CN114606410A - Cu-Ni-Si-based copper alloy strip and method for producing same - Google Patents
Cu-Ni-Si-based copper alloy strip and method for producing same Download PDFInfo
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- CN114606410A CN114606410A CN202210264105.2A CN202210264105A CN114606410A CN 114606410 A CN114606410 A CN 114606410A CN 202210264105 A CN202210264105 A CN 202210264105A CN 114606410 A CN114606410 A CN 114606410A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 39
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims description 36
- 238000005097 cold rolling Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000005098 hot rolling Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 21
- 229920005989 resin Polymers 0.000 abstract description 21
- 239000011260 aqueous acid Substances 0.000 abstract 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract 2
- 235000010344 sodium nitrate Nutrition 0.000 abstract 1
- 239000004317 sodium nitrate Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 230000035882 stress Effects 0.000 description 9
- 229910005883 NiSi Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 229910018098 Ni-Si Inorganic materials 0.000 description 2
- 229910018529 Ni—Si Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention relates to a Cu-Ni-Si-based copper alloy strip and a method for producing the same. The invention provides a Cu-Ni-Si copper alloy strip which has improved strength, properly inhibits dirt generation and has excellent adhesion with resin and a manufacturing method thereof. The Cu-Ni-Si-based copper alloy strip of the present invention contains Ni: 1.5 to 4.5 mass%, Si: 0.4 to 1.1 mass%, and the balance of Cu and unavoidable impurities, the electric conductivity of which is 30% IACS or more, the tensile strength of which is 800MPa or more, and the amount of which is 40wt% of sodium nitrate at room temperatureImmersing in an aqueous acid solution for 10 seconds, and then adding an aqueous acid solution to the aqueous acid solution to obtain a solution having an L value defined in JIS-Z8781:2013*a*b*Luminance L in the color system*Is 50 to 75.
Description
Technical Field
The present application is a divisional application of PCT application with application number 201880022125.0 (international application date is 2018, 03, 23), entitled "Cu — Ni — Si based copper alloy strip and method for manufacturing the same", which is at the state of entry. The present invention relates to a Cu — Ni — Si-based copper alloy strip which can be suitably used for manufacturing electronic components such as electronic materials, and a method for manufacturing the same.
Background
In recent years, with the miniaturization of IC packages, there has been a demand for the miniaturization and further increase in the number of pins of lead frames, various terminals of electronic devices, connectors, and the like. In particular, a structure called QFN (Quad Flat Non-leaded package) has been developed in which an electrode pad is disposed on a ground pad of an LSI package without exposing a lead pin, and a multi-pin and a narrow pitch have been demanded. In order to make the lead frame and the like have a plurality of leads, it is necessary to perform fine processing by etching, and therefore, it is required to improve the strength of the copper alloy as a material, and to improve etching properties, plating adhesion properties, resin adhesion properties, and the like. From this situation, an age-precipitation type Cu-Ni-Si copper alloy has been developed.
However, when a Cu — Ni — Si copper alloy is used for an electronic component such as a lead frame, pickling is performed as a pretreatment, but a Ni — Si compound is oxidized at the time of pickling and sometimes remains on the surface of the material as dirt. When the amount of the residue of the dirt increases, the residue may be sandwiched between the lead frame and the mold resin during the assembly process of the IC package, thereby reducing the adhesion of the resin or the adhesion of the solder or plating.
Thus, the following techniques are proposed: the particle size of Ni — Si precipitates of a Cu — Ni — Si copper alloy is controlled, and the contents of Ni and Si are limited to suppress the residue of contaminants during pickling, thereby improving solder adhesion and plating properties (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 8-319527.
Disclosure of Invention
Problems to be solved by the invention
However, in the case of the technique described in patent document 1, in order to improve solder adhesion and plating properties, it is desired to remove almost completely the dirt of the NiSi particles by acid washing. Therefore, there are problems as follows: the surface of the material exposed after pickling hardly generates unevenness due to the precipitates, and the anchoring effect by the unevenness is reduced, and the adhesion to the resin is poor. Therefore, for example, the adhesion between the lead frame and the mold resin in the assembly process of the IC package is affected.
That is, the present invention has been made to solve the above problems, and an object thereof is to provide a Cu — Ni — Si-based copper alloy strip having improved strength, suitably suppressed generation of stain, and excellent adhesion to a resin, and a method for producing the same.
Means for solving the problems
The present inventors have conducted various studies and, as a result, have found that: in the pickling of the Cu — Ni — Si-based copper alloy strip, although the adhesion to the resin is reduced in a state where the stain is excessively generated until the stain is layered, even if the stain is excessively removed, the unevenness due to the NiSi precipitates is eliminated, the anchoring effect due to the unevenness is reduced, and the adhesion to the resin is reduced. In other words, it was found that: by appropriately leaving the stain during the pickling, unevenness on the surface remains, and the adhesion to the resin improves. In addition, the following findings are provided: as a method for suppressing the generation of the stain in this way, the solution treatment conditions in the production of the copper alloy strip are adjusted.
That is, the Cu — Ni — Si-based copper alloy strip of the present invention contains Ni: 1.5 to 4.5 mass%, Si: 0.4 to 1.1 mass%, the balance being Cu and unavoidable impurities, an electrical conductivity of 30% IACS or more and a tensile strength of 800MPa or more, immersing the alloy in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then adding L specified in JIS-Z8781:2013*a*b*Luminance L in the color system*Is 50 to 75.
Further, it is preferable to contain 0.005 to 0.8 mass% in total of at least one selected from the group consisting of Mg, Fe, P, Mn, Co and Cr.
In the method for producing a Cu — Ni — Si-based copper alloy strip of the present invention, the Cu — Ni — Si-based copper alloy strip containing Ni: 1.5 to 4.5 mass%, Si: 0.4 to 1.1 mass% and the balance of Cu and unavoidable impurities, and then hot rolling and cold rolling the ingot, and then performing solutionizing treatment and aging treatment in order, further performing aging treatment at a working degree of 40% or more, and then cold rolling, and adjusting the solutionizing treatment so that the ingot is to be processed into a productAfter the solution treatment and before the aging treatment, the material was immersed in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then measured for L as defined in JIS-Z8781:2013*a*b*Luminance L in the color system*The time is 40-70.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a Cu — Ni — Si-based copper alloy strip having high strength, suitably suppressing the generation of stains, and excellent adhesion to a resin can be obtained.
Detailed Description
Hereinafter, a Cu — Ni — Si based copper alloy strip according to an embodiment of the present invention will be described. In the present invention,% represents mass% unless otherwise specified.
First, the reason for limiting the composition of the copper alloy strip will be described.
< Ni and Si >
By aging Ni and Si, Ni and Si are formed into fine Ni2The precipitation particles of the intermetallic compound mainly containing Si significantly increase the strength of the alloy. In addition, with Ni in aging treatment2Si precipitates and the conductivity is improved. However, when the Ni concentration is less than 1.5% or the Si concentration is less than 0.4%, the desired strength cannot be obtained even if another component is added. In addition, when the Ni concentration exceeds 4.5% or the Si concentration exceeds 1.1%, sufficient strength can be obtained, but the conductivity is low, and coarse Ni — Si-based particles (crystals and precipitates) that do not contribute to strength improvement are generated in the matrix phase, resulting in a reduction in bending workability, etching properties, and plating properties. Therefore, the Ni content is set to 1.5 to 4.5%, and the Si content is set to 0.4 to 1.1%. Preferably, the Ni content is 1.6 to 3.0%, and the Si content is 0.4 to 0.7%.
< other elements >
Further, the alloy may further contain 0.005 to 0.8 mass% in total of at least one selected from the group consisting of Mg, Fe, P, Mn, Co and Cr for the purpose of improving the strength, heat resistance, stress relaxation resistance and the like of the alloy. If the total amount of these elements is less than 0.005% by mass, the above-described effects are not produced, and if it exceeds 0.8% by mass, the conductivity and bending workability may be lowered although desired characteristics can be obtained.
< conductivity and tensile Strength TS >
The Cu-Ni-Si-based copper alloy strip according to the embodiment of the present invention has an electrical conductivity of 30% IACS or more and a tensile strength TS of 800MPa or more.
Since heat generation by energization increases as the operating frequency of the semiconductor element increases, the conductivity of the copper alloy strip is set to 30% IACS or more.
The tensile strength TS is set to 800MPa or more in order to prevent deformation of the lead frame during wire bonding and to maintain the shape.
<Luminance L*>
The Cu-Ni-Si copper alloy strip according to the embodiment of the present invention is immersed in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then subjected to L treatment as defined in JIS Z8781:2013*a*b*Luminance L in the color system*Is 50 to 75.
When a sample is immersed in a nitric acid aqueous solution, stains are generated and remain on the surface of the sample, and the color of the surface of the sample becomes dark. Therefore, by measuring the color tone of the sample surface, it is possible to determine whether or not stains have been generated.
If the brightness L is*When the color is close to 0, the color becomes black, and when the color is close to 100, the color becomes white.
Luminance L obtained by immersing Cu — Ni — Si-based copper alloy strip according to embodiment of the present invention in an aqueous nitric acid solution*The surface roughness is 50 to 75, and the surface of the pickled material has an uneven surface with a moderate amount of NiSi precipitates left thereon, and the adhesion between the resin and the material is improved by the anchor effect.
On the other hand, if the brightness L is*If the amount is less than 50, a large amount of dirt is generated after pickling to cover the surface of the material in a layered form, and the dirt layer and the copper alloy layer are peeled off, thereby reducing the adhesion of the resin. Luminance L*When the amount exceeds 75, the stain is excessively removed by the acid cleaning, and NiSi precipitates on the surface are reduced, resulting in reduced surface irregularities. As a result, the anchoring effect is not obtained or the surface area of the copper alloy (matrix) on the surface of the material is increased to promote CuThe oxide film grows, and the oxide film peels off, and the adhesion to the resin is lowered.
As the brightness L of the copper alloy strip*The control to 50 to 75 may be performed by adjusting the solution treatment conditions described later. The conditions for the solutionizing treatment will be described in detail later.
< production of Cu-Ni-Si based copper alloy strip >
The Cu — Ni — Si-based copper alloy strip according to the embodiment of the present invention can be usually produced by subjecting an ingot to hot rolling, cold rolling, solutionizing, aging, cold rolling after aging, and stress relief annealing in this order. The cold rolling before the solutionizing treatment is not essential, and may be performed as needed. Further, cold rolling may be performed after the solutionizing treatment and before the aging treatment, as necessary. Grinding, polishing, shot blasting, pickling, and the like for removing the surface scale may be appropriately performed between the above steps.
The solution treatment is a heat treatment for dissolving a silicide such as a Ni — Si compound in a Cu matrix and recrystallizing the Cu matrix.
In the method for producing a Cu-Ni-Si-based copper alloy strip according to the embodiment of the present invention, the solution treatment conditions are adjusted so that the material after the solution treatment and before the aging treatment is immersed in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then L is measured as defined in JIS-Z8781:2013*a*b*Luminance L in the color system*The time is 40-70.
By adjusting the solution treatment conditions as described above, Ni and Si which cause contamination are moderately dissolved in Cu, and the amount of NiSi precipitates is controlled to be small or large, whereby the brightness L of the obtained Cu-Ni-Si based copper alloy strip can be adjusted*Controlling the temperature to 50-75.
Brightness L of the solutionized material*If the amount is less than 40, the solution treatment is insufficient, and the amount of NiSi precipitates as contaminants becomes excessive.
Brightness L of the solutionized material*When the amount exceeds 70, the solution treatment becomes excessive, and the amount of NiSi precipitates as contaminants becomes too small.
The temperature and time of the solutionizing treatment may be controlled to change the solutionizing treatment conditions, but the specific temperature and time of the solutionizing treatment are not specified because: the amount and particle size of the Ni — Si compound before the solution treatment vary depending on the amount of Ni, Si, and the like added to the copper alloy strip and the conditions of the pre-step of the solution treatment.
< aging treatment >
In the aging treatment, a silicide which is solid-dissolved by the solution treatment is made to be Ni2Fine particles of an intermetallic compound mainly containing Si are precipitated. The strength and conductivity are improved by the aging treatment. The aging treatment can be performed, for example, under conditions of 375 to 625 ℃ for 1 to 50 hours, thereby improving the strength.
When the aging time is less than 1 hour, the amount of Ni-Si precipitates precipitated may be small and the strength may be insufficient. When the aging temperature exceeds 625 ℃ or the aging time exceeds 50 hours, precipitates may be coarsened and resolubilized, the amount of generation of dirt may increase, the strength may become insufficient, and the electrical conductivity may decrease.
< Cold Rolling >
Next, after the aging treatment, cold rolling is performed at a reduction ratio of 40% or more (cold rolling after the aging treatment).
When cold rolling is performed with a degree of working of 40% or more, the tensile strength is increased to 800MPa or more by work hardening.
If the degree of working is less than 40%, the strength may be insufficient.
More preferably, the steel sheet is cold-rolled after aging treatment at a working ratio of 40 to 90%. When the degree of working exceeds 90%, the electric conductivity may be significantly reduced by working strain, and even if stress relief annealing is performed, the electric conductivity may be low.
The cold rolling reduction after the aging treatment is the rate of change in the thickness of the cold rolled sheet after the aging treatment with respect to the thickness of the cold rolled sheet immediately before the cold rolling after the aging treatment.
The thickness of the Cu-Ni-Si based copper alloy strip of the present invention is not particularly limited, and may be, for example, 0.03 to 0.6 mm.
< stress relief annealing >
Stress relief annealing may be performed after cold rolling after the aging treatment. The stress relief annealing may be performed under a common condition, and may be performed, for example, at 300 to 550 ℃ for a holding time of 5 to 300 seconds. Thereby enabling removal of residual stresses within the material.
Example 1
Samples of each example and each comparative example were produced as follows.
A copper alloy having a composition shown in tables 1 and 2 was melted in an air melting furnace using electrolytic copper as a raw material, and cast into an ingot having a thickness of 20mm × a width of 60 mm. The ingot was hot-rolled at 950 ℃ until the thickness became 10 mm. After hot rolling, grinding is performed in sequence, and cold rolling is performed.
Next, under the conditions shown in tables 1 and 2, the solutionizing treatment and the aging treatment were performed in this order. Thereafter, the steel sheet was subjected to aging treatment at the working degrees shown in tables 1 and 2, then cold-rolled to a thickness of 0.150mm, and stress relief annealing was performed at 450 ℃ for 30 seconds, thereby obtaining samples.
< conductivity (% IACS) >
The obtained sample was measured for electrical conductivity (% IACS) at 25 ℃ by a four-terminal method in accordance with JIS H0505.
< Tensile Strength (TS) >
The Tensile Strength (TS) in the direction parallel to the rolling direction of each of the obtained samples was measured by a tensile tester in accordance with JIS-Z2241. First, a JIS13B test piece was prepared from each sample using a press machine so that the stretching direction was the rolling direction. The conditions for the tensile test were: the test piece has a width of 12.7mm, a room temperature (15-35 ℃), a drawing speed of 5mm/min, and a measurement length of 50 mm.
<Luminance L*>
One surface of the sample after the solution treatment and before the aging treatment and the sample after the stress relief annealing was immersed in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then rinsed with running water. The brightness L was obtained for the treated sample surface by using a color difference meter.
The color difference meter was used for measurement using CR-200 manufactured by KONICA MINOLTA INC.
< adhesion to resin >
The stress-relieved annealed sample was cut into a length of 100mm and a width of 20mm in the direction parallel to the rolling direction, immersed in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds on one surface of the sample, and then rinsed with running water. Next, the sample was heated at 240 ℃ for 5 minutes in the atmosphere. After heating in the air, the acid-resistant tape was adhered to the above-mentioned one surface in a length of 60mm, and then peeled off, and the presence or absence of the adhering matter on the adhering surface of the acid-resistant tape was determined by image processing. Specifically, the image of the adhesive surface of the acid-resistant tape was binarized, and the ratio of the total area of the black image region to be attached matter to the area of the adhesive surface of the acid-resistant tape was calculated and evaluated according to the following criteria. When evaluated as O, the adhesion to the resin is excellent.
O: the total area of the attachments is 10% or less of the area of the adhesive surface of the adhesive tape
X: the total area of the attachments is more than 10% of the area of the adhesive surface of the adhesive tape
The results are shown in Table 1.
As is clear from table 1: at a luminance L*In each of the examples of 50 to 75, the strength was high and the adhesion to the resin was excellent.
On the other hand, at a luminance L*In the case of comparative example 1 in which the amount exceeds 75, the adhesion to the resin is poor. This is considered to be because: the amount of NiSi precipitates on the surface of the material was too small, Cu on the surface was significantly oxidized, and the surface oxide film was peeled off, thereby reducing the adhesion to the resin.
At a luminance L*In comparative example 2 having a particle size of less than 50, the amount of stain generated increased, and the adhesion to the resin was poor.
In comparative example 3 in which the cold rolling degree after the aging treatment exceeded 90%, the electric conductivity was less than 30% IACS.
In comparative example 4 in which the cold rolling workability after the aging treatment was less than 40%, the tensile strength was less than 800 MPa.
In comparative example 5 in which the contents of Ni and Si exceed the predetermined ranges, the conductivity was less than 30% IACS.
In the case of comparative example 7 containing more than 0.8 mass% in total of one or more selected from Mg, Fe, P, Mn, Co and Cr, the conductivity was less than 30% IACS.
In the case of comparative example 8 in which the aging temperature was less than 625 ℃ and comparative example 10 in which the aging time was less than 1 hour, the aging was inferior and the tensile strength was less than 800 MPa.
In the case of comparative example 9 in which the aging temperature exceeded 625 ℃ and comparative example 11 in which the aging time exceeded 50 hours, overaging was exhibited, and the tensile strength was less than 800 MPa. In addition, the Ni-Si precipitates were significantly precipitated by the overaging, and the luminance L was obtained*When the amount is less than 50, the amount of stain generated increases, and the adhesion to the resin is poor.
Claims (3)
1. A Cu-Ni-Si-based copper alloy strip containing Ni: 1.5 to 4.5 mass%, Si: 0.4 to 1.1 mass%, and the balance consisting of Cu and unavoidable impurities,
an electric conductivity of 30% IACS or more, a tensile strength of 800MPa or more,
immersing the resultant in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then, adjusting the pH to L as defined in JIS-Z8781:2013*a*b*Luminance L in the color system*Is 50 to 75.
2. The Cu-Ni-Si based copper alloy strip according to claim 1, further comprising 0.005 to 0.8 mass% in total of at least one selected from the group consisting of Mg, Fe, P, Mn, Co and Cr.
3. A method for producing a Cu-Ni-Si-based copper alloy strip, wherein a Cu-Ni-Si-based copper alloy strip containing Ni: 1.5 to 4.5 mass%, Si: 0.4 to 1.1 mass% and the balance of Cu and unavoidable impurities, hot rolling and cold rolling an ingot of a Cu-Ni-Si copper alloy strip, then subjecting the ingot to solutionizing treatment and aging treatment in this order, further subjecting the ingot to aging treatment at a working degree of 40% or more, and then cold rolling,
the solutionizing treatment is adjusted so that the material after the solutionizing treatment and before the aging treatment is immersed in a 40wt% nitric acid aqueous solution at room temperature for 10 seconds, and then L specified in JIS-Z8781:2013 is measured*a*b*Luminance L in the color system*The time is 40-70.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-067999 | 2017-03-30 | ||
| JP2017067999A JP6811136B2 (en) | 2017-03-30 | 2017-03-30 | Cu-Ni-Si based copper alloy strip and its manufacturing method |
| CN201880022125.0A CN110446796A (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si series copper alloy strip and its manufacturing method |
| PCT/JP2018/011573 WO2018180940A1 (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si-BASED COPPER ALLOY STRIP AND METHOD FOR MANUFACTURING SAME |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880022125.0A Division CN110446796A (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si series copper alloy strip and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114606410A true CN114606410A (en) | 2022-06-10 |
Family
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Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311529623.3A Pending CN117551910A (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si copper alloy strip and method for producing same |
| CN201880022125.0A Pending CN110446796A (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si series copper alloy strip and its manufacturing method |
| CN202210264105.2A Pending CN114606410A (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si-based copper alloy strip and method for producing same |
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| CN201880022125.0A Pending CN110446796A (en) | 2017-03-30 | 2018-03-23 | Cu-Ni-Si series copper alloy strip and its manufacturing method |
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| JP (1) | JP6811136B2 (en) |
| KR (1) | KR102285168B1 (en) |
| CN (3) | CN117551910A (en) |
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| KR102640972B1 (en) | 2021-05-28 | 2024-02-23 | 부산대학교 산학협력단 | Manufacturing method for copper with surface coated silicon, copper with permanent oxidation resistance by silicon-coated surface thereof and semiconductor system thereof |
| JPWO2023167230A1 (en) | 2022-03-04 | 2023-09-07 | ||
| KR20230153296A (en) | 2022-04-28 | 2023-11-06 | 부산대학교 산학협력단 | Nickel with permanent oxidation resistance by silicon-coated surface and manufacturing method for nickel with permanent oxidation resistance by silicon-coated surface |
| KR20230153295A (en) | 2022-04-28 | 2023-11-06 | 부산대학교 산학협력단 | Iron with permanent oxidation resistance by silicon-coated surface and manufacturing method for iron with permanent oxidation resistance by silicon-coated surface |
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| JP3056394B2 (en) | 1995-05-25 | 2000-06-26 | 株式会社神戸製鋼所 | Copper alloy excellent in solder adhesion and plating properties and easy to clean, and method for producing the same |
| JP5468423B2 (en) * | 2010-03-10 | 2014-04-09 | 株式会社神戸製鋼所 | High strength and high heat resistance copper alloy material |
| JP6223057B2 (en) * | 2013-08-13 | 2017-11-01 | Ｊｘ金属株式会社 | Copper alloy sheet with excellent conductivity and bending deflection coefficient |
| JP6301618B2 (en) * | 2013-09-17 | 2018-03-28 | 古河電気工業株式会社 | Copper alloy material and method for producing the same |
| TWI621721B (en) * | 2014-07-10 | 2018-04-21 | Furukawa Electric Co Ltd | Copper alloy sheet, connector, and method for manufacturing copper alloy sheet |
| JP6328166B2 (en) * | 2015-03-30 | 2018-05-23 | Ｊｘ金属株式会社 | Cu-Ni-Si rolled copper alloy and method for producing the same |
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2017
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| KR20190112059A (en) | 2019-10-02 |
| TWI647320B (en) | 2019-01-11 |
| CN110446796A (en) | 2019-11-12 |
| JP2018168437A (en) | 2018-11-01 |
| JP6811136B2 (en) | 2021-01-13 |
| CN117551910A (en) | 2024-02-13 |
| KR102285168B1 (en) | 2021-08-04 |
| TW201840870A (en) | 2018-11-16 |
| WO2018180940A1 (en) | 2018-10-04 |
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