CN101184870A - Gravure cylinder-use copper plating method and device - Google Patents
Gravure cylinder-use copper plating method and device Download PDFInfo
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- CN101184870A CN101184870A CNA2006800183468A CN200680018346A CN101184870A CN 101184870 A CN101184870 A CN 101184870A CN A2006800183468 A CNA2006800183468 A CN A2006800183468A CN 200680018346 A CN200680018346 A CN 200680018346A CN 101184870 A CN101184870 A CN 101184870A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/03—Chemical or electrical pretreatment
- B41N3/032—Graining by laser, arc or plasma means
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/008—Current shielding devices
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/06—Suspending or supporting devices for articles to be coated
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/06—Filtering particles other than ions
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
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Abstract
Gravure cylinder-use copper plating method and device which can perform a uniform-thickness copper plating on a gravure cylinder over its entire length without causing defects such as rashes and pits regardless of the size of a gravure cylinder, can automatically control the concentration of copper plating solution, reduce the consumption of an additive, enable a short-time plating treatment, reduce power supply costs, and are easy to handle with good visibility. A hollow cylindrical gravure cylinder is gripped at the opposite longitudinal-direction ends, is placed in a plating tank filled with copper plating solution, and is energized so as to function as a cathode while rotated at a specified speed; a pair of long-box anode chambers that are vertically suspended slidably on the opposite sides of the gravure cylinder in the plating tank and incorporate insoluble anodes so energized as to function as anodes are allowed to come close to the opposite side surfaces of the gravure cylinder with specified intervals; and the outer peripheral surface of the gravure cylinder is copper plated.
Description
Technical field
The outer surface that the present invention relates to the gravure cylinder (gravurecylinder) (also being called the plate-making roller) at the hollow cylindrical that is used in intaglio printing is implemented the copper plating as gravure cylinder-use copper plating method and the device of space of a whole page formation with plate, relates in particular to and uses insoluble anode to implement the gravure cylinder-use copper plating method and the device of copper plating.
Background technology
In intaglio printing, gravure cylinder is formed the small recess (unit) of corresponding plate-making information, thereby make the space of a whole page, in this unit, fill black liquid, thereby transfer printing is printed thing.In the common gravure cylinder, as base material, on the outer surface of this base material, form a plurality of layers such as stratum basale or peel ply, form the space of a whole page thereon and form with copper plating layer (plate) as iron core cylindraceous or aluminium core.Then, on this copper plating layer, utilize laser explosure device to form unit, implement to be used to increase the chromium plating etc. of the brushability of gravure cylinder then, finish plate-making (making of the space of a whole page) corresponding to plate-making information.
In the past, as the method and the device that are used for implementing the copper plating to the outer surface of gravure cylinder, that widely knows is to use method and the device of phosphorous copper ball as soluble anode, it uses the length direction two ends of pair of rolls chuck clamping gravure cylinder, and described gravure cylinder can be rotated and can switch on, and be housed in the plating coating groove that stores plating solution, make the gravure cylinder rotation, flow through the electric current about current density 10～15A/dm2 between phosphorous copper ball (soluble anode) in plating solution and the gravure cylinder (negative electrode), copper is separated out at the outer surface as the gravure cylinder of negative electrode, thereby carry out copper plating (for example, with reference to patent documentation 1 and 2).
But, usually the phosphorous copper ball that uses in gravure cylinder-use copper plating method and device contains phosphorus: 350～700ppm, oxygen: 2～5ppm, residue is made of copper and impurity, because the impurity that contains inevitably, produce the anode sludge in plating is handled, the outer surface that these mud become at gravure cylinder produces pit (microspike) or pit defective cupric oxide powder D reasons such as (pin holes).In semi-conductor is made purposes etc., use highly purified phosphorous copper ball, but since its at high price,, do not adopt in the gravure cylinder purposes from cost consideration.In addition, for the meltage that prevents the phosphorous copper ball in the copper plating solution becomes too much, the concentration of cupric ion uprises, causing carrying out suitable plating handles, need regularly to extract plating solution out it is diluted, be adjusted to suitable copper ion concentration, perhaps also need to dispose waste liquid.And then, owing near the both ends of gravure cylinder, concentrate electric current, therefore, to compare with vertical tube part, near the plating thickness of the side face the both ends is thick, thereby need wait the thickness homogenizing that makes plating by grinding separately afterwards.
On the other hand, except using the method for phosphorous copper ball as soluble anode, use the copper plating method of insoluble anode in addition, as gravure cylinder-use copper plating method and device based on it, following method is arranged, that is: for example, use has the plate of iridium oxide as insoluble anode in the surface applied of titanium plate, prepare the dissolving tank of plating coating groove and copper, dissolved copper plating material in dissolving tank (for example, cupric oxide or copper carbonate), to supply with in its plating solution in plating coating groove, between the gravure cylinder of insoluble anode and formation negative electrode, switch on, implement copper plating (for example, with reference to patent documentation 3).
According to aforesaid method and device, do not produce defectives such as pit or pit though do not produce the anode sludge, still there is near the thick defective of plating thickness of the side face the both ends of gravure cylinder.Therefore, in order to eliminate these problems, the applicant has proposed gravure cylinder-use copper plating method as described below and device, that is: in plating coating groove, lifting constitutes the below cupric oxide powder D insoluble anode that is positioned at gravure cylinder freely, gravure cylinder according to various size, keeping 5mm～30mm makes insoluble anode near below the gravure cylinder with gap, make thus current concentration does not take place near the both ends of gravure cylinder, the roughly uniform plating of thickness can be on the total length of gravure cylinder, implemented, the copper concentration and the sulfuric acid concentration (patent documentation 4) of plating solution can be regulated automatically.
But, in such scheme, have following problem.Because insoluble anode is set directly in the plating solution, therefore, the consumption of additives such as gloss-imparting agent or incipient scorch retarding agent significantly change is many (for example, use phosphorous copper ball as under the situation of soluble anode as about 100cc/1000AH, relative therewith, be about 600cc/1000AH under situation about insoluble anode being arranged in the plating solution).Because in order to prevent incipient scorch, current density is 15～20A/dm
2About, voltage is about 10～15V, therefore, plating needs for a long time, cost electric power supply cost.The homogenizing of plating thickness is insufficient.Because insoluble anode is positioned at the below of gravure cylinder, therefore, the visuognosis variation, operability is variation also.
Patent documentation 1: special public clear 57-36995 communique
Patent documentation 2: the spy opens flat 11-61488 communique
Patent documentation 3: the spy opens the 2005-29876 communique
Patent documentation 4: the spy opens the 2005-133139 communique
Summary of the invention
The present invention makes in view of the above problems, no matter the size of gravure cylinder is provided to provide its purpose, can both be under the situation that does not produce defectives such as pit or pit, on the total length of gravure cylinder, implement the copper plating of homogeneous thickness, can manage the concentration of copper plating solution automatically, and can reduce the consumption of additive, can carry out plating at short notice handles, can reduce the electric power supply cost, good and maneuverable gravure cylinder-use copper plating method of visuognosis and device.
Gravure cylinder-use copper plating method of the present invention, it is characterized in that, at the two ends of length direction clamping hollow cylindrical gravure cylinder, and described gravure cylinder is housed in the plating coating groove that fills up the copper plating solution, described gravure cylinder is rotated with fixing speed, and switch on to described gravure cylinder according to the mode that becomes negative electrode, and making a pair of rectangular case shape (Long chi case shape) anolyte compartment keeps the two sides of predetermined distance near described gravure cylinder, thereby the outer surface to gravure cylinder is implemented the copper plating, hang down to being located at the both sides of gravure cylinder in described plating coating groove sliding freely in wherein said anolyte compartment, and in be provided with to be energized and be the anodic insoluble anode.
Promptly, insoluble anode directly is not set in plating solution, and be arranged in the anolyte compartment, this anolyte compartment is arranged to possess the sliding type anolyte compartment of mechanism freely of sliding in the both sides of gravure cylinder, carry out the copper plating with state thus and handle near the two sides of gravure cylinder.Thus, do not have the situation of defectives such as pit or pit take place, can implement the more uniform copper plating of thickness, reduce the consumption of additive, the gravure cylinder of tackling all sizes can be realized the homogenizing of plating thickness.Can handle shortening or the electric power supply cost of required time by plating,, therefore, become the more superior mode of visuognosis or operability because the anolyte compartment is positioned at the both sides of gravure cylinder.
Preferably set up cationic exchange membrane in the side of the gravure cylinder side of described anolyte compartment, described anolyte compartment has the above length of total length of the length direction of gravure cylinder.Why be in order on the total length of gravure cylinder, to implement the copper plating of homogeneous thickness.In addition, preferably acid electrolyte is arranged, get under the insufficient situation of liquid outlet quantity make up water by the liquid measure of measuring described anolyte compartment described anolyte compartment solid.
Preferred described copper plating solution contains copper sulfate, sulfuric acid, chlorine and additive, draws under the too high situation of proportion by proportion and the sulfuric acid concentration of measuring described copper plating solution, and make up water, under the too high situation of sulfuric acid concentration, the supplemental copper powder.Thus, the maintenance or the liquid waste disposal that do not need the copper plating solution that in the past regularly carried out.In addition, preferred described copper plating solution is to have removed impurity with strainer.
Described predetermined distance (making the anolyte compartment near the lateral interval of gravure cylinder) is about 1mm～50mm, about preferred 3mm～40mm, most preferably about 5mm～30mm.Approaching interval from narrow more plating thickness at interval more the viewpoint of homogenizing be preferred, if but excessively narrow, then in plating is handled, the trouble that causes the anolyte compartment to contact with gravure cylinder.
Gravure cylinder-use copper plating device of the present invention, it is used for implementing the copper plating to the outer surface of gravure cylinder, it is characterized in that possessing: the plating coating groove that fills up plating solution; Chuck mechanism, it is according to the length direction two ends of the mode clamping hollow cylindrical gravure cylinder that gravure cylinder can be rotated and can switch on, and described gravure cylinder is housed in the described plating coating groove; With a pair of rectangular case shape anolyte compartment, it hangs down sliding freely in described plating coating groove and is located at the both sides of gravure cylinder, and in be provided with to be energized and be the anodic insoluble anode.
Preferably set up cationic exchange membrane in the side of the gravure cylinder side of described anolyte compartment, described anolyte compartment has the above length of total length of the length direction of gravure cylinder.In addition, preferably described anolyte compartment solid acid electrolyte is arranged, described gravure cylinder-use copper plating device also possesses: anolyte compartment's liquid measure supplementary mechanism, it gets under the insufficient situation of liquid outlet quantity by the liquid measure of measuring described anolyte compartment, make up water.
Preferred described copper plating solution contains copper sulfate, sulfuric acid, chlorine and additive, described gravure cylinder-use copper plating device also possesses: the automatic administration of copper plating solution, it draws under the too high situation of proportion by proportion and the sulfuric acid concentration of measuring described copper plating solution, make up water, under the too high situation of sulfuric acid concentration, the supplemental copper powder.Preferably also possess: the strainer of removing the impurity in the described copper plating solution.
According to the present invention as can be known, play following significant effect, that is: no matter provide the size of gravure cylinder, can both be under the situation that does not produce defectives such as pit or pit, on the total length of gravure cylinder, implement the copper plating of homogeneous thickness, can manage the concentration of copper plating solution automatically, and can reduce the consumption of additive, can carry out plating at short notice handles, can reduce the electric power supply cost, good and maneuverable gravure cylinder-use copper plating method of visuognosis and device.
Description of drawings
Fig. 1 is that the master of an example of wanting bilge construction of expression gravure cylinder-use copper plating device of the present invention looks explanatory view.
Fig. 2 be expression gravure cylinder-use copper plating device of the present invention an example of wanting bilge construction overlook explanatory view.
Fig. 3 is the side illustration figure of an example of wanting bilge construction of expression gravure cylinder-use copper plating device of the present invention.
Fig. 4 is the schematic illustration of an example of expression anolyte compartment of the present invention.
Fig. 5 is the diagrammatic illustration figure of an example of the basic structure of expression gravure cylinder-use copper plating device of the present invention.
Fig. 6 is the conceptual illustration figure of an example of the automatic administration of expression copper plating solution of the present invention.
Fig. 7 is the conceptual illustration figure of an example of expression anolyte compartment of the present invention liquid measure supplementary mechanism.
Among the figure: 2-gravure cylinder-use copper plating device; The 4-pallet; The 6-bearing; The 8-cover plate; The 10-plating coating groove; The 11-vapor pipe; The 12-accumulator tank; The 14-chuck mechanism; 15-prevents the liquid shifting coupling; 16-axle (spindle); The 18-sprocket wheel; The 20-anolyte compartment; 22-guide rod (1ead bar); The 23-anode box; The 24-insoluble anode; The 25-sectional fixture; The 26-cationic exchange membrane; The 27-sectional fixture; 28-pushes flange; The 30-geared motor; 31-installs angle bar; 32,33,34,35, the 38-spurn wheel; 39,40-installs metalwork; 43,44,45,46,47, the 48-sprocket wheel; 50, the 52-linear track; 54, the 55-guide member; 58, the 59-installation frame; 60, the 62-shelf; The 70-storagetank; The 80-strainer; The 86-well heater; The 88-heat exchanger; The automatic adding set of 90-; The automatic administration of 100-copper plating solution; The 102-dissolving tank; The 104-powder feeding device; The 105-worm conveyor; 106-powder storage bucket; 108-pure water pressurized tank; The 110-controller; 112-proportion transmitter; 114-sulfuric acid transmitter; 200-anolyte compartment liquid measure supplementary mechanism; 210-pure water groove; The 212-buoy; 220-pure water pressurized tank; C, C
1, C
2, C
3-chain; The D-cupric oxide powder; F-copper plating solution; M-cylinder rotation motor; P
1, P
2, P
3, P
4-pump; The R-gravure cylinder; The S-acid electrolyte; V
T-variable valve; V
E-magnetic valve; The W-pure water.
Embodiment
Below, with reference to the accompanying drawings embodiments of the present invention are described, but illustrated example is only represented illustration, therefore self-evident, in the scope that does not break away from technological thought of the present invention, can carry out various distortion.
Fig. 1 is that the master of an example of wanting bilge construction of expression gravure cylinder-use copper plating device of the present invention looks explanatory view.Fig. 2 be expression gravure cylinder-use copper plating device of the present invention an example of wanting bilge construction overlook explanatory view.Fig. 3 is the side illustration figure of an example of wanting bilge construction of expression gravure cylinder-use copper plating device of the present invention.Fig. 4 is the schematic illustration of an example of expression anolyte compartment of the present invention.Fig. 5 is the diagrammatic illustration figure of an example of the basic structure of expression gravure cylinder-use copper plating device of the present invention.Fig. 6 is the conceptual illustration figure of an example of the automatic administration of expression copper plating solution of the present invention.Fig. 7 is the conceptual illustration figure of an example of expression anolyte compartment of the present invention liquid measure supplementary mechanism.
Gravure cylinder-use copper plating device 2 of the present invention is to implement the device of copper plating to the outer surface of the gravure cylinder R of hollow cylindrical, and possesses plating coating groove 10, chuck mechanism 14, a pair of anolyte compartment 20,20 (with reference to Fig. 1～Fig. 5).About plating coating groove 10 or chuck mechanism 14, have and the roughly the same structure of device (with reference to patent documentation 1～patent documentation 3) in the past, it is omitted repeat specification, but plating coating groove 10 is the plating processing of filling up copper plating solution F uses groove, gravure cylinder R can be immersed among the copper plating solution F fully.Around plating coating groove 10, be provided with the accumulator tank 9 (overflow downcomer) (with reference to Fig. 2, Fig. 3, Fig. 5) of the copper plating solution F that reclaims overflow, below plating coating groove 10, possess the storagetank 70 (with reference to Fig. 5, Fig. 6) that communicates with accumulator tank 12 and store copper plating solution F.(for example in storagetank 70, be provided with the liquid temperature that is used for copper plating solution F is remained on regulation, about 40 ℃) well heater 86 and heat exchanger 88, and be provided with the strainer 80 of the impurity that is used for removing copper plating solution F or draw copper plating solution F and make it at plating coating groove 10 round-robin pump P from storagetank 70
1Deng (with reference to Fig. 5, Fig. 6).Chuck mechanism 14 is length direction two ends of clamping gravure cylinder R, and it is housed in roller chuck device (with reference to patent documentation 1～patent documentation 3) in the plating coating groove 10, and possess with the axle 16 of 6 supportings of bearing and prevent the anti-liquid shifting coupling 15 that copper plating solution F enters, and the cylinder rotation motor M by being located at pallet 4 by chain C and sprocket wheel 18 with fixing speed (for example, about 120rpm) the rotation driving, in addition, can be by making it become negative electrode (with reference to Fig. 5) to gravure cylinder R energising.In addition, also suitably possess above plating coating groove 10 (with reference to Fig. 1, Fig. 5) such as the cover plate 8 that opens and closes freely or vapor pipes 11.
Also have, in gravure cylinder-use copper plating device 2 of the present invention, a pair of anolyte compartment 20,20 forms (Fig. 1～Fig. 5) of sliding type anolyte compartment of the both sides that are located at gravure cylinder of hanging down sliding freely in plating coating groove 10.Anolyte compartment 20, the 20th, the rectangular case shape parts with the above length of the total length of length direction of gravure cylinder R are (with reference to Fig. 2～Fig. 5), as shown in Figure 4, acid electrolyte S such as aqueous sulfuric acid are filled in the anode box 23, and insoluble anode 24 utilizes in the sectional fixture 25 and is located at wherein.As insoluble anode 24, use the surface applied of titanium plate that the anode of iridium oxide etc. is arranged, and make it become anode to its energising via guide rod 22.The side of 20 gravure cylinder side utilizes sectional fixture 27 and pushes flange 28 and set up cationic exchange membrane 26 in the anolyte compartment.
The mechanism that is slided freely in the both sides of gravure cylinder R in a pair of anolyte compartment 20 is not particularly limited, but one example is described according to Fig. 1～Fig. 3.Erect in the positive foreign side of plating coating groove 10 and to be provided with pallet 4, be provided with linear track 50,52 at the inner-wall surface of pallet 4. Shelf 60,62 is made as the positive and negative rotation and the linear track 50,52 that utilize spurn wheel 35,38 and does back and forth movement abreast, and is connected in 54,55. ends that link the guide rod 22,22 that anolyte compartment 20,20 is arranged in the upper end of installation frame 58,59 respectively that can engage with linear track 50,52 sliding contacts ground (with reference to Fig. 1～Fig. 3) via installation frame 58,59.
As the lateral interval that makes anolyte compartment 20 near gravure cylinder R, be about 1mm～50mm, about preferred 3mm～40mm, most preferably about 5mm～30mm.From the viewpoint of the homogenizing of plating thickness, we can say preferred more near anolyte compartment 20 more, if but excessively approaching, then exist the copper plating handle in the trouble that contacts with gravure cylinder R of anolyte compartment 20.
Gravure cylinder-use copper plating device 2 of the present invention preferably also possesses the automatic administration 100 of copper plating solution and anolyte compartment's liquid measure supplementary mechanism 200 (with reference to Fig. 6 and Fig. 7).Below plating coating groove 10, possess the storagetank 70 that stores copper plating solution F, copper plating solution F utilizes strainer 80 to remove wherein impurity, and is drawn and supply in the plating coating groove 10 by pump P1.The automatic adding set 90 (with reference to Fig. 6) of the pump P4 that possesses additives such as supplying with gloss-imparting agent and incipient scorch retarding agent suitably is set in addition.
The automatic administration 100 of copper plating solution is used for regulating the copper concentration of the copper plating solution F that is stored in storagetank 70 and the administration of sulfuric acid concentration.At copper plating solution F for example by copper sulfate (CuSO
45H
2O) concentration: 200～250g/L, sulfuric acid (H
2SO
4) concentration: 50～70g/L, chlorine (Cl) concentration: 50～200ppm and gloss-imparting agent or incipient scorch retarding agent etc. add under the situation that concentration: 1～10mL/L constitute, along with copper plating progress to gravure cylinder R, copper ion concentration in the aromatic series reduces, and free sulfuric acid increases.Therefore, CuO+H takes place by adding cupric oxide (CuO) in the copper ion concentration of minimizing
2SO
4-＞CuSO
4+ H
2Copper ion concentration is regulated in the O reaction, thereby, import the copper automatic administration 100 of plating solution (with reference to Fig. 6).Thus, do not need maintenance or the liquid waste disposal of regular copper plating solution F in the past, therefore preferred.
The automatic administration 100 of copper plating solution utilizes the copper plating solution F in the 110 pairs of storagetanks of controller 70 that possess proportion transmitter 112 and sulfuric acid transmitter 114 to take a sample, and carries out necessary adjusting in dissolving tank 102, utilizes pump P
3Draw copper plating solution F after the adjusting from dissolving tank 102, it is supplied in the storagetank 70.That is, use pump P
2Draw the copper plating solution F in the storagetank 70, measure proportion (copper concentration) and the sulfuric acid concentration of copper plating solution F with proportion transmitter 112 that is provided in controller 110 and sulfuric acid transmitter 114, and in that to be judged as proportion (copper concentration) too high (for example, surpass under the situation of concentration range 200～250g/L) controller 110 control magnetic valve V
EMake from pure water pressurized tank 108 make up water to dissolving tank 102, sulfuric acid concentration is too high (for example being judged as, surpass under the situation of concentration range 50～70g/L), controller 110 controls possess the powder feeding device 104 of worm conveyor 105, make from powder storage bucket 106 to dissolving tank 102 supplemental copper powder D (with reference to Fig. 5).Open magnetic valve V
EThe time service discharge can be by opening and closing variable valve V
TRegulate.By the automatic administration 100 of the copper plating solution of such formation, the concentration adjustment that can manage copper plating solution F automatically for example, is the centre management concentration of copper sulfate with 200～250g/L, is the centre management sulfuric acid concentration with 50～70g/L.Also have, powder as a supplement will use the situation of cupric oxide powder to be illustrated as preference, but also can be the powder of copper carbonate, copper sulfate etc.
In addition, the liquid measure of the acid electrolyte S that fill the inside of anolyte compartment's liquid measure supplementary mechanism 200 mensuration anolyte compartments 20, make up water under the insufficient situation of liquid measure.In the anode box 23 of anolyte compartment 20, fill the acid electrolyte S (with reference to Fig. 4 and Fig. 7) that constitutes by the aqueous sulfuric acid about sulfuric acid concentration 40～150g/L etc., but, produce oxygen, consume water owing to insoluble anode 24 makes water electrolysis, therefore, supply with water automatically to it.That is, communicate with the anode box 23 of anolyte compartment 20 and be provided with pure water groove 210, in pure water groove 210, store pure water W, detect the liquid level of pure water W by buoy 212.Reduce if detect liquid level, then control magnetic valve V by buoy 212
E, make and replenish pure water W (with reference to Fig. 7) from pure water pressurized tank 220.Open magnetic valve V
EThe time service discharge can be by opening and closing variable valve V
TRegulate.By anolyte compartment's liquid measure supplementary mechanism 200 of such formation, can keep necessary liquid measure automatically by antianode chamber 20 interior acid electrolyte S.
Embodiment
Below, enumerate embodiment and further specify the present invention, but self-evident, these embodiment are used for illustration, do not have limited explanation effect.
In following embodiment 1～embodiment 4, use following common formation.As the copper plating solution, use and contain concentration of copper sulfate 220g/L, sulfuric acid concentration 60g/L, cl concn 120g/L, " Ke Simo (コ ス モ) RS-MU " (big and special (strain) manufacturing is sold) 5m/L, the copper sulfate plating solution of " Ke Simo (コ ス モ) RS-1 " (big and special (strain) makes sale) 2m/L as additive.As the powder that utilizes the automatic administration of copper plating solution to replenish, use " processable cupric oxide (ES-CuO) " (crane sees that Cao Da (strain) makes sale) as cupric oxide powder.As the insoluble anode in the anolyte compartment, use has the anode of iridium oxide in the surface applied of titanium plate, as the acid electrolyte that is filled in the anolyte compartment, use the aqueous sulfuric acid of sulfuric acid concentration 100g/L, as cationic exchange membrane, use " Sai Limiweng (セ レ ミ オ Application) " (Asahi Glass's (strain) makes and sells).As the automatic administration of copper plating solution and anolyte compartment's liquid measure supplementary mechanism, constitute the device of described mechanism, as the proportion transmitter in the automatic administration of copper plating solution, use " SG-1 " (Japanese Ya Keya (ア Network ア) (strain) makes sale), as the sulfuric acid concentration transmitter, use " DM-1 " (Japanese Ya Keya (strain) makes sale).
(embodiment 1)
As gravure cylinder, use circumference 450mm, the round shape base material of the aluminium core of total length 1100mm, the two ends of clamping gravure cylinder, and it is installed in the plating coating groove, utilize computer-controlled slide mechanism that the anolyte compartment is approached to from 20mm place, gravure cylinder side, make the overflow of copper plating solution, fully the submergence gravure cylinder.The rotating speed of gravure cylinder is made as 120rpm, with 40 ℃ of liquid temperature, current density 18A/dm
2, voltage 5.4V carries out copper and is plating to 80 μ m.It is about 20 minutes that plating is handled the required time.Plating surface does not produce pit or pit, can form the uniform plating of thickness on the total length of gravure cylinder.In addition, the automatic administration of copper plating solution normally moves, and the composition of copper plating solution can be remained in the suitable scope.Anolyte compartment's liquid measure supplementary mechanism normally moves, and the liquid measure in the anolyte compartment can be remained on suitable amount.The consumption of additive significantly reduces, and is 60cc/1000AH.
(embodiment 2)
As gravure cylinder, use circumference 600mm, the round shape base material of the aluminium core of total length 1100mm, the two ends of clamping gravure cylinder, and it is installed in the plating coating groove, utilize computer-controlled slide mechanism that the anolyte compartment is approached to from 20mm place, gravure cylinder side, make the overflow of copper plating solution, fully the submergence gravure cylinder.The rotating speed of gravure cylinder is made as 120rpm, with 40 ℃ of liquid temperature, current density 18A/dm
2, voltage 6.0V carries out copper and is plating to 80 μ m.It is about 20 minutes that plating is handled the required time.Plating surface does not produce pit or pit, can form the uniform plating of thickness on the total length of gravure cylinder.In addition, the automatic administration of copper plating solution normally moves, and the composition of copper plating solution can be remained in the suitable scope.Anolyte compartment's liquid measure supplementary mechanism normally moves, and the liquid measure in the anolyte compartment can be remained on suitable amount.The consumption of additive significantly reduces, and is 60cc/1000AH.
(embodiment 3)
As gravure cylinder, use circumference 940mm, the round shape base material of the aluminium core of total length 1100mm, the two ends of clamping gravure cylinder, and it is installed in the plating coating groove, utilize computer-controlled slide mechanism that the anolyte compartment is approached to from 20mm place, gravure cylinder side, make the overflow of copper plating solution, fully the submergence gravure cylinder.The rotating speed of gravure cylinder is made as 120rpm, with 40 ℃ of liquid temperature, current density 18A/dm
2, voltage 7.7V carries out copper and is plating to 80 μ m.It is about 20 minutes that plating is handled the required time.Plating surface does not produce pit or pit, can form the uniform plating of thickness on the total length of gravure cylinder.In addition, the automatic administration of copper plating solution normally moves, and the composition of copper plating solution can be remained in the suitable scope.Anolyte compartment's liquid measure supplementary mechanism normally moves, and the liquid measure in the anolyte compartment can be remained on suitable amount.The consumption of additive significantly reduces, and is 60cc/1000AH.
(embodiment 4)
As gravure cylinder, use circumference 450mm, the round shape base material of the aluminium core of total length 1100mm, the two ends of clamping gravure cylinder, and it is installed in the plating coating groove, utilize computer-controlled slide mechanism that the anolyte compartment is approached to from 5mm place, gravure cylinder side, make the overflow of copper plating solution, fully the submergence gravure cylinder.The rotating speed of gravure cylinder is made as 120rpm, with 40 ℃ of liquid temperature, current density 30A/dm
2, voltage 7.9V carries out copper and is plating to 80 μ m.It is about 12 minutes that plating is handled the required time.Plating surface does not produce pit or pit, can form the uniform plating of thickness on the total length of gravure cylinder.In addition, the automatic administration of copper plating solution normally moves, and the composition of copper plating solution can be remained in the suitable scope.Anolyte compartment's liquid measure supplementary mechanism normally moves, and the liquid measure in the anolyte compartment can be remained on suitable amount.The consumption of additive significantly reduces, and is 60cc/1000AH.
Claims (13)
1. a gravure cylinder-use copper plating method is characterized in that,
At the two ends of length direction clamping hollow cylindrical gravure cylinder, and described gravure cylinder is housed in the plating coating groove that is full of the copper plating solution, described gravure cylinder is rotated with fixing speed, and switch on to described gravure cylinder in the mode that constitutes negative electrode, and make a pair of rectangular case shape anolyte compartment keep the two sides of predetermined distance ground near described gravure cylinder, thereby the outer surface to gravure cylinder is implemented the copper plating, hang down to being located at the both sides of gravure cylinder in described plating coating groove sliding freely in wherein said anolyte compartment, and in be provided with to be energized and constitute the anodic insoluble anode.
2. gravure cylinder-use copper plating method according to claim 1 is characterized in that,
Cationic exchange membrane has been set up in side in the gravure cylinder side of described anolyte compartment.
3. gravure cylinder-use copper plating method according to claim 1 and 2 is characterized in that,
Described anolyte compartment has the above length of total length of the length direction of gravure cylinder.
4. according to each described gravure cylinder-use copper plating method in the claim 1～3, it is characterized in that,
Being full of in the inside of described anolyte compartment has acid electrolyte, by measuring the liquid measure of described anolyte compartment, and under the insufficient situation of liquid measure, make up water.
5. according to each described gravure cylinder-use copper plating method in the claim 1～4, it is characterized in that,
Described copper plating solution contains copper sulfate, sulfuric acid, chlorine and additive, by proportion and the sulfuric acid concentration of measuring described copper plating solution, and under the too high situation of proportion, make up water, under the too high situation of sulfuric acid concentration, the supplemental copper powder.
6. according to each described gravure cylinder-use copper plating method in the claim 1～5, it is characterized in that,
Described copper plating solution is to have removed impurity with strainer.
7. according to each described gravure cylinder-use copper plating method in the claim 1～6, it is characterized in that,
Described predetermined distance is 1mm～50mm.
8. gravure cylinder-use copper plating device, it is used for implementing the copper plating to the outer surface of gravure cylinder, it is characterized in that possessing:
Fill up the plating coating groove of plating solution;
Chuck mechanism, it is according to the length direction two ends of the mode clamping hollow cylindrical gravure cylinder that gravure cylinder can be rotated and can switch on, and described gravure cylinder is housed in the described plating coating groove; With
The anolyte compartment of a pair of rectangular case shape, it hangs down sliding freely in described plating coating groove and is located at the both sides of gravure cylinder, and in be provided with to be energized and constitute the anodic insoluble anode.
9. gravure cylinder-use copper plating device according to claim 8 is characterized in that,
Cationic exchange membrane has been set up in side in the gravure cylinder side of described anolyte compartment.
10. according to Claim 8 or 9 described gravure cylinder-use copper plating devices, it is characterized in that,
Described anolyte compartment has the above length of total length of the length direction of gravure cylinder.
11. each described gravure cylinder-use copper plating device is characterized in that according to Claim 8～10,
Described anolyte compartment solid acid electrolyte is arranged, described gravure cylinder-use copper plating device also possesses: anolyte compartment's liquid measure supplementary mechanism, and it is by measuring the liquid measure of described anolyte compartment, under the insufficient situation of liquid measure, make up water.
12. each described gravure cylinder-use copper plating device is characterized in that according to Claim 8～11,
Described copper plating solution contains copper sulfate, sulfuric acid, chlorine and additive, described gravure cylinder-use copper plating device also possesses: the automatic administration of copper plating solution, it is by measuring the proportion and the sulfuric acid concentration of described copper plating solution, under the too high situation of proportion, make up water, under the too high situation of sulfuric acid concentration, the supplemental copper powder.
13. each described gravure cylinder-use copper plating device is characterized in that according to Claim 8～12,
Also possess: the strainer of removing the impurity in the described copper plating solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005152187 | 2005-05-25 | ||
| JP152187/2005 | 2005-05-25 |
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| CN101184870A true CN101184870A (en) | 2008-05-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800183468A Pending CN101184870A (en) | 2005-05-25 | 2006-05-23 | Gravure cylinder-use copper plating method and device |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20090095633A1 (en) |
| EP (1) | EP1887108A1 (en) |
| JP (1) | JPWO2006126518A1 (en) |
| KR (1) | KR20070118694A (en) |
| CN (1) | CN101184870A (en) |
| WO (1) | WO2006126518A1 (en) |
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| CN101917089A (en) * | 2010-07-09 | 2010-12-15 | 江苏佳成机械有限公司 | Driving device of working shafts on copper plating trolley |
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| DE102009023124A1 (en) * | 2008-05-28 | 2009-12-03 | Ipt International Plating Technologies Gmbh | Process for the galvanic copper coating and apparatus for carrying out such a process |
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| JPS6360295A (en) * | 1986-08-29 | 1988-03-16 | Mitsubishi Metal Corp | Device for controlling silver concentration in silver electrolyte |
| JP3083968B2 (en) * | 1995-01-12 | 2000-09-04 | 株式会社三井ハイテック | Method and apparatus for controlling concentration of plating solution |
| JP2000017495A (en) * | 1998-06-30 | 2000-01-18 | Rix Corp | Plating aperture for electronic parts |
| JP3903120B2 (en) * | 2003-03-07 | 2007-04-11 | 大阪府 | Copper sulfate plating method |
| JP2005029876A (en) * | 2003-07-11 | 2005-02-03 | Think Laboratory Co Ltd | Copper sulfate plating method |
-
2006
- 2006-05-23 US US11/913,257 patent/US20090095633A1/en not_active Abandoned
- 2006-05-23 WO PCT/JP2006/310209 patent/WO2006126518A1/en active Application Filing
- 2006-05-23 JP JP2007517828A patent/JPWO2006126518A1/en active Pending
- 2006-05-23 CN CNA2006800183468A patent/CN101184870A/en active Pending
- 2006-05-23 EP EP06756465A patent/EP1887108A1/en not_active Withdrawn
- 2006-05-23 KR KR1020077025754A patent/KR20070118694A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2006126518A1 (en) | 2008-12-25 |
| EP1887108A1 (en) | 2008-02-13 |
| WO2006126518A1 (en) | 2006-11-30 |
| US20090095633A1 (en) | 2009-04-16 |
| KR20070118694A (en) | 2007-12-17 |
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