CN105200479A - Additive, electroplating liquid and method for roughening rolled copper foil - Google Patents
Additive, electroplating liquid and method for roughening rolled copper foil Download PDFInfo
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- CN105200479A CN105200479A CN201510731422.0A CN201510731422A CN105200479A CN 105200479 A CN105200479 A CN 105200479A CN 201510731422 A CN201510731422 A CN 201510731422A CN 105200479 A CN105200479 A CN 105200479A
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- electroplate liquid
- copper foil
- rolled copper
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- roughening treatment
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Abstract
The invention discloses an additive, an electroplating liquid and a method for roughening rolled copper foil. The electroplating liquid is prepared from the novel additive, properties of the electroplating liquid are improved, then mutual cooperation and promotion of the additive and sulfuric acid and copper sulfate in the electroplating liquid on the basis are realized, further, other process steps and process parameters are optimized, the original surface roughening process is improved in three aspects of the additive, the electroplating liquid and/or the roughening method, so that the bonding force of copper particles or copper plating on the rolled copper foil to a matrix of the rolled copper foil is increased, the copper powder falling degree is decreased, the surface roughness of the roughened rolled copper foil is in a reasonable range, the surface roughness is prevented from being too high or too low, the bonding force of the roughened rolled copper foil to a resin substrate of a printed board is increased, and the roughening effect is improved.
Description
Technical field
The present invention relates to rolled copper foil processing technique field, especially relate to a kind of rolled copper foil roughening treatment additive, electroplate liquid and coarsing processing method.
Background technology
Rolled copper foil is that copper is first processed into ingot casting through melting, then through hot rolling cogging, is rolled into the Copper Foil mother metal of 0.1mm ~ 0.15mm through roughing and finish rolling, and form finally by Copper Foil milling train repeat-rolling, its thickness is generally 6 μm ~ 70 μm.So the crystallographic texture of rolled copper foil is sheet structure, in strength and toughness, be better than electrolytic copper foil.In addition the density of rolled copper foil is higher, and surface is comparatively level and smooth, is more conducive to the signal fast transport after circuit card, the printed circuit board of high-frequency high-speed transmission, fine-line has a wide range of applications.
Rolled copper foil, in the application of high-end flexible print wiring board, has to pass through roughening treatment, resistance to chemical reagents process and anti-oxidation process, and in above surface treatment, roughening treatment decides the size of the profile tolerance after the process of high precision rolled copper foil and peel strength.
Rolled copper foil surface unusual light, surfaceness (Ra) generally only has about 0.2 μm, for ensureing there are enough bonding forces between rolled copper foil energy and printed board resin substrate, must carry out surface coarsening process to it.The essence of surface coarsening process is under the condition of high electric current, peracid, lower concentration cupric ion and lower temperature of electroplating solution, electroplating surface one deck of rolled copper foil large, warty copper particle, to improve the surfaceness of rolled copper foil.
At present, the surface coarsening treatment process of rolled copper foil uses for reference from the roughening treatment technique of electrolytic copper foil, because electrolytic copper foil hair side roughness is larger, surfaceness Rz is generally greater than 4 μm, and electrolytic copper foil can easily and firmly be attached on electrolytic copper foil hair side carrying out roughening treatment time institute copper facing particle.But, due to rolled copper foil surface unusual light, surfaceness much smaller than electrolytic copper foil, adopt with the similar roughening process process of electrolytic copper foil after, the bonding force of the copper particle on rolled copper foil or copper electrolytic coating and rolled copper foil matrix is lower, very easily occurs copper powder obscission; Coating surface roughness is excessive, the rolled copper foil after roughening treatment and the bonding force between printed board resin substrate lower, substantially cannot form copper-clad plate with the pressing of printed board resin substrate.
Therefore, how to improve the surface coarsening technique of rolled copper foil, copper particle on raising rolled copper foil or the bonding force of copper electrolytic coating and rolled copper foil matrix, and the bonding force between the rolled copper foil improved after roughening treatment and printed board resin substrate is the technical problem that current those skilled in the art need solution badly.
Summary of the invention
The object of this invention is to provide a kind of rolled copper foil roughening treatment additive, this additive is used to carry out surface coarsening process to rolled copper foil, the bonding force of copper particle on rolled copper foil or copper electrolytic coating and rolled copper foil matrix can be improved, and the bonding force between the rolled copper foil improved after roughening treatment and printed board resin substrate.Another object of the present invention is to provide a kind of rolled copper foil roughening treatment electroplate liquid adopting above-mentioned additive to prepare as starting material.Another object of the present invention is to provide a kind of rolled copper foil coarsing processing method using above-mentioned additive or electroplate liquid.
For solving above-mentioned technical problem, technical scheme provided by the invention is:
A kind of rolled copper foil roughening treatment additive, comprises the component of following weight percent: the ferrous sulfate of 27.30% ~ 63.60% and the Sodium orthomolybdate of 36.40% ~ 72.70%.
Preferably, above-mentioned rolled copper foil roughening treatment additive comprises the component of following weight percent: the ferrous sulfate of 36.40% ~ 54.50% and the Sodium orthomolybdate of 45.50% ~ 63.60%.
The present invention also provides a kind of rolled copper foil roughening treatment electroplate liquid, and be prepared from as one of raw material by the additive described in above-mentioned any one, described electroplate liquid comprises the component of following weight percent: the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4, 0.3g/L ~ 0.7g/L FeSO
4, 0.4g/L ~ 0.8g/L Na
2moO
4.
Preferably, described electroplate liquid comprises the component of following weight percent: the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4, 0.4g/L ~ 0.6g/L FeSO
4, 0.5g/L ~ 0.7g/L Na
2moO
4.
The present invention also provides a kind of rolled copper foil coarsing processing method, and its main technical process comprises the one-step solidification carried out successively, an alligatoring, secondary alligatoring and regelate, specifically comprises the following steps:
1) rolled copper foil and positive plate are placed in solidification groove, switch on power, supply circulation electroplate liquid, starts plating, carries out one-step solidification process;
2) additive is dissolved into additive solution in configured slot, described additive is the additive described in above-mentioned any one, then described additive solution is delivered in alligatoring circulation groove and mixes with the electroplate liquid in it, after controlling mixing, the composition of electroplate liquid meets the component of the electroplate liquid described in above-mentioned any one, then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 1) rolled copper foil after one-step solidification process and positive plate be immersed in the electroplate liquid in described alligatoring plating tank; Switch on power, supply circulation electroplate liquid, starts plating, carries out a roughening treatment;
3) additive is dissolved into additive solution in configured slot, described additive is the additive described in claim 1 or 2, then described additive solution is delivered in alligatoring circulation groove and mixes with the electroplate liquid in it, after controlling mixing, the composition of electroplate liquid meets the component of the electroplate liquid described in claim 3 or 4, then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 2) rolled copper foil after a roughening treatment and positive plate be immersed in the electroplate liquid in described alligatoring plating tank, and switch on power, supply circulation electroplate liquid, starts plating, carries out secondary roughening treatment;
4) by step 3) rolled copper foil after secondary roughening treatment and positive plate be placed in solidification groove, and switch on power, supply circulation electroplate liquid, starts plating, carries out regelate process, obtain the rolled copper foil after roughening treatment.
Preferably, described step 1) before the thickness of described rolled copper foil be 6 μm ~ 70 μm, the surfaceness Rz value of described rolled copper foil is 0.1 μm ~ 0.2 μm.
Preferably, described step 1) in, described in solidification groove, the temperature of electroplate liquid is 48 DEG C ~ 54 DEG C, and the circular flow of described electroplate liquid is 120L/min ~ 140L/min, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min, and current density used is 15A/dm
2~ 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L ~ 130g/L
2sO
4, 75g/L ~ 80g/L CuSO
4.
Preferably, described step 2) in, the temperature of described electroplate liquid is 20 DEG C ~ 25 DEG C, and the circular flow of described electroplate liquid is 90L/min ~ 110L/min, and current density used is 35A/dm
2~ 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min.
Preferably, described step 3) in, the temperature of described electroplate liquid is 20 DEG C ~ 25 DEG C, and the circular flow of described electroplate liquid is 90L/min ~ 110L/min, and current density used is 35A/dm
2~ 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min.
Preferably, described step 4) in, described in solidification groove, the temperature of electroplate liquid is 48 DEG C ~ 54 DEG C, and the circular flow of described electroplate liquid is 120L/min ~ 140L/min, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min, and current density used is 15A/dm
2~ 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L ~ 130g/L
2sO
4, 75g/L ~ 80g/L CuSO
4.
Compared with prior art, the invention provides a kind of rolled copper foil roughening treatment additive, comprise ferrous sulfate and Sodium orthomolybdate, the present invention, by adopting new additive agent preparation electroplate liquid, improves the proterties of electroplate liquid, and then cooperatively interact with the sulfuric acid in electroplate liquid and copper sulfate on this basis, mutually promote, further by optimizing other processing step and processing parameter, adopt the current density matched with Novel electric plating solution, circular flow, the processing parameters such as temperature of electroplating solution, from additive, electroplate liquid and/or coarsing processing method three aspects improve original surface coarsening treatment process, thus the bonding force of the copper particle that improve on rolled copper foil or copper electrolytic coating and rolled copper foil matrix, reduce the degree that copper powder comes off, and make the rolled copper foil surfaceness after roughening treatment be in a reasonably interval, avoid surfaceness too high or too low rolled copper foil after roughening treatment and the bonding force between printed board resin substrate are produced slacken impact significantly, thus improve the rolled copper foil after roughening treatment and the bonding force between printed board resin substrate, improve the effect of roughening treatment.
Accompanying drawing explanation
Fig. 1 is the SEM figure on the surface adopting 18 μm of rolled copper foils after traditional roughening process process;
Fig. 2 is the SEM figure on the surface of 18 μm of rolled copper foils in embodiment;
Fig. 3 is the SEM figure on the surface of 18 μm of rolled copper foils in embodiment;
Fig. 4 is the SEM figure on the surface of 18 μm of rolled copper foils in embodiment.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these descriptions just further illustrate feature of the present invention and advantage, instead of limiting to the claimed invention.
The invention provides a kind of rolled copper foil roughening treatment additive, comprise the component of following weight percent: the ferrous sulfate of 27.30% ~ 63.60% and the Sodium orthomolybdate of 36.40% ~ 72.70%.Preferably, above-mentioned additive comprises the component of following weight percent: the ferrous sulfate of 36.40% ~ 54.50% and the Sodium orthomolybdate of 45.50% ~ 63.60%.Sodium orthomolybdate and ferrous sulfate be added with the dispersive ability and covering power that are beneficial to and improve cupric ion in electroplate liquid, make the copper coating of copper foil surface finer and close, more firmly, come off without copper powder, peel strength is high for institute's copper facing crystal grain and copper foil surface.And Sodium orthomolybdate and ferrous sulfate medicine comparatively common, and addition is few, economical and practical, administration measure.The present invention finds after deliberation, after roughening treatment, the surfaceness of rolled copper foil is not be the bigger the better, too low or mistake metropolitan reduces the bonding force between the rolled copper foil after roughening treatment and printed board resin substrate, namely excessive roughness means that coating copper grain diameter is larger, space between copper particle is larger, contact surface between copper particle and rolled copper foil matrix is less, reduce the bonding force of copper particle on rolled copper foil or copper electrolytic coating and rolled copper foil matrix, very easily occur the phenomenon that copper powder comes off.
The present invention is by adopting new additive agent preparation electroplate liquid, improve the proterties of electroplate liquid, original surface coarsening treatment process is improved from this aspect of additive, improve the bonding force of copper particle on rolled copper foil or copper electrolytic coating and rolled copper foil matrix, reduce the degree that copper powder comes off, and make the rolled copper foil surfaceness after roughening treatment be in a reasonably interval, avoid surfaceness too high or too low rolled copper foil after roughening treatment and the bonding force between printed board resin substrate are produced slacken impact significantly, thus improve the rolled copper foil after roughening treatment and the bonding force between printed board resin substrate, improve the effect of roughening treatment.
Present invention also offers a kind of rolled copper foil roughening treatment electroplate liquid, be prepared from as one of raw material by the additive described in above-mentioned any one, described electroplate liquid comprises the component of following weight percent: the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4, 0.3g/L ~ 0.7g/L FeSO
4, 0.4g/L ~ 0.8g/L Na
2moO
4.Preferably, described electroplate liquid comprises the component of following weight percent: the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4, 0.4g/L ~ 0.6g/L FeSO
4, 0.5g/L ~ 0.7g/L Na
2moO
4.The present invention is by adopting new additive agent preparation electroplate liquid, improve the proterties of electroplate liquid, the content controlling sulfuric acid and copper sulfate in electroplate liquid is on this basis the level adapted with new-type additive, make sulfuric acid, copper sulfate, cooperatively interact between ferrous sulfate and Sodium orthomolybdate, mutually promote, original surface coarsening treatment process is improved from additive and/or electroplate liquid two aspects, thus the bonding force of the copper particle that improve on rolled copper foil or copper electrolytic coating and rolled copper foil matrix, reduce the degree that copper powder comes off, and make the rolled copper foil surfaceness after roughening treatment be in a reasonably interval, avoid surfaceness too high or too low rolled copper foil after roughening treatment and the bonding force between printed board resin substrate are produced slacken impact significantly, thus improve the rolled copper foil after roughening treatment and the bonding force between printed board resin substrate, improve the effect of roughening treatment.
Present invention also offers a kind of rolled copper foil coarsing processing method, its main technical process comprises the one-step solidification carried out successively, an alligatoring, secondary alligatoring and regelate, specifically comprises the following steps:
1) rolled copper foil and positive plate are placed in solidification groove, switch on power, supply circulation electroplate liquid, starts plating, carries out one-step solidification process;
2) additive is dissolved into additive solution in configured slot, described additive is the additive described in claim 1 or 2, then described additive solution is delivered in alligatoring circulation groove and mixes with the electroplate liquid in it, after controlling mixing, the composition of electroplate liquid meets the component of the electroplate liquid described in claim 3 or 4, then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 1) rolled copper foil after one-step solidification process and positive plate be immersed in the electroplate liquid in described alligatoring plating tank; Switch on power, supply circulation electroplate liquid, starts plating, carries out a roughening treatment;
3) additive is dissolved into additive solution in configured slot, described additive is the additive described in claim 1 or 2, then described additive solution is delivered in alligatoring circulation groove and mixes with the electroplate liquid in it, after controlling mixing, the composition of electroplate liquid meets the component of the electroplate liquid described in claim 3 or 4, then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 2) rolled copper foil after a roughening treatment and positive plate be immersed in the electroplate liquid in described alligatoring plating tank, and switch on power, supply circulation electroplate liquid, starts plating, carries out secondary roughening treatment;
4) by step 3) rolled copper foil after secondary roughening treatment and positive plate be placed in solidification groove, and switch on power, supply circulation electroplate liquid, starts plating, carries out regelate process, obtain the rolled copper foil after roughening treatment.
In one embodiment of the invention, described step 1) before the thickness of described rolled copper foil be 6 μm ~ 70 μm, the surfaceness Rz value of described rolled copper foil is 0.1 μm ~ 0.2 μm.
In one embodiment of the invention, described step 1) in, described in solidification groove, the temperature of electroplate liquid is 48 DEG C ~ 54 DEG C, and the circular flow of described electroplate liquid is 120L/min ~ 140L/min, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min, and current density used is 15A/dm
2~ 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L ~ 130g/L
2sO
4, 75g/L ~ 80g/L CuSO
4.
In one embodiment of the invention, described step 2) in, the temperature of described electroplate liquid is 20 DEG C ~ 25 DEG C, and the circular flow of described electroplate liquid is 90L/min ~ 110L/min, and current density used is 35A/dm
2~ 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min.
In one embodiment of the invention, described step 3) in, the temperature of described electroplate liquid is 20 DEG C ~ 25 DEG C, and the circular flow of described electroplate liquid is 90L/min ~ 110L/min, and current density used is 35A/dm
2~ 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min.
In one embodiment of the invention, described step 4) in, described in solidification groove, the temperature of electroplate liquid is 48 DEG C ~ 54 DEG C, and the circular flow of described electroplate liquid is 120L/min ~ 140L/min, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min, and current density used is 15A/dm
2~ 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L ~ 130g/L
2sO
4, 75g/L ~ 80g/L CuSO
4.
First the present invention carries out one-step solidification process to rolled copper foil, at the fine and closely woven copper particle of rolled copper foil plated surface last layer, improves surfaceness, to be got off realization by the condition of low current and high density cupric ion; Then, then carry out a roughening treatment, one-step solidification obtain the outside surface re-plating last layer of electrolytic coating large, warty copper particle, improve peel strength, the condition of logical excessive current, lower concentration cupric ion and additive reaches; Then, for making alligatoring better effects if, then secondary roughening treatment is carried out, an alligatoring obtain the outside surface re-plating last layer of electrolytic coating large, warty copper particle, further strengthening alligatoring effect, improves peel strength, and the condition of logical excessive current, lower concentration cupric ion and additive reaches; Finally, by regelate, between warty copper particle, fill fine and closely woven copper particle, make copper plate more firm.
In one-step solidification, an alligatoring, secondary alligatoring and regelate, described positive plate is preferably titanium plating iridium positive plate.
The present invention is by adopting new additive agent preparation electroplate liquid, improve the proterties of electroplate liquid, and then cooperatively interact with the sulfuric acid in electroplate liquid and copper sulfate on this basis, mutually promote, further by optimizing other processing step and processing parameter, adopt the current density matched with Novel electric plating solution, circular flow, the processing parameters such as temperature of electroplating solution, from additive, electroplate liquid and/or coarsing processing method three aspects improve original surface coarsening treatment process, thus the bonding force of the copper particle that improve on rolled copper foil or copper electrolytic coating and rolled copper foil matrix, reduce the degree that copper powder comes off, and make the rolled copper foil surfaceness after roughening treatment be in a reasonably interval, avoid surfaceness too high or too low rolled copper foil after roughening treatment and the bonding force between printed board resin substrate are produced slacken impact significantly, thus improve the rolled copper foil after roughening treatment and the bonding force between printed board resin substrate, improve the effect of roughening treatment.
In order to understand the present invention further, be described in detail to a kind of rolled copper foil roughening treatment additive provided by the invention, electroplate liquid and coarsing processing method below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
A kind of rolled copper foil coarsing processing method, its main technical process comprises the one-step solidification carried out successively, an alligatoring, secondary alligatoring and regelate, specifically comprises the following steps:
1) rolled copper foil and positive plate are placed in solidification groove, switch on power, supply circulation electroplate liquid, starts plating, carries out one-step solidification process; The thickness of rolled copper foil used is 6 μm, and the surfaceness Rz value of described rolled copper foil is 0.2 μm; The temperature controlling electroplate liquid described in solidification groove is 48 DEG C, and the circular flow of described electroplate liquid is 140L/min, and the speed of travel of described rolled copper foil is 17m/min, and current density used is 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L
2sO
4, 80g/L CuSO
4;
2) additive is dissolved into additive solution in configured slot, described additive comprises the component of following weight percent: the ferrous sulfate of 27.30% and the Sodium orthomolybdate of 72.70%; Then be delivered in alligatoring circulation groove by described additive solution and mix with the electroplate liquid in it, after controlling mixing, electroplate liquid comprises the component of following weight percent: the H of 175g/L
2sO
4, 32g/L CuSO
4, 0.3g/L FeSO
4, 0.8g/L Na
2moO
4; Then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 1) rolled copper foil after one-step solidification process and positive plate be immersed in the electroplate liquid in described alligatoring plating tank; Switch on power, supply circulation electroplate liquid, starts plating, carries out a roughening treatment; The temperature controlling described electroplate liquid is 20 DEG C, and the circular flow of described electroplate liquid is 110L/min, and current density used is 35A/dm
2, the speed of travel of described rolled copper foil is 19m/min;
3) additive is dissolved into additive solution in configured slot, described additive comprises the component of following weight percent: the ferrous sulfate of 27.30% and the Sodium orthomolybdate of 72.70%; Then be delivered in alligatoring circulation groove by described additive solution and mix with the electroplate liquid in it, after controlling mixing, electroplate liquid comprises the component of following weight percent: the H of 175g/L
2sO
4, 32g/L CuSO
4, 0.3g/L FeSO
4, 0.8g/L Na
2moO
4; Then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 2) rolled copper foil after a roughening treatment and positive plate be placed in alligatoring plating tank, and switch on power, supply circulation electroplate liquid, starts plating, carries out secondary roughening treatment; The temperature controlling described electroplate liquid is 20 DEG C, and the circular flow of described electroplate liquid is 110L/min, and current density used is 35A/dm
2, the speed of travel of described rolled copper foil is 19m/min;
4) by step 3) rolled copper foil after secondary roughening treatment and positive plate be placed in solidification groove, and switch on power, supply circulation electroplate liquid, starts plating, carries out regelate process; The temperature controlling electroplate liquid described in solidification groove is 48 DEG C, and the circular flow of described electroplate liquid is 140L/min, and the speed of travel of described rolled copper foil is 17m/min, and current density used is 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L
2sO
4, 80g/L CuSO
4, obtain the rolled copper foil after roughening treatment.
There is not the phenomenon that obvious copper powder comes off in the rolled copper foil in the present embodiment after roughening treatment, obtains the rolled copper foil after roughening treatment and carry out Performance Detection, the results are shown in Table 1 and Fig. 2 to the present embodiment.
Embodiment 2
A kind of rolled copper foil coarsing processing method, its main technical process comprises the one-step solidification carried out successively, an alligatoring, secondary alligatoring and regelate, specifically comprises the following steps:
1) rolled copper foil and positive plate are placed in solidification groove, switch on power, supply circulation electroplate liquid, starts plating, carries out one-step solidification process; The thickness of rolled copper foil used is 30 μm, and the surfaceness Rz value of described rolled copper foil is 0.1 μm; The temperature controlling electroplate liquid described in solidification groove is 50 DEG C, and the circular flow of described electroplate liquid is 130L/min, and the speed of travel of described rolled copper foil is 18m/min, and current density used is 18A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 125g/L
2sO
4, 77g/L CuSO
4;
2) additive is dissolved into additive solution in configured slot, described additive comprises the component of following weight percent: the ferrous sulfate of 40% and the Sodium orthomolybdate of 60%; Then be delivered in alligatoring circulation groove by described additive solution and mix with the electroplate liquid in it, after controlling mixing, electroplate liquid comprises the component of following weight percent: the H of 180g/L
2sO
4, 30g/L CuSO
4, 0.5g/L FeSO
4, 0.6g/L Na
2moO
4; Then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 1) rolled copper foil after one-step solidification process and positive plate be immersed in the electroplate liquid in described alligatoring plating tank; Switch on power, supply circulation electroplate liquid, starts plating, carries out a roughening treatment; The temperature controlling described electroplate liquid is 22 DEG C, and the circular flow of described electroplate liquid is 100L/min, and current density used is 37A/dm
2, the speed of travel of described rolled copper foil is 18m/min;
3) additive is dissolved into additive solution in configured slot, described additive comprises the component of following weight percent: the ferrous sulfate of 40% and the Sodium orthomolybdate of 60%; Then be delivered in alligatoring circulation groove by described additive solution and mix with the electroplate liquid in it, after controlling mixing, electroplate liquid comprises the component of following weight percent: the H of 180g/L
2sO
4, 30g/L CuSO
4, 0.5g/L FeSO
4, 0.6g/L Na
2moO
4; Then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 2) rolled copper foil after a roughening treatment and positive plate be placed in alligatoring plating tank, and switch on power, supply circulation electroplate liquid, starts plating, carries out secondary roughening treatment; The temperature controlling described electroplate liquid is 23 DEG C, and the circular flow of described electroplate liquid is 100L/min, and current density used is 38A/dm
2, the speed of travel of described rolled copper foil is 18m/min;
4) by step 3) rolled copper foil after secondary roughening treatment and positive plate be placed in solidification groove, and switch on power, supply circulation electroplate liquid, starts plating, carries out regelate process; The temperature controlling electroplate liquid described in solidification groove is 50 DEG C, and the circular flow of described electroplate liquid is 130L/min, and the speed of travel of described rolled copper foil is 18m/min, and current density used is 18A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 125g/L
2sO
4, 78g/L CuSO
4, obtain the rolled copper foil after roughening treatment.
There is not the phenomenon that obvious copper powder comes off in the rolled copper foil in the present embodiment after roughening treatment, obtains the rolled copper foil after roughening treatment and carry out Performance Detection, the results are shown in Table 1 and Fig. 3 to the present embodiment.
Embodiment 3
A kind of rolled copper foil coarsing processing method, its main technical process comprises the one-step solidification carried out successively, an alligatoring, secondary alligatoring and regelate, specifically comprises the following steps:
1) rolled copper foil and positive plate are placed in solidification groove, switch on power, supply circulation electroplate liquid, starts plating, carries out one-step solidification process; The thickness of rolled copper foil used is 70 μm, and the surfaceness Rz value of described rolled copper foil is 0.1 μm; The temperature controlling electroplate liquid described in solidification groove is 54 DEG C, and the circular flow of described electroplate liquid is 120L/min, and the speed of travel of described rolled copper foil is 19m/min, and current density used is 15A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 130g/L
2sO
4, 75g/L CuSO
4;
2) additive is dissolved into additive solution in configured slot, described additive comprises the component of following weight percent: the ferrous sulfate of 63.60% and the Sodium orthomolybdate of 36.40%; Then be delivered in alligatoring circulation groove by described additive solution and mix with the electroplate liquid in it, after controlling mixing, electroplate liquid comprises the component of following weight percent: the H of 185g/L
2sO
4, 28g/L CuSO
4, 0.7g/L FeSO
4, 0.4g/L Na
2moO
4; Then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 1) rolled copper foil after one-step solidification process and positive plate be immersed in the electroplate liquid in described alligatoring plating tank; Switch on power, supply circulation electroplate liquid, starts plating, carries out a roughening treatment; The temperature controlling described electroplate liquid is 25 DEG C, and the circular flow of described electroplate liquid is 90L/min, and current density used is 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min;
3) additive is dissolved into additive solution in configured slot, described additive comprises the component of following weight percent: the ferrous sulfate of 63.60% and the Sodium orthomolybdate of 36.40%; Then be delivered in alligatoring circulation groove by described additive solution and mix with the electroplate liquid in it, after controlling mixing, electroplate liquid comprises the component of following weight percent: the H of 185g/L
2sO
4, 28g/L CuSO
4, 0.7g/L FeSO
4, 0.4g/L Na
2moO
4; Then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 2) rolled copper foil after a roughening treatment and positive plate be placed in alligatoring plating tank, and switch on power, supply circulation electroplate liquid, starts plating, carries out secondary roughening treatment; The temperature controlling described electroplate liquid is 25 DEG C, and the circular flow of described electroplate liquid is 90L/min, and current density used is 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min;
4) by step 3) rolled copper foil after secondary roughening treatment and positive plate be placed in solidification groove, and switch on power, supply circulation electroplate liquid, starts plating, carries out regelate process; The temperature controlling electroplate liquid described in solidification groove is 54 DEG C, and the circular flow of described electroplate liquid is 120L/min, and the speed of travel of described rolled copper foil is 19m/min, and current density used is 15A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 130g/L
2sO
4, 75g/L CuSO
4, obtain the rolled copper foil after roughening treatment.
There is not the phenomenon that obvious copper powder comes off in the rolled copper foil in the present embodiment after roughening treatment, obtains the rolled copper foil after roughening treatment and carry out Performance Detection, the results are shown in Table 1 and Fig. 4 to the present embodiment.
Comparative example 1
Adopt traditional roughening process to carry out roughening treatment to rolled copper foil, electroplating bath components is the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4.
Having there is the phenomenon that obvious copper powder comes off in the rolled copper foil in the present embodiment after roughening treatment, obtains the rolled copper foil after roughening treatment and carry out Performance Detection, the results are shown in Table 1 and Fig. 1 to the present embodiment.
The performance detection data table of rolled copper foil prepared by table 1 embodiment and comparative example
| Group | Roughness (Rz)/μm | Peel strength/N/mm |
| Embodiment 1 | 3.1 | 1.6 |
| Embodiment 2 | 3.5 | 1.4 |
| Embodiment 3 | 3.2 | 1.5 |
| Comparative example 1 | 4.5 | 1.1 |
According to the contrast of above-described embodiment and comparative example, visible, through rolled copper foil roughening treatment additive provided by the invention, after electroplate liquid and coarsing processing method process, copper particle on rolled copper foil or between copper electrolytic coating and rolled copper foil matrix, there is higher bonding force, there is not the phenomenon that obvious copper powder comes off, and make the rolled copper foil surfaceness after roughening treatment be in a reasonably interval, avoid surfaceness too high or too low rolled copper foil after roughening treatment and the bonding force between printed board resin substrate are produced slacken impact significantly, make the rolled copper foil after roughening treatment and between printed board resin substrate, there is higher bonding force, improve the effect of roughening treatment.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.Multiple amendment for these embodiments is that apparent, defined herein General Principle can without departing from the spirit or scope of the present invention, realize in other embodiments for those skilled in the art.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the most wide region consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a rolled copper foil roughening treatment additive, is characterized in that, comprises the component of following weight percent: the ferrous sulfate of 27.30% ~ 63.60% and the Sodium orthomolybdate of 36.40% ~ 72.70%.
2. rolled copper foil roughening treatment additive according to claim 1, is characterized in that, comprise the component of following weight percent: the ferrous sulfate of 36.40% ~ 54.50% and the Sodium orthomolybdate of 45.50% ~ 63.60%.
3. a rolled copper foil roughening treatment electroplate liquid, is characterized in that, is prepared from as one of raw material by the additive described in claim 1 or 2, and described electroplate liquid comprises the component of following weight percent: the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4, 0.3g/L ~ 0.7g/L FeSO
4, 0.4g/L ~ 0.8g/L Na
2moO
4.
4. rolled copper foil roughening treatment electroplate liquid according to claim 3, it is characterized in that, described electroplate liquid comprises the component of following weight percent: the H of 175g/L ~ 185g/L
2sO
4, 28g/L ~ 32g/L CuSO
4, 0.4g/L ~ 0.6g/L FeSO
4, 0.5g/L ~ 0.7g/L Na
2moO
4.
5. a rolled copper foil coarsing processing method, is characterized in that, its main technical process comprises the one-step solidification carried out successively, an alligatoring, secondary alligatoring and regelate, specifically comprises the following steps:
1) rolled copper foil and positive plate are placed in solidification groove, switch on power, supply circulation electroplate liquid, starts plating, carries out one-step solidification process;
2) additive is dissolved into additive solution in configured slot, described additive is the additive described in claim 1 or 2, then described additive solution is delivered in alligatoring circulation groove and mixes with the electroplate liquid in it, after controlling mixing, the composition of electroplate liquid meets the component of the electroplate liquid described in claim 3 or 4, then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 1) rolled copper foil after one-step solidification process and positive plate be immersed in the electroplate liquid in described alligatoring plating tank; Switch on power, supply circulation electroplate liquid, starts plating, carries out a roughening treatment;
3) additive is dissolved into additive solution in configured slot, described additive is the additive described in claim 1 or 2, then described additive solution is delivered in alligatoring circulation groove and mixes with the electroplate liquid in it, after controlling mixing, the composition of electroplate liquid meets the component of the electroplate liquid described in claim 3 or 4, then by mixed electroplate liquid through interchanger heat exchange, then the electroplate liquid after heat exchange is delivered in alligatoring plating tank through single filter, cascade filtration and three poles after filtering; By step 2) rolled copper foil after a roughening treatment and positive plate be immersed in the electroplate liquid in described alligatoring plating tank, and switch on power, supply circulation electroplate liquid, starts plating, carries out secondary roughening treatment;
4) by step 3) rolled copper foil after secondary roughening treatment and positive plate be placed in solidification groove, and switch on power, supply circulation electroplate liquid, starts plating, carries out regelate process, obtain the rolled copper foil after roughening treatment.
6. rolled copper foil coarsing processing method according to claim 5, is characterized in that, described step 1) before the thickness of described rolled copper foil be 6 μm ~ 70 μm, the surfaceness Rz value of described rolled copper foil is 0.1 μm ~ 0.2 μm.
7. rolled copper foil coarsing processing method according to claim 5, it is characterized in that, described step 1) in, described in solidification groove, the temperature of electroplate liquid is 48 DEG C ~ 54 DEG C, the circular flow of described electroplate liquid is 120L/min ~ 140L/min, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min, and current density used is 15A/dm
2~ 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L ~ 130g/L
2sO
4, 75g/L ~ 80g/L CuSO
4.
8. rolled copper foil coarsing processing method according to claim 5, is characterized in that, described step 2) in, the temperature of described electroplate liquid is 20 DEG C ~ 25 DEG C, and the circular flow of described electroplate liquid is 90L/min ~ 110L/min, and current density used is 35A/dm
2~ 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min.
9. rolled copper foil coarsing processing method according to claim 5, is characterized in that, described step 3) in, the temperature of described electroplate liquid is 20 DEG C ~ 25 DEG C, and the circular flow of described electroplate liquid is 90L/min ~ 110L/min, and current density used is 35A/dm
2~ 40A/dm
2, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min.
10. rolled copper foil coarsing processing method according to claim 5, it is characterized in that, described step 4) in, described in solidification groove, the temperature of electroplate liquid is 48 DEG C ~ 54 DEG C, the circular flow of described electroplate liquid is 120L/min ~ 140L/min, the speed of travel of described rolled copper foil is 17m/min ~ 19m/min, and current density used is 15A/dm
2~ 20A/dm
2, described electroplate liquid comprises the component of following weight percent: the H of 120g/L ~ 130g/L
2sO
4, 75g/L ~ 80g/L CuSO
4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319585A (en) * | 2016-10-31 | 2017-01-11 | 中色奥博特铜铝业有限公司 | Surface treatment method of high-precision blackened rolled copper foil |
| CN110712419A (en) * | 2019-09-24 | 2020-01-21 | 无锡乐普金属科技有限公司 | Preparation method of copper-molybdenum-copper alloy material |
| CN110760862A (en) * | 2019-11-26 | 2020-02-07 | 江东电子材料有限公司 | Production process of smooth-surface roughened electrolytic copper foil |
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| CN1940145A (en) * | 2005-09-27 | 2007-04-04 | 日立电线株式会社 | Nickel plating solution and its preparation method, nickel plating method and printed wiring board copper foil |
| CN102418129A (en) * | 2011-11-18 | 2012-04-18 | 山东金宝电子股份有限公司 | Surface treatment process of copper foil for high-Tg halogen-free plate |
| CN103052278A (en) * | 2012-12-27 | 2013-04-17 | 建滔（连州）铜箔有限公司 | Additive for roughening surface of copper foil |
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| US5792333A (en) * | 1994-10-06 | 1998-08-11 | Circuit Foil Japan Co., Ltd. | Method of surface-roughening treatment of copper foil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106319585A (en) * | 2016-10-31 | 2017-01-11 | 中色奥博特铜铝业有限公司 | Surface treatment method of high-precision blackened rolled copper foil |
| CN110712419A (en) * | 2019-09-24 | 2020-01-21 | 无锡乐普金属科技有限公司 | Preparation method of copper-molybdenum-copper alloy material |
| CN110760862A (en) * | 2019-11-26 | 2020-02-07 | 江东电子材料有限公司 | Production process of smooth-surface roughened electrolytic copper foil |
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Application publication date: 20151230 |