the present invention can carry out suitable dilution as required when dyeing, these all belong to the known technology in a field.
According to the above description of this invention as can be seen, the active group of introducing can be micromolecular form, and for example method 2.1,2.3,2.5, also can be the polymer chain that has these active groups, and for example method 2.2,2.4,2.6.
The present invention has the following advantages.
1. do not contain the aromatics organic dye fully, avoided the carcinogenic danger of aromatics organic dye and other harm of human health.
2. product yield height 〉=95%, production process is polluted little, helps the protection of environment and human health.
3. the product photostabilization is good, and color matching is convenient, and dyestuff specific absorption height is better than the aromatics organic dye during dyeing.
4. raw material sources are abundant, and cheap, production process is simple, and economic benefit is better than the aromatics organic dye.
5. applied range not only is suitable for leather, natural fiber and fabric thereof, and man-made fiber and coloration of textile materials thereof also can be used for the painted of coating and plastics.
6. modified inorganic color compositions of the present invention is more as shown in table 1 with the salient features that mineral dye and aromatics organic dye are used for leather coloring.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
1. the modified inorganic color compositions prepares embodiment
1.1 the activation of mineral dye is as shown in table 2
1.2 the introducing and the preparation of compositions of mineral dye active group are as shown in table 3
2 modified inorganic color compositions are used for painted embodiment
2.1 with 100 parts of chrome tanning pigskin garment grain leathers, add 200 parts of entry, 1 part of 1 part of sodium-acetate and sodium bicarbonate 35 ℃ of reactions of temperature 30 minutes, are removed reaction solution in dyeing caldron, washing pig leather for making garment 20 minutes is standby.
2.2 with 10 parts of the modified inorganic pigment of either party's method preparation of the introducing of 1.2 mineral dye active groups among the embodiment and preparation of compositions, 300 parts in water and the pig leather for making garment of handling through 2.1 methods add in the dyeing caldron in the lump, 50 ℃ of reactions of temperature 30 minutes, add 0.3 part in formic acid again, rotated 10 minutes, washing then, dyeing are promptly accused and are finished.
Table 1 is used for the salient features comparison of leather coloring for modified inorganic color compositions and mineral dye and fragrant ammonia dyestuff
* sample A. is a black pigment cream, and B. is the carboxyl polymer modified carbon black, and C. is the activation of fragrant azo material erie black (ATT) table 2 for mineral dye
| Sample * | ????A | ?????B | ????C | Analytical procedure |
| Tinting strength | ???0.5 | ?????2 | ???1.5 | Black dyes tinting strength check " leather analytical study " P134, the Light Industry Press |
| Remaining quantity (%) dyes in the waste liquid | ???＞10 | ???＜0.001 | ??＞0.5 | The colorimetric analysis of dyeing waste liquid |
| Light fastness | ～6 grades | ＞6 grades | ～4 grades | Fastness that coloured leather is fast light test, " leather analytical study " P695 |
| Fastness to rubbing | 1.5 level | 3 grades | 4 grades | Fastness to rubbing test " leather analytical study " P705 |
| Numbering | There is not basic pigment | Activator | Temperature of reaction | Reaction times | Regulate pH value | ||
| Title | Consumption | Title | Consumption | ||||
| 1. haloalkylene oxide activated inorganic pigment | Carbon black, titanium oxide, ferric oxide, chromic oxide, zinc oxide, any one of molybdenum oxide | 100 parts | Epoxy chloropropane or epoxy bromopropane, preferred epoxy chloropropane, sodium hydroxide | 250 parts 2 parts | ??150℃ | 300 minutes | |
| 2. aldehyde activates nothingization pigment | Carbon black, titanium oxide, ferric oxide, chromic oxide, zinc oxide, any one of molybdenum oxide | 100 parts | Formaldehyde, acetaldehyde or glutaraldehyde, preferred formaldehyde, deionized water sodium hydroxide | 50 parts 200 parts 0.5 part | ??40℃ | 120 minutes | |
Table 3 is the introducing and the preparation of compositions of mineral dye active group
| Numbering | There is not basic pigment | Activator | Temperature of reaction | Reaction times | Regulate pH value | ||
| Title | Consumption | Title | Consumption | ||||
| 1. carboxyl is introduced modification | Epoxy chloropropane activated inorganic pigment or aldehyde activated inorganic pigment | 100 parts | Lactic acid, citric acid, alcohol acid, a-amino acid, any deionized water of vinylformic acid | 5 parts 200 parts | 100℃ | 300 minutes | ??6～9 |
| 2. be with the carboxyl polymer modification | Epoxy chloropropane activated inorganic pigment or aldehyde activated inorganic pigment | 100 parts | Vinylformic acid or methyl acrylate Potassium Persulphate sodium lauryl sulphate deionized water | 6 parts 3 parts 4 parts 200 parts | 80℃ | 360 minutes | ??6～9 |
| 3. sulfonic group modified | Epoxy chloropropane activated inorganic pigment or aldehyde activated inorganic pigment | 100 parts | Hydroxyl sulfoacid or cysteic acid salt deionized water | 5 parts 250 parts | 120℃ | 120 minutes | ??6～9 |
| 4. be with the sulfosalicylic polymer modification | Epoxy chloropropane activated inorganic pigment or aldehyde activated inorganic pigment | 100 parts | Sodium allylsulfonate or methylpropene sodium sulfonate Potassium Persulphate sulfonated castor oil deionized water | 5 parts 3 parts 5 parts 300 parts | 90℃ | 450 minutes | ??6～9 |
| 5. amino introducing modification | Epoxy chloropropane activated inorganic pigment or aldehyde activated inorganic pigment | 100 parts | 1～6 carbocyclic aliphatic family diamines, preferred ethylenediaminetetraacetic acid cats product | 5 parts 0.5 part 3 parts | 90℃ | 450 minutes | ??6.5～7.5 |
| 6. be with the amido polymer modification | Epoxy chloropropane activated inorganic pigment or aldehyde activated inorganic pigment | 100 parts | Acrylamide Potassium Persulphate cats product | 5 parts 3 parts 4 parts | 90℃ | 480 minutes | |
Claims (10)
1. can be used for painted modified inorganic color compositions, said composition contains inorganic pigment microparticles, tensio-active agent and solvent, the particle diameter that it is characterized in that this modified inorganic pigment particle is less than 1 micron, inorganic pigment microparticles surface through modification has a) carboxyl and/or sulfonic group or b) amino and/or the such active group of amide group, based on the gross weight of said composition, the weight percent of each component is:
Modified inorganic pigment particle 5～35
Tensio-active agent 0.05～5
The solvent surplus
2. can be used for painted modified inorganic color compositions according to claim 1 is described, the particle diameter that it is characterized in that the modified inorganic pigment particle is less than 0.1 micron.
3. can be used for painted modified inorganic color compositions according to claim 1 is described, the particle diameter that it is characterized in that the modified inorganic pigment particle is 0.02～0.05 micron.
4. describedly can be used for painted modified inorganic color compositions according to claim 1 or 2, the active group that it is characterized in that modified inorganic pigment particle surface is with chemical bond form and inorganic pigment microparticles bonded.
5. can be used for painted modified inorganic color compositions according to claim 3 is described, the active group that it is characterized in that modified inorganic pigment particle surface is with chemical bond form and inorganic pigment microparticles bonded.
6. describedly can be used for painted modified inorganic color compositions according to claim 1 or 2, it is characterized in that mineral dye is selected from least a of carbon black, titanium oxide, ferric oxide, chromic oxide, zinc oxide, molybdenum oxide.
7. can be used for painted modified inorganic color compositions according to claim 3 is described, it is characterized in that mineral dye is selected from least a of carbon black, titanium oxide, ferric oxide, chromic oxide, zinc oxide, molybdenum oxide.
8. describedly can be used for painted modified inorganic color compositions according to claim 1 or 2, it is characterized in that solvent be water and/or can with water with arbitrary proportion blended solvent alcohol and/or ketone.
9. can be used for painted modified inorganic color compositions according to claim 3 is described, it is characterized in that solvent be water and/or can with water with arbitrary proportion blended solvent alcohol and/or ketone.
10. according to the described purposes that can be used for painted modified inorganic color compositions of claim 1～9, it is characterized in that composition is used for leather, natural fiber and fabric thereof, man-made fiber and coloration of textile materials thereof.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107422A CN1058037C (en) | 1997-04-03 | 1997-04-03 | Modified inorganic pigment composition for dyeing and its use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107422A CN1058037C (en) | 1997-04-03 | 1997-04-03 | Modified inorganic pigment composition for dyeing and its use |
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| Publication Number | Publication Date |
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| CN1195004A true CN1195004A (en) | 1998-10-07 |
| CN1058037C CN1058037C (en) | 2000-11-01 |
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| CN97107422A Expired - Fee Related CN1058037C (en) | 1997-04-03 | 1997-04-03 | Modified inorganic pigment composition for dyeing and its use |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942770A (en) * | 2010-08-19 | 2011-01-12 | 苏州世名科技股份有限公司 | Ecotypic liquid pigment for synthetic leather and preparation method thereof |
| CN105862470A (en) * | 2016-05-27 | 2016-08-17 | 无锡润新染料有限公司 | Inorganic compound dye and preparation method thereof |
| CN107700207A (en) * | 2017-08-22 | 2018-02-16 | 安徽省霍山县金园竹艺有限公司 | A kind of colouring method of ultraviolet resistant textiles |
| CN108165054A (en) * | 2017-12-27 | 2018-06-15 | 南京工业大学 | Preparation method of cationic carbon black |
| CN109897399A (en) * | 2019-03-04 | 2019-06-18 | 吉林大学 | A kind of modified iron oxide red and the preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3897586A (en) * | 1970-08-05 | 1975-07-29 | Du Pont | Polymer coated pigment particles and a process for their preparation |
-
1997
- 1997-04-03 CN CN97107422A patent/CN1058037C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942770A (en) * | 2010-08-19 | 2011-01-12 | 苏州世名科技股份有限公司 | Ecotypic liquid pigment for synthetic leather and preparation method thereof |
| CN105862470A (en) * | 2016-05-27 | 2016-08-17 | 无锡润新染料有限公司 | Inorganic compound dye and preparation method thereof |
| CN107700207A (en) * | 2017-08-22 | 2018-02-16 | 安徽省霍山县金园竹艺有限公司 | A kind of colouring method of ultraviolet resistant textiles |
| CN108165054A (en) * | 2017-12-27 | 2018-06-15 | 南京工业大学 | Preparation method of cationic carbon black |
| CN108165054B (en) * | 2017-12-27 | 2020-07-07 | 南京工业大学 | Preparation method of cationic carbon black |
| CN109897399A (en) * | 2019-03-04 | 2019-06-18 | 吉林大学 | A kind of modified iron oxide red and the preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1058037C (en) | 2000-11-01 |
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