CN103785823A - Metal nano particle and method for surface treating the same - Google Patents
Metal nano particle and method for surface treating the same Download PDFInfo
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- CN103785823A CN103785823A CN201310455118.9A CN201310455118A CN103785823A CN 103785823 A CN103785823 A CN 103785823A CN 201310455118 A CN201310455118 A CN 201310455118A CN 103785823 A CN103785823 A CN 103785823A
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- China
- Prior art keywords
- metal nanoparticle
- described metal
- chlorion
- lip
- alkanolamine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
Abstract
The application discloses a method for surface treating a metal nano particle and a metal nano particle generated through the same. Disclosed herein is a method for surface treating metal nano particles, including: surface treating metal nano particles with an alkanol amine containing solution.
Description
Quoting of related application
The application requires the rights and interests of the korean patent application sequence number 10-2012-0120361 that the autograph submitted on October 29th, 2012 is " metal nanoparticle and for its method of surface treatment ", by incorporated herein by reference its full content.
Technical field
The present invention relates to metal nanoparticle and for its method of surface treatment, and more specifically, relate to can effectively remove remain in the impurity that has in highly purified metal nanoparticle for the method for surface-treated metal nano particle and therefore synthetic metal nanoparticle.
Background technology
Conventionally, manufacture multilayer chiop element as multilayer ceramic capacitor (MLCC) by form above-mentioned of internal electrode, lamination in multiple dielectric piece to manufacture laminate and form outer electrode on laminate.As the material for internal electrode, use the metal thickener that comprises various types of metal nanoparticles.As an example, exist the nickel thickener that comprises nano nickel particles by use to form the technology of the internal electrode of multilayer ceramic capacitor.
By metal nanoparticle as synthetic in methods such as the methods of liquid phase method, vapor phase method, use plasma and laser.For example, can synthesize nano nickel particles with the organic solvent that comprises surfactant.The nano nickel particles of synthesized can easily disperse by non-polar solven, and adds polar solvent as alcohol, acetone etc., is then reclaimed with powder type by whizzer.
But, organic solvent and the surfactant in the lip-deep impurity of staying metal nanoparticle can be relatively easily removed for the synthesis of the method for metal nanoparticle, but the organic substance in impurity may be difficult to remove.Especially,, in the time that the slaine of chloride ion-containing is used as to reacting precursor, possibly cannot easily remove the lip-deep chlorion that is attached to synthetic metal nanoparticle.Impurity can reduce the purity of metal nanoparticle as chlorion etc., and when plan is when utilizing low-purity metal nanoparticle to be formed as the fine electrode of chip component, electrode characteristic can be deteriorated.
[correlation technique document]
[patent documentation]
(patent documentation 1) Korean Patent special permission publication number 2001-0110693
Summary of the invention
An object of the present invention is to provide and there is highly purified metal nanoparticle, and for the method for surface-treated metal nano particle.
Another object of the present invention is to provide the synthetic metal nanoparticle with low impurity concentration, and can effectively remove the method for surface-treated metal nano particle of the lip-deep impurity of staying metal nanoparticle.
Another object of the present invention is to provide the metal nanoparticle with low chlorine ion concentration, and can effectively remove the method for surface-treated metal nano particle of the lip-deep chlorion of staying synthetic metal nanoparticle.
According to an exemplary embodiment of the present invention, the method for surface-treated metal nano particle is provided, the method comprises: use containing the solution surface of alkanolamine and process metal nanoparticle.
The surface treatment of metal nanoparticle can comprise use alkanolamine remove the lip-deep chlorion that is attached to metal nanoparticle.
The surface treatment of metal nanoparticle can further comprise the surperficial chlorion that is attached to metal nanoparticle is replaced and enters alkanolamine.
The surface treatment of metal nanoparticle can further comprise: at least one the cleaning solution that preparation comprises monoethanolamine, diethanol amine and triethanolamine; And by making metal nanoparticle mix to prepare mixed solution with cleaning solution.
The concentration of the alkanolamine of this solution can be more than 10wt%.
Method for surface-treated metal nano particle can further comprise: use alcohol or toluene clean metal nano particle to remove the lip-deep surfactant at metal nanoparticle.
Method for surface-treated metal nano particle can further comprise: dry metal nanoparticle.
After dry metal nanoparticle, the concentration of lip-deep chlorion of the metal nanoparticle by utilizing ion-chromatographic determination can be lower than 100ppm.
After dry metal nanoparticle, the concentration of lip-deep chlorion of the metal nanoparticle by utilizing ion-chromatographic determination can be lower than 10ppm.
Can use containing the solution surface of alkanolamine and process metal nanoparticle, and after dry metal nanoparticle, the concentration of lip-deep chlorion of the metal nanoparticle by utilizing ion-chromatographic determination can be lower than 100ppm.
The concentration of chlorion can be to be less than 10ppm.
Accompanying drawing explanation
Fig. 1 is the flow chart illustrating according to the method for surface-treated metal nano particle of an exemplary embodiment of the present invention.
Fig. 2 is the schematic diagram of the method for describing surface-treated metal nano particle according to an illustrative embodiment of the invention.
Fig. 3 is the schematic diagram that the multilayer ceramic capacitor by using nano nickel particles (it has been applied to the method for surface-treated metal nano particle according to an illustrative embodiment of the invention) manufacturing is shown.
The specific embodiment
By the following description of embodiment and with reference to accompanying drawing, various advantage and disadvantages of the present invention and the method that completes it will become apparent.But, can be with many multi-form the present invention that improve, and should not be limited to the embodiment of statement herein.These embodiments can be provided, so that this disclosure content will be thorough and complete, and will give full expression to scope of the present invention to those skilled in the art.The same identical key element of denotion numeral in whole description.
The term using is in this manual for explaining embodiment rather than restriction the present invention.In this manual, describe on the contrary unless clear and definite, singulative comprises plural form.Wording " comprises " and its modification was stated being understood to include as " comprising " or " containing " composition, step, operation and/or key element, but do not get rid of any other composition, step, operation and/or key element.
Hereinafter, describe in detail with reference to the accompanying drawings according to the metal nanoparticle of an exemplary embodiment of the present invention with for the method for surface-treated metal nano particle.
Fig. 1 illustrates the flow chart for the method for surface-treated metal nano particle according to an exemplary embodiment of the present invention, and Fig. 2 is the schematic diagram of the principle for describing surface-treated metal nano particle according to an illustrative embodiment of the invention.
With reference to Fig. 1 and 2, the method for surface-treated metal nano particle according to an illustrative embodiment of the invention can comprise removes the lip-deep impurity 120(S110 that remains in synthetic metal nanoparticle 110), use comprise alkanolamine 130 solution-treated metal nanoparticle 110(S120) and dry metal nanoparticle 110(S130).
Can prepare metal nanoparticle 110 by the whole bag of tricks that uses synthesis of nano particle.For example, can be by using vapor phase method, liquid phase method and using any method of the method for plasma and laser to prepare various metal nanoparticles 110.As an example, use the slaine of chloride ion-containing to prepare nano nickel particles as reacting precursor synthetic can the comprising of metal nanoparticle 110.The surperficial form that various impurity 120 can be attached to metal nanoparticle 110 with impurity 120 remains in synthetic metal nanoparticle 110.Impurity 120 can comprise organic solvent, surfactant, organic substance etc.Organic substance can comprise chlorion.
Can remove the lip-deep impurity 120(S110 that remains in metal nanoparticle 110).Can be by processing metal nanoparticle 110 with alcohol or toluene to carry out removing of impurity 120.Can remove organic solvent or surfactant in impurity 120, and no matter the polarity in the process that uses alcohol or O for toluene metal nanoparticle 110 or nonpolar.But, only, by using alcohol or toluene to process, may be difficult to remove the organic substance in impurity.The surperficial organic substance that is attached to metal nanoparticle 110 can reduce the purity of metal nanoparticle 110.
Thereby, can pass through to use alkanolamine 130 surface-treated metal nano particle 110(S120).Can provide the surface treatment of metal nanoparticle 110 to remove the organic substance in the lip-deep impurity 120 that is attached to metal nanoparticle 110.In more detail, in the surface treatment of the metal nanoparticle 110 that uses alkanolamine 130 to carry out, metal nanoparticle 110 can be mixed with cleaning solution.Therefore be, that the chlorion that is attached to the surperficial organic substance of metal nanoparticle 110 is substituted in alkanolamine 130, so that can remove chlorion from metal nanoparticle.
In this article, as cleaning solution, can use at least one the solution that comprises monoethanolamine (EA), diethanol amine (DEA), triethanolamine (TEA).In addition, cleaning solution can further add alcohols as ethanol.In this case, can control cleaning solution so that the concentration of alkanolamine become at least 10wt% or more than.When the concentration of alkanolamine is during lower than 10wt%, the removal efficiency of chlorion is lower, so that may be difficult to expect the high removal efficiency of impurity.
Meanwhile, the surface treatment of metal nanoparticle 110 (S120) may further include under predetermined temperature and heats by cleaning solution being added to the prepared mixed solution of metal nanoparticle 110.The heating-up temperature of mixed solution can be approximately 60 ℃ to 100 ℃.Especially, in the time that ethanol is added to mixed solution, the heating-up temperature of mixed solution can be higher than 78 ℃, and it is the boiling point of ethanol.But, can, in the situation that not heating mixed solution, carry out the substitution reaction between alkanolamine 130 and chlorion, so that can carry out alternatively the heating of mixed solution.
In addition, can be dried metal nanoparticle 110(S130).The dry of metal nanoparticle 110 can be for removing the lip-deep alkanolamine 130 that is attached to metal nanoparticle 110.The dry of metal nanoparticle 110 can comprise: heat-treated metal nano particle 110 at least 50 ℃ or above temperature.Therefore, be dried and remove the alkanolamine 130 that is attached to metal nanoparticle 110, so that can obtain metal nanoparticle 110, its chlorine ion concentration is less than about 100ppm.Especially, according to illustrative embodiments of the present invention, can obtain high purity metal nano particle 110 for the method for surface-treated metal nano particle, its chlorine ion concentration is about 10ppm or less, is more preferably less than 5ppm.
[embodiment 1]
After synthetic metal nanoparticle, use respectively the synthetic metal nanoparticle of twice cleaning of twice of ethanol and toluene, and added the cleaning solution being formed by triethanolamine and ethanol to prepare mixed solution.At the temperature of 80 ℃, heat mixed solution.In addition, after dry metal nanoparticle, utilize ion chromatography analysis to remain in the amount of the lip-deep chlorion of nano particle.Following table 1 is illustrated in the removal effect of the chlorion on surface treatment time of the solution that comprises triethanolamine as described above.
[table 1]
| Department | Chlorine ion concentration (ppm) |
| Before the surface treatment of use alkanolamine | 1780 |
| Using alkanolamine surface treatment after 30 minutes | 5.6 |
| Using alkanolamine surface treatment after 10 hours | 2.3 |
As described above, than initial metal nanoparticle, use the final chlorine ion concentration of the cleaning solution surface-treated metal nanoparticle that comprises alkanolamine to show more than 99% clearance.That is, the only surface treatment of the short time by approximately 30 minutes, the cleaning solution that comprises alkanolamine can show the clearance of the high chloride ion of metal nanoparticle, so that shown significantly to improve the manufacturing process output with highly purified nano particle.Especially, only, by means of the surface treatment of 30 minutes, the chlorine ion concentration of metal nanoparticle can be reduced to lower than 10ppm, and chlorine ion concentration can be reduced to lower than 5ppm.
As described above, according to the method for surface-treated metal nano particle of illustrative embodiments of the present invention use alkanolamine solution effectively to remove to be attached to synthetic metal nanoparticle 110 lip-deep impurity 120 be relatively difficult to the chlorion removed.Especially, illustrative embodiments of the present invention can be removed more than 99% chlorion within the relatively short processing time, thereby significantly improves surface treatment efficiency.Therefore, according to an illustrative embodiment of the invention for the method for surface-treated metal nano particle, by using the synthetic metal nanoparticle of chain triacontanol amine solution surface treatment to be relatively difficult to effectively to remove the chlorion removed in the lip-deep impurity that remains in synthetic metal nanoparticle, there is thereby obtain the 100ppm of being about, preferably lower than the high purity metal nano particle of the chlorine ion concentration of 5ppm.
Then, as described above in detail, the various application of removing the metal nanoparticle 110 of impurity from it by surface treatment method according to an illustrative embodiment of the invention will be described.
Metal nanoparticle after surface treatment according to an illustrative embodiment of the invention can be used to form the material of the internal wiring of electronic circuit.Especially, metal nanoparticle is in the situation of nano nickel particles therein, nano nickel particles has relatively high purity and tap density, thereby, can be suitable as the material of the electrode that is used to form the multilayer ceramic capacitor (MLCC) that is recently gradually little and attenuation.
Fig. 3 is the schematic diagram that the multilayer ceramic capacitor by using nano nickel particles manufacturing is shown, has wherein applied the method for surface-treated metal nano particle according to an illustrative embodiment of the invention for above-mentioned nano nickel particles.With reference to Fig. 3, can be by organic bond and organic solvent being added by synthetic nano nickel particles and carrying out nano nickel particles that described surface treatment obtains and prepare nickel thickener (about synthetic nano nickel particles with reference to Fig. 1 and 2).The example of organic bond can comprise ethyl cellulose etc., and the example of organic solvent can comprise terpinol, dihydroxy terpinol, 1-octanol kerosene etc.In this case, the content that can control nickel thickener is to have nano nickel particles, the organic bond of 0.8wt% to 4wt% and the organic solvent of 40wt% to 60wt% of 40wt% to 60wt%.In this article, conducting paste according to an illustrative embodiment of the invention can further comprise any additive in plasticizer, resistance to bond agent and dispersant.
In addition, after the multiple dielectric piece 20 of preparation, can in each dielectric piece 20, form by silk screen print method the predetermined internal electrode 30 of metal thickener.By dielectric piece 20 laminations and burn, thereby manufacture laminate 40.Can form the outer electrode 50 being electrically connected with internal electrode 30 at the two ends of laminate 40.In this case, can use nickel thickener to form outer electrode 50.In the time forming outer electrode 50 by nickel thickener, can not be used to form the independent electroplating process of outer electrode 50.By said process, can manufacture the multilayer ceramic capacitor 10 with high electrode characteristic.
Aforesaid illustrative embodiments of the present invention, by way of example, describe such situation, wherein metal nanoparticle according to the present invention has been applied to chip element as multilayer ceramic capacitor, but metal nanoparticle according to the present invention can be applied to various fields.As another example, can be by metal nanoparticle as catalyst.In more detail, can be by metal nanoparticle with acting on the catalyst, hydrogenation catalyst of fuel cell, in various chemical reactions the alternative catalysts etc. of Pt.
According to an illustrative embodiment of the invention, the chloride ion impurities that use alkanolamine solution-treated is difficult to remove relatively, effectively to remove chloride ion impurities, has highly purified metal nanoparticle thereby obtain.
According to an illustrative embodiment of the invention, be used for the method for surface-treated metal nano particle by utilizing alkanolamine solution surface to process synthetic metal nanoparticle, in the lip-deep impurity that remains in synthetic metal nanoparticle, be relatively difficult to effectively to remove the chlorion removed, there is highly purified metal nanoparticle thereby obtain.
More than describe in detail and illustrate the present invention.In addition, above content is explanation and description the preferred embodiment of the present invention just, and can under various combinations, variation and environment, use the present invention.That is, it should be understood by those skilled in the art that in these embodiments and can replace, improve and change, and do not depart from principle and the spirit of total inventive concept, limit the scope of the invention to and enclose in claim and their equivalence statement.Although, disclosing for illustrative purposes illustrative embodiments of the present invention, those skilled in the art will understand, various improvement, additive and replacement are possible, and do not depart from as in the scope and spirit of the present invention of enclosing and disclosing in claim.Thereby detailed description of the present invention is not used for the present invention to be limited to disclosed embodiment.In addition, should understand, the claim of enclosing even comprises another kind of embodiment.
Claims (11)
1. for a method for surface-treated metal nano particle, comprising:
Use containing the solution surface of alkanolamine and process metal nanoparticle.
2. method according to claim 1, wherein, the surface treatment of described metal nanoparticle comprise use described alkanolamine remove the lip-deep chlorion that is attached to described metal nanoparticle.
3. method according to claim 1, wherein, the surface treatment of described metal nanoparticle further comprises the lip-deep chlorion that is attached to described metal nanoparticle is replaced and enters described alkanolamine.
4. method according to claim 1, wherein, the surface treatment of described metal nanoparticle further comprises:
Preparation comprises at least one the cleaning solution in monoethanolamine, diethanol amine and triethanolamine; With
By making described metal nanoparticle and described cleaning solution be mixed with mixed solution.
5. method according to claim 1, wherein, the concentration of the described alkanolamine of described solution is more than 10wt%.
6. method according to claim 1, further comprises and cleans described metal nanoparticle to remove the lip-deep surfactant of described metal nanoparticle with alcohol or toluene.
7. method according to claim 1, further comprises:
Dry described metal nanoparticle.
8. method according to claim 7, wherein, after dry described metal nanoparticle, the concentration of lip-deep described chlorion of the described metal nanoparticle by utilizing ion-chromatographic determination is to be less than 100ppm.
9. method according to claim 8, wherein, after dry described metal nanoparticle, the concentration of lip-deep described chlorion of the described metal nanoparticle by utilizing ion-chromatographic determination is to be less than 10ppm.
10. a metal nanoparticle, wherein, described metal nanoparticle is what to use containing the solution surface processing of alkanolamine, and after described metal nanoparticle is dry, the concentration of lip-deep chlorion of the described metal nanoparticle by utilizing ion-chromatographic determination is to be less than 100ppm.
11. metal nanoparticles according to claim 10, wherein, the concentration of described chlorion is to be less than 10ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120120361A KR101472634B1 (en) | 2012-10-29 | 2012-10-29 | Metal nano particle, and method for surface treating the same |
| KR10-2012-0120361 | 2012-10-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103785823A true CN103785823A (en) | 2014-05-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310455118.9A Pending CN103785823A (en) | 2012-10-29 | 2013-09-29 | Metal nano particle and method for surface treating the same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20140119978A1 (en) |
| KR (1) | KR101472634B1 (en) |
| CN (1) | CN103785823A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593843B (en) * | 2015-02-04 | 2017-06-30 | 广东羚光新材料股份有限公司 | Chip multilayer ceramic capacitor electroplates normal temperature pre-treating method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078641A1 (en) * | 2003-03-08 | 2004-09-16 | Mijitech Co. Ltd. | Metal nano-particles coated with silicon oxide and manufacturing method thereof |
| CN1967752A (en) * | 2006-11-06 | 2007-05-23 | 乳源瑶族自治县东阳光化成箔有限公司 | A low-voltage anode foil used for aluminium electrolytic capacitor and its manufacturing method |
| US20080166474A1 (en) * | 2006-02-17 | 2008-07-10 | Masahiro Deguchi | Conductive composite particle, method of manufacturing the same, electrode using the same, lithium ion secondary battery |
| CN102166574A (en) * | 2010-02-26 | 2011-08-31 | 三星电机株式会社 | Method for cleaning metal nanoparticles |
| CN102618082A (en) * | 2012-03-16 | 2012-08-01 | 金华双宏化工有限公司 | Method for preparing water-soluble ink jet dye |
| CN102660320A (en) * | 2012-05-18 | 2012-09-12 | 金浦新材料股份有限公司 | Antichlor and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4356323B2 (en) * | 2003-01-17 | 2009-11-04 | 堺化学工業株式会社 | Surface-treated nickel metal powder and method for producing the same |
| JP4665499B2 (en) * | 2004-12-10 | 2011-04-06 | 三菱マテリアル株式会社 | Metal fine particles, production method thereof, composition containing the same, and use thereof |
| JP5234389B2 (en) * | 2007-08-02 | 2013-07-10 | 地方独立行政法人山口県産業技術センター | Method for producing metal nanoparticles |
| JP2009185363A (en) * | 2008-02-08 | 2009-08-20 | Matsumoto Fine Chemical Co Ltd | Surface treating composition |
-
2012
- 2012-10-29 KR KR1020120120361A patent/KR101472634B1/en not_active IP Right Cessation
-
2013
- 2013-09-29 CN CN201310455118.9A patent/CN103785823A/en active Pending
- 2013-10-28 US US14/065,120 patent/US20140119978A1/en not_active Abandoned
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004078641A1 (en) * | 2003-03-08 | 2004-09-16 | Mijitech Co. Ltd. | Metal nano-particles coated with silicon oxide and manufacturing method thereof |
| US20080166474A1 (en) * | 2006-02-17 | 2008-07-10 | Masahiro Deguchi | Conductive composite particle, method of manufacturing the same, electrode using the same, lithium ion secondary battery |
| CN1967752A (en) * | 2006-11-06 | 2007-05-23 | 乳源瑶族自治县东阳光化成箔有限公司 | A low-voltage anode foil used for aluminium electrolytic capacitor and its manufacturing method |
| CN102166574A (en) * | 2010-02-26 | 2011-08-31 | 三星电机株式会社 | Method for cleaning metal nanoparticles |
| CN102618082A (en) * | 2012-03-16 | 2012-08-01 | 金华双宏化工有限公司 | Method for preparing water-soluble ink jet dye |
| CN102660320A (en) * | 2012-05-18 | 2012-09-12 | 金浦新材料股份有限公司 | Antichlor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140119978A1 (en) | 2014-05-01 |
| KR101472634B1 (en) | 2014-12-15 |
| KR20140054634A (en) | 2014-05-09 |
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Application publication date: 20140514 |