CN109183018A - A kind of copper foil chromium-free passivation liquid and preparation method thereof - Google Patents
A kind of copper foil chromium-free passivation liquid and preparation method thereof Download PDFInfo
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- CN109183018A CN109183018A CN201811213628.4A CN201811213628A CN109183018A CN 109183018 A CN109183018 A CN 109183018A CN 201811213628 A CN201811213628 A CN 201811213628A CN 109183018 A CN109183018 A CN 109183018A
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- Prior art keywords
- copper foil
- chromium
- free passivation
- parts
- passivation liquid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The present invention provides a kind of copper foil chromium-free passivation liquids.In parts by weight, the raw material components of the copper foil chromium-free passivation liquid include: 1.5-15 parts of silane coupling agent, 0.05-0.5 parts of vfanadium compound, 0-15 parts of silica solution, 25-75 parts of organic solvent, 5-40 parts of water.The present invention also provides the preparation methods of above-mentioned copper foil chromium-free passivation liquid.Copper foil chromium-free passivation liquid of the invention is compared with traditional chromium hydrochlorate passivation technology, and antioxygenic property is more preferably；The electric conductivity of the negative collector of copper foil is not influenced, reduces internal resistance, promotes battery capacity；Passivating film hydrophily is strong, can remove, does not influence the production of circuit board；And because not containing heavy metal Cr VI, no poisonous and harmful substance discharge meets RoHS Directive；Preparation and passivation technology is simple, strong operability, it is green non-poisonous.
Description
Technical field
The present invention relates to a kind of copper foil chromium-free passivation liquids and preparation method thereof, belong to field of material technology.
Background technique
Currently, the negative copper foil collector in lithium ion battery is during transport, storage and copper coated foil plate production operation,
It due to extraneous steam, dust fall, oxidation, the pollution of even impression of the hand, can make copper foil surface that oxidation stain occur, not only influence copper foil
Appearance, it is often more important that influence the performance of battery, such as increase internal resistance, influence electric conductivity；Reduce the mechanical property of negative electrode material.
And in the manufacturing process of printed circuit board, the oxidizable formation of copper foil surface changes colour spot, influence copper face solderability,
Affinity, adhesion with ink, and line resistance can be made to increase, at this moment need the anti-oxidation processing of carry out two-sided to copper foil.
In view of the above-mentioned problems, tradition is the method using chromating；Chromating is to form one in copper foil surface
Layer oxidation film, it is generally several at one layer of copper foil surface electro-deposition so as to improve the heat resistance and mechanical behavior under high temperature of copper foil
Copper, zinc or the nickel alloy of ten nano thickness.This processing mode increases technologic complexity.
In addition, containing heavy metal Cr VI in traditional chromating liquid, since Cr VI is carcinogenic, environment is polluted,
It is expressly provided by European Union RoHS, content of 6-valence Cr ions is no more than 0.1%, Chinese corresponding mating instruction of also having gone on a journey.Therefore, nothing
By being lithium battery industry or printed circuit board industry all needs the high-performance of a alternative chromating and is passivated product.
Summary of the invention
It in view of the problems of the above-mentioned prior art, can the object of the present invention is to provide a kind of copper foil chromium-free passivation liquid
Copper foil antioxygenic property is improved, the discharge of pollutant is reduced.
The purpose of the present invention is achieved by the following technical programs:
A kind of copper foil chromium-free passivation liquid, in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
In above-mentioned copper foil chromium-free passivation liquid, silica solution is this field conventional reagent.Silane coupling agent forms Si-O-Si skeleton
Network, compactness is good, and is formed and be covalently attached with copper, improves binding force.Vfanadium compound (vanadium copper oxide) surface, forms one layer of cause
Close sull.Silica solution nanoparticle is mainly filling pore, Si-O-Si skeleton can also be formed with silane, into film
In skeleton structure.Silane coupling agent, vfanadium compound, silica solution three synergistic effect, form inorganic-organic composite membrane, high temperature resistant
Performance is more preferable.
In above-mentioned copper foil chromium-free passivation liquid, it is preferred that the silane coupling agent include γ-mercaptopropyl trimethoxysilane,
Gamma-mercaptopropyltriethoxysilane, γ-mercapto hydroxypropyl methyl dimethoxysilane, γ-mercapto hydroxypropyl methyl diethoxy silane, 3-
Thiocyanatopropyltriethoxysilane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3- (the third oxygen of 2,3- epoxy) propyl
Methyl dimethoxysilane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) second
The combination of one or more of bis- (triethoxy silicon substrate) ethane of base trimethoxy silane, 1,2- and ethyl orthosilicate.
In above-mentioned copper foil chromium-free passivation liquid, it is preferred that the vfanadium compound includes vanadic anhydride, sodium metavanadate and positive vanadium
The combination of one or more of sour sodium.
In above-mentioned copper foil chromium-free passivation liquid, it is preferred that the organic solvent includes pyridine and its derivatives, alcohols and alcohol ether
The combination of one or more of class.
In above-mentioned copper foil chromium-free passivation liquid, it is preferred that the organic solvent includes ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol
The combination of one or more of methyl ether, ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, pyridine and 2- picoline.
The present invention also provides the preparation methods of above-mentioned copper foil chromium-free passivation liquid, include the following steps:
Silane coupling agent, organic solvent and partial water are mixed, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting PH is acidity, obtains copper foil chromium-free passivation liquid.
In above-mentioned preparation method, it is preferred that when adjusting PH is acid, pH value 4-6.
In above-mentioned preparation method, it is preferred that when adjusting PH is acid, pH value 4.8.
In above-mentioned preparation method, be conducive to silane hydrolyzate in acid condition, and be unfavorable for polycondensation, mainly extends and produce
The stationary phase of product.
In above-mentioned preparation method, it is preferred that when adjusting PH is acid, glacial acetic acid is used to adjust liquid as acidity.
Protrusion effect of the invention are as follows:
Compared with the prior art, the invention has the following advantages: (1) is compared with traditional chromium hydrochlorate passivation technology, it is anti-oxidant
Performance is more preferably；(2) electric conductivity of the negative collector of copper foil is not influenced, reduces internal resistance, promotes battery capacity；(3) passivating film hydrophily
By force, it can remove, do not influence the production of circuit board；(4) it is discharged without poisonous and harmful substance, meets RoHS Directive；(5) it is passivated work
Skill is simple, strong operability.
Detailed description of the invention
Fig. 1 is the copper foil surface of 30min and 1h after the copper foil chromium-free passivation liquid obtained using embodiment under the conditions of 150 DEG C
Digital comparison diagram.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.Institute in following embodiments
Experimental method is stated, is conventional method unless otherwise specified；The reagent and material unless otherwise specified can be from business ways
Diameter obtains.
Embodiment 1
The present embodiment provides copper foil chromium-free passivation liquids, and in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
Silane coupling agent: 2.8 parts of γ-mercaptopropyl trimethoxysilanes, 2.8 parts of three ethoxies of 3- (the third oxygen of 2,3- epoxy) propyl
Base silane),
The method that is prepared by the following procedure of the copper foil chromium-free passivation liquid of the present embodiment is prepared:
By silane coupling agent, organic solvent and (20 parts) of partial water mixing, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting pH value using glacial acetic acid is 4.8, obtains copper foil chromium-free passivation liquid.
Embodiment 2
The present embodiment provides copper foil chromium-free passivation liquids, and in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
Silane coupling agent: 1 part of gamma-mercaptopropyltriethoxysilane or 1.5 parts of 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyls three
Methoxy silane,
The method that is prepared by the following procedure of the copper foil chromium-free passivation liquid of the present embodiment is prepared:
By silane coupling agent, organic solvent and (6 parts) of partial water mixing, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting pH value using glacial acetic acid is 4.8, obtains copper foil chromium-free passivation liquid.
Embodiment 3
The present embodiment provides copper foil chromium-free passivation liquids, and in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
Silane coupling agent: 7 parts of γ-mercapto hydroxypropyl methyl dimethoxysilane and 8 parts of 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyls
Diethoxy silane,
The method that is prepared by the following procedure of the copper foil chromium-free passivation liquid of the present embodiment is prepared:
By silane coupling agent, organic solvent and (20 parts) of partial water mixing, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting pH value using glacial acetic acid is 4.8, obtains copper foil chromium-free passivation liquid.
Embodiment 4
The present embodiment provides copper foil chromium-free passivation liquids, and in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
Silane coupling agent: 5 parts of γ-mercapto hydroxypropyl methyl diethoxy silane and 6 parts of 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyls
Dimethoxysilane,
Vfanadium compound: 0.1 part of sodium metavanadate and 0.3 part of sodium vanadate,
10 parts of silica solution,
50 parts of organic solvent (ethylene glycol ethyl ether),
25 parts of water.
The method that is prepared by the following procedure of the copper foil chromium-free passivation liquid of the present embodiment is prepared:
By silane coupling agent, organic solvent and (20 parts) of partial water mixing, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting pH value using glacial acetic acid is 4.8, obtains copper foil chromium-free passivation liquid.
Embodiment 5
The present embodiment provides copper foil chromium-free passivation liquids, and in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
Silane coupling agent: 1 part of γ-mercapto hydroxypropyl methyl dimethoxysilane, 3 parts of γ-mercapto hydroxypropyl methyl diethoxy silane,
5 parts of 3- thiocyanatopropyltriethoxysilanes and 6 parts of 3- (2,3- the third oxygen of epoxy) propyl-triethoxysilicanes,
Vfanadium compound: 0.2 part of vanadic anhydride and 0.3 part of sodium metavanadate,
15 parts of silica solution,
Organic solvent: 40 parts of butyl glycol ether, 35 parts of pyridine,
Water: 40 parts.
The method that is prepared by the following procedure of the copper foil chromium-free passivation liquid of the present embodiment is prepared:
By silane coupling agent, organic solvent and (35 parts) of partial water mixing, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting pH value using glacial acetic acid is 4.8, obtains copper foil chromium-free passivation liquid.
Embodiment 6
The copper foil chromium-free passivation liquid obtained using embodiment 1-5 is passivated processing to copper foil surface.
Copper foil electroplating technology is acid copper plating, and additive uses the product E B-209 of ElectroChem of the U.S., coating
8 μm of thickness.Copper foil passivating solution passivation technology condition is carried out to the copper foil are as follows: be passivated 10s at 10 DEG C.
Copper foil after Passivation Treatment is put into 150 DEG C of baking ovens after 30min, 1h and is taken out, color change is observed.Such as Fig. 1 institute
Show, wherein 1:150 DEG C, the digital figure of 30min high-temperature behavior test, 2:150 DEG C, the digital figure of 1h high-temperature behavior test.
Passivating film is fully transparent on copper foil, does not cover the color of copper foil itself, and hydrophily meets industry requirement, is passivated
The film later period can be removed with degreasing powder etc., not influence circuit board etching.Multimeter shows that resistance value is 0 when measuring its electric conductivity, table
Passivating film is on copper foil electric conductivity entirely without influence in the bright present invention, and compared with traditional chromium hydrochlorate passivating film, internal resistance reduces, battery
Capacity boost.1 is toasts the outside drawing after 30min under the conditions of 150 DEG C in Fig. 1, and copper foil color does not change substantially, illustrates this hair
The bright copper foil passivating solution antioxygenic property is excellent, and when extending baking time to 1h (as shown in figure 1 shown in 2), copper foil color is only
Only slightly deepen, shows excellent antioxygenic property, hence it is evident that be better than chromating method in the prior art.
In conclusion no matter being used for the protection against oxidation of copper foil in lithium ion battery or printed circuit board, the present invention is real
Applying the above-mentioned copper foil chromium-free passivation liquid of example all has excellent performance, fully achieves industry requirement.It is passivated with traditional chromium hydrochlorate
Technique is compared, and antioxygenic property is more preferably；The electric conductivity of the negative collector of copper foil is not influenced, reduces internal resistance, promotes battery capacity；Passivation
Film hydrophily meets industry requirement, can remove, does not influence the production of circuit board.And because heavy metal Cr VI, institute are not contained
It is discharged with no poisonous and harmful substance, meets RoHS Directive.Preparation and passivation technology is simple, strong operability, it is green non-poisonous.
Claims (9)
1. a kind of copper foil chromium-free passivation liquid, in parts by weight, the raw material components of the copper foil chromium-free passivation liquid include:
2. copper foil chromium-free passivation liquid according to claim 1, it is characterised in that: the silane coupling agent includes γ-mercapto propyl
Trimethoxy silane, gamma-mercaptopropyltriethoxysilane, γ-mercapto hydroxypropyl methyl dimethoxysilane, γ-mercapto hydroxypropyl methyl two
Ethoxysilane, 3- thiocyanatopropyltriethoxysilane, 3- (the third oxygen of 2,3- epoxy) propyl-triethoxysilicane, 3- (2,3-
The third oxygen of epoxy) hydroxypropyl methyl dimethoxysilane, 3- (the third oxygen of 2,3- epoxy) hydroxypropyl methyl diethoxy silane, 2- (3,4- ring
Oxygen cyclohexyl) ethyl trimethoxy silane, 1,2- bis- (triethoxy silicon substrate) one of ethane and ethyl orthosilicate or several
The combination of kind.
3. copper foil chromium-free passivation liquid according to claim 1, it is characterised in that: the vfanadium compound include vanadic anhydride,
The combination of one or more of sodium metavanadate and sodium vanadate.
4. copper foil chromium-free passivation liquid according to claim 1, it is characterised in that: the organic solvent includes pyridine and its derivative
The combination of one or more of object, alcohols and alcohol ethers.
5. copper foil chromium-free passivation liquid according to claim 4, it is characterised in that: the organic solvent include ethyl alcohol, normal propyl alcohol,
One of isopropanol, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, pyridine and 2- picoline or
Several combinations.
6. the preparation method of the described in any item copper foil chromium-free passivation liquids of claim 1-5, includes the following steps:
Silane coupling agent, organic solvent and partial water are mixed, the first solution is obtained；
Vfanadium compound, the water of rest part, silica solution are mixed, the second solution is obtained；
First solution and the second solution are mixed, adjusting PH is acidity, obtains copper foil chromium-free passivation liquid.
7. preparation method according to claim 6, it is characterised in that: when adjusting PH is acid, pH value 4-6.
8. preparation method according to claim 7, it is characterised in that: when adjusting PH is acid, pH value 4.8.
9. preparation method according to claim 6, it is characterised in that: when adjusting PH is acid, use glacial acetic acid as acid
Property adjust liquid.
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| CN201811213628.4A CN109183018A (en) | 2018-10-18 | 2018-10-18 | A kind of copper foil chromium-free passivation liquid and preparation method thereof |
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| CN201811213628.4A CN109183018A (en) | 2018-10-18 | 2018-10-18 | A kind of copper foil chromium-free passivation liquid and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111962082A (en) * | 2020-08-11 | 2020-11-20 | 湖北工程学院 | Green and environment-friendly copper foil antioxidant and anti-oxidation process using same |
| CN112048721A (en) * | 2020-08-11 | 2020-12-08 | 湖北工程学院 | Azole compound-based copper foil anti-oxidation additive and preparation method thereof |
| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471891A (en) * | 2009-08-11 | 2012-05-23 | 赢创德固赛有限公司 | Aqueous silane systems for bare corrosion protection and corrosion protection of metals |
| CN105695977A (en) * | 2016-02-04 | 2016-06-22 | 南昌大学 | Method for carrying out surface treatment on electrolytic copper foil by virtue of high-heat-resistance organosiloxane film-forming material |
| CN106756941A (en) * | 2016-12-15 | 2017-05-31 | 天长市润达金属防锈助剂有限公司 | A kind of water base brass antioxidant of high corrosion-resistant for adding Ludox and preparation method thereof |
| CN107460464A (en) * | 2017-08-28 | 2017-12-12 | 厦门大学 | A kind of surface treatment method of copper-bearing materials |
| JP2018016886A (en) * | 2016-07-15 | 2018-02-01 | ナミックス株式会社 | Production method of copper foil used for printed wiring board |
| CN107881496A (en) * | 2017-12-11 | 2018-04-06 | 浙江三瑞铜业有限公司 | A kind of copper strips passivator and its application process |
-
2018
- 2018-10-18 CN CN201811213628.4A patent/CN109183018A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471891A (en) * | 2009-08-11 | 2012-05-23 | 赢创德固赛有限公司 | Aqueous silane systems for bare corrosion protection and corrosion protection of metals |
| CN105695977A (en) * | 2016-02-04 | 2016-06-22 | 南昌大学 | Method for carrying out surface treatment on electrolytic copper foil by virtue of high-heat-resistance organosiloxane film-forming material |
| JP2018016886A (en) * | 2016-07-15 | 2018-02-01 | ナミックス株式会社 | Production method of copper foil used for printed wiring board |
| CN106756941A (en) * | 2016-12-15 | 2017-05-31 | 天长市润达金属防锈助剂有限公司 | A kind of water base brass antioxidant of high corrosion-resistant for adding Ludox and preparation method thereof |
| CN107460464A (en) * | 2017-08-28 | 2017-12-12 | 厦门大学 | A kind of surface treatment method of copper-bearing materials |
| CN107881496A (en) * | 2017-12-11 | 2018-04-06 | 浙江三瑞铜业有限公司 | A kind of copper strips passivator and its application process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111962082A (en) * | 2020-08-11 | 2020-11-20 | 湖北工程学院 | Green and environment-friendly copper foil antioxidant and anti-oxidation process using same |
| CN112048721A (en) * | 2020-08-11 | 2020-12-08 | 湖北工程学院 | Azole compound-based copper foil anti-oxidation additive and preparation method thereof |
| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
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