JP5138170B2 - Copper alloy plastic working material and method for producing the same - Google Patents

Description

  The present invention relates to a plastic work material made of a fine crystal grain copper alloy obtained by cold working and / or hot working a Cu-Sn copper alloy or Cu-Sn-Zn copper alloy, and a method for producing the same. .

  As the copper alloy containing Sn, in general, phosphor bronze defined by JIS H3110, H3270 C5111, C5102, C5191, C5212, JIS H5120 CAC502A, CAC502B, JIS H3100 C4250, C4430, etc. are well known. There are drawbacks such as inferior workability or castability in hot or cold, and the use has been greatly limited. Such a defect is attributed to the inclusion of Sn, which is a low melting point metal, mainly due to macro segregation of Sn.

  By the way, as an effective means for eliminating such macro segregation of Sn, it is conceivable to refine crystal grains.

  Thus, as a basic form in which the crystal grain size of the copper alloy is refined, generally, (A) the crystal grain is refined when the copper alloy is melt-solidified, and (B) the copper alloy (ingot after melt-solidification) , Ingots such as slabs, cast products such as die casts, and melt cast products) are subjected to deformation processing such as rolling or heat treatment, so that the stored energy such as strain energy becomes the driving force to refine crystal grains In both cases (A) and (B), Zr is known as an element that effectively acts on the refinement of crystal grains.

  However, in the case of (A), the crystal grain refining action of Zr in the melt-solidification stage is greatly influenced by other elements and their contents, so that the desired level of crystal grain refinement is not achieved. It is a fact. For this reason, in general, the method (B) is widely used, and heat treatment is performed on the ingot and cast product after being melted and solidified to further refine the crystal grains. Has been done.

For example, JP-B-38-20467 may, Zr, P, and water quenched after solution treatment lines Tsu Na at 800 ° C. in a copper alloy containing Ni, facilities cold working and then at 75% of working ratio In addition, the average crystal grain size after the heat treatment was examined. From 280 μm when Zr is not contained, 170 μm (Zr: 0.05 mass% contained), 50 μm (Zr: 0.13 mass% contained), It teaches that it is refined in proportion to the increase in the Zr content, such as 29 μm (Zr: 0.22 mass% contained) and 6 μm (Zr: 0.89 mass% contained). In this publication, it is proposed to contain 0.05 to 0.3 mass% of Zr in order to avoid an adverse effect due to excessive Zr content.

Further , referring to Japanese Patent Application Laid-Open No. 2004-100042 , when a copper alloy containing 0.15 to 0.5 mass% of Zr is subjected to deformation treatment for solution treatment and strain addition after casting, an average crystal It is disclosed that the particle size is refined to a level of about 20 μm or less.

Japanese Patent Publication No. 38-20467 JP 2004-100042 A

  However, as in the method (B), it is expensive to perform these treatments and processing after casting in order to reduce the crystal grain size. In addition, depending on the shape of the cast product, there are some that cannot be deformed to add strain. For this reason, it is preferable that the crystal grains are refined by the method (A) when the copper alloy is melted and solidified. However, in the case of the method (A), as described above, Zr in the melt-solidification stage is greatly affected by other elements and their contents. Therefore, even if the Zr content is increased, the increase in the Zr content is increased. It is not always possible to obtain a crystal grain refinement effect corresponding to the above. Moreover, since Zr has a very strong affinity for oxygen, when Zr is added by dissolution in the atmosphere, it is likely to be an oxide and has a very poor yield. For this reason, even if the amount contained in the product after casting is a small amount, it is necessary to input a considerable amount of raw material at the casting stage. On the other hand, if the amount of oxide generated during dissolution is too large, the oxide is likely to be caught during casting, which may cause casting defects. In addition, in order to avoid the production | generation of an oxide, although melt | dissolution and casting can be performed in a vacuum or inert gas atmosphere, it causes a high cost.

The present invention provides a significant improvement in strength, workability, etc. due to the refinement of crystal grains without causing the above-mentioned problems when the crystal grains are refined when the copper alloy is melted and solidified by the method (A). It is an object of the present invention to provide a copper alloy plastic working material capable of achieving the above and a production method capable of suitably producing it.

The present invention firstly proposes first to fourth plastic working materials made of Cu-Sn copper alloy as follows.

That is, the first plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less, which has the composition of (1) and (9) described later, to an α phase area ratio of 94.5. % Or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more) and the total area ratio of the γ phase, δ phase and ε phase is 5% or less (preferably 3.5% Hereinafter, it has a metal structure that is more preferably 1.5% or less, and most preferably 0.5% or less), and has a crystal structure with an average crystal grain size of 150 μm or less. In the present invention, the content of each phase, that is, the area ratio, is measured by image analysis. Specifically, a 200-fold optical microscope tissue is obtained with image processing software “WinROOF” (Tech Jam Co., Ltd.). It is obtained by binarization and is an average value of area ratios measured in three visual fields. In the following description, [a] indicates a content value of the element a, and the content of the element a is expressed by [a] mass%.

The second plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less, which has the composition of (2), (9), and (11) described later, to an area ratio of α phase. 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5% or less (preferably 3 0.5% or less, more preferably 1.5% or less, optimally 0.5% or less), and a crystal structure having an average crystal grain size of 150 μm or less.

Further, the third plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less, which has a composition of (3), (9), and (12) described later, to an area ratio of α phase. 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5% or less (preferably 3 0.5% or less, more preferably 1.5% or less, optimally 0.5% or less), and a crystal structure having an average crystal grain size of 150 μm or less.

The fourth plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less, which has the composition of (4), (9), (11), and (12) described later, to α-phase. The area ratio is 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5% or less ( The metal structure is preferably 3.5% or less, more preferably 1.5% or less, and most preferably 0.5% or less, and has a crystal structure with an average crystal grain size of 150 μm or less.

  Secondly, the present invention proposes fifth to eighth plastic working materials made of a Cu—Sn—Zn copper alloy as follows.

That is, the fifth plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less having the composition of (5), (9), and (10), which will be described later, to an α phase area ratio. 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5% or less (preferably 3 0.5% or less, more preferably 1.5% or less, optimally 0.5% or less), and a crystal structure having an average crystal grain size of 150 μm or less.

The sixth plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less, which has the composition of (6), (9), (10), and (11) described later, to α-phase. The area ratio is 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5% or less ( The metal structure is preferably 3.5% or less, more preferably 1.5% or less, and most preferably 0.5% or less, and has a crystal structure with an average crystal grain size of 150 μm or less.

The seventh plastic working material is obtained by subjecting a casting material having an average crystal grain size of 300 μm or less, which has the composition of (7), (9), (10), and (12) described later, to α-phase. The area ratio is 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5% or less ( The metal structure is preferably 3.5% or less, more preferably 1.5% or less, and most preferably 0.5% or less, and has a crystal structure with an average crystal grain size of 150 μm or less.

The eighth plastic work material is obtained by subjecting a cast material having an average crystal grain size of 300 μm or less, which has the composition of (8), (9), (10), (11), and (12) described later, to plastic processing, The area ratio of the α phase is 94.5% or more (preferably 96% or more, more preferably 98% or more, optimally 99.5% or more), and the total area ratio of the γ phase, δ phase, and ε phase is 5 % Or less (preferably 3.5% or less, more preferably 1.5% or less, optimally 0.5% or less), and a crystal structure having an average crystal grain size of 150 μm or less. is there.

(1) Sn: 4.2 ~15mass% ( preferably 4.2 ~13mass%, more preferably 4.2 ~12.5mass%, optimally 4.2 ~12mass%) and, Zr: 0.001 ~0.049mass% (preferably 0.0015~0.039mass%, more preferably 0.002~0.029mass%, optimally 0.003~0.019mass%) and, P: 0.01 to 0 consisting of the balance: .14 mass% (preferably 0.015 to 0.14 mass%, more preferably 0.02 to 0.14 mass%, and optimally 0.03~0.13mass%) and, Cu Making a composition.

(2) Sn: 4.2 ~15mass% ( preferably 4.2 ~13mass%, more preferably 4.2 ~12.5mass%, optimally 4.2 ~12mass%) and, Zr: 0.001 ~0.049mass% (preferably 0.0015~0.039mass%, more preferably 0.002~0.029mass%, optimally 0.003~0.019mass%) and, P: 0.01 to 0 .14 mass% (preferably 0.015 to 0.14 mass%, more preferably 0.02 to 0.14 mass%, and optimally 0.03~0.13mass%) and, Ti: 0.002 to 0.049 mass% (preferably 0.003-0.039 mass%, optimally 0.005-0.029 mass%), Hf: 0.002-0.049 mass% ( Preferably 0.003-0.039 mass%, optimally 0.005-0.029 mass%), B: 0.001-0.03 mass% (preferably 0.0015-0.025 mass%, optimally 0.002 to 0.02 mass%), Mg: 0.001 to 0.3 mass% (preferably 0.005 to 0.2 mass%, optimally 0.01 to 0.1 mass%), Mn: 0.03 ~ 1 mass% (preferably 0.05 to 0.7 mass%, optimally 0.1 to 0.5 mass%) and Al: 0.01 to 1 mass% (preferably 0.02 to 0.8 mass%, more preferably 0.05 to 0.5 mass%), As: 0.02 to 0.2 mass% (preferably 0.025 to 0.15 mass%, optimally 0.03 to 0.1 mass%), and Sb: A composition comprising one or more elements selected from 0.02 to 0.2 mass% (preferably 0.025 to 0.15 mass%, optimally 0.03 to 0.1 mass%), and Cu: the balance. To do.

(3) Sn: 4.2 ~15mass% ( preferably 4.2 ~13mass%, more preferably 4.2 ~12.5mass%, optimally 4.2 ~12mass%) and, Zr: 0.001 ~0.049mass% (preferably 0.0015~0.039mass%, more preferably 0.002~0.029mass%, optimally 0.003~0.019mass%) and, P: 0.01 to 0 .14 mass% (preferably 0.015 to 0.14 mass%, more preferably 0.02 to 0.14 mass%, and optimally 0.03~0.13mass%) and, Fe: 0.01 to 0.2 mass% (preferably 0.02 to 0.15 mass%, optimally 0.03 to 0.1 mass%), Co: 0.01 to 0.2 mass% (preferably 0.02 to 0) 15 mass%, optimally 0.03-0.1 mass%) and Si: 0.01-0.8 mass% (preferably 0.03-0.5 mass%, optimally 0.05-0.3 mass%) The composition which consists of 1 or more types of elements selected from these, and Cu: remainder.

(4) Sn: 4.2 ~15mass% ( preferably 4.2 ~13mass%, more preferably 4.2 ~12.5mass%, optimally 4.2 ~12mass%) and, Zr: 0.001 ~0.049mass% (preferably 0.0015~0.039mass%, more preferably 0.002~0.029mass%, optimally 0.003~0.019mass%) and, P: 0.01 to 0 .14 mass% (preferably 0.015 to 0.14 mass%, more preferably 0.02 to 0.14 mass%, and optimally 0.03~0.13mass%) and, Ti: 0.002 to 0.049 mass% (preferably 0.003-0.039 mass%, optimally 0.005-0.029 mass%), Hf: 0.002-0.049 mass% ( Preferably 0.003-0.039 mass%, optimally 0.005-0.029 mass%), B: 0.001-0.03 mass% (preferably 0.0015-0.025 mass%, optimally 0.002 to 0.02 mass%), Mg: 0.001 to 0.3 mass% (preferably 0.005 to 0.2 mass%, optimally 0.01 to 0.1 mass%), Mn: 0.03 ~ 1 mass% (preferably 0.05 to 0.7 mass%, optimally 0.1 to 0.5 mass%) and Al: 0.01 to 1 mass% (preferably 0.02 to 0.8 mass%, more preferably 0.05 to 0.5 mass%), As: 0.02 to 0.2 mass% (preferably 0.025 to 0.15 mass%, optimally 0.03 to 0.1 mass%), and Sb: 0 One or more elements selected from 0.02 to 0.2 mass% (preferably 0.025 to 0.15 mass%, optimally 0.03 to 0.1 mass%), and Fe: 0.01 to 0. 2 mass% (preferably 0.02-0.15 mass%, optimally 0.03-0.1 mass%), Co: 0.01-0.2 mass% (preferably 0.02-0.15 mass%, optimal Selected from 0.03 to 0.1 mass%) and Si: 0.01 to 0.8 mass% (preferably 0.03 to 0.5 mass%, optimally 0.05 to 0.3 mass%). The composition which consists of 1 or more types of elements and Cu: remainder is made.

(5) Sn: 0.2-15 mass% (preferably 0.6-13 mass%, more preferably 1.5-12.5 mass%, optimally 2-12 mass%), and Zr: 0.001-0 0.049 mass% (preferably 0.0015 to 0.039 mass%, more preferably 0.002 to 0.029 mass%, optimally 0.003 to 0.019 mass%), and P: 0.01 to 0.25 mass % (Preferably 0.015-0.2 mass%, more preferably 0.02-0.18 mass%, optimally 0.03-0.13 mass%) and Zn: 0.01-35 mass% (preferably 0.05 to 31 mass%, more preferably 0.3 to 27 mass%, and most preferably 4 to 15 mass%), and Cu: the balance.

(6) Sn: 0.2-15 mass% (preferably 0.6-13 mass%, more preferably 1.5-12.5 mass%, optimally 2-12 mass%), and Zr: 0.001-0 0.049 mass% (preferably 0.0015 to 0.039 mass%, more preferably 0.002 to 0.029 mass%, optimally 0.003 to 0.019 mass%), and P: 0.01 to 0.25 mass % (Preferably 0.015-0.2 mass%, more preferably 0.02-0.18 mass%, optimally 0.03-0.13 mass%) and Zn: 0.01-35 mass% (preferably 0.05 to 31 mass%, more preferably 0.3 to 27 mass%, optimally 4 to 15 mass%) and Ti: 0.002 to 0.049 mass% (preferably 0.003-0.039 mass%, optimally 0.005-0.029 mass%), Hf: 0.002-0.049 mass% (preferably 0.003-0.039 mass%, optimally 0) 0.005 to 0.029 mass%), B: 0.001 to 0.03 mass% (preferably 0.0015 to 0.025 mass%, optimally 0.002 to 0.02 mass%), Mg: 0.001 to 0.3 mass% (preferably 0.005 to 0.2 mass%, optimally 0.01 to 0.1 mass%), Mn: 0.03 to 1 mass% (preferably 0.05 to 0.7 mass%, optimal 0.1 to 0.5 mass%) and Al: 0.01 to 1 mass% (preferably 0.02 to 0.8 mass%, more preferably 0.05 to 0.5 mass%) , As: 0.02-0.2 mass% (preferably 0.025-0.15 mass%, optimally 0.03-0.1 mass%) and Sb: 0.02-0.2 mass% (preferably 0 0.025 to 0.15 mass%, optimally 0.03 to 0.1 mass%) and a composition comprising Cu: the balance.

(7) Sn: 0.2-15 mass% (preferably 0.6-13 mass%, more preferably 1.5-12.5 mass%, optimally 2-12 mass%), and Zr: 0.001-0 0.049 mass% (preferably 0.0015 to 0.039 mass%, more preferably 0.002 to 0.029 mass%, optimally 0.003 to 0.019 mass%), and P: 0.01 to 0.25 mass % (Preferably 0.015-0.2 mass%, more preferably 0.02-0.18 mass%, optimally 0.03-0.13 mass%) and Zn: 0.01-35 mass% (preferably 0.05 to 31 mass%, more preferably 0.3 to 27 mass%, optimally 4 to 15 mass%) and Fe: 0.01 to 0.2 mass% (preferably 0.02-0.15 mass%, optimally 0.03-0.1 mass%), Co: 0.01-0.2 mass% (preferably 0.02-0.15 mass%, optimally 0.03 -0.1 mass%) and Si: 0.01-0.8 mass% (preferably 0.03-0.5 mass%, optimally 0.05-0.3 mass%). And a composition consisting of Cu: the balance.

(8) Sn: 0.2 to 15 mass% (preferably 0.6 to 13 mass%, more preferably 1.5 to 12.5 mass%, optimally 2 to 12 mass%), and Zr: 0.001 to 0 0.049 mass% (preferably 0.0015 to 0.039 mass%, more preferably 0.002 to 0.029 mass%, optimally 0.003 to 0.019 mass%), and P: 0.01 to 0.25 mass % (Preferably 0.015-0.2 mass%, more preferably 0.02-0.18 mass%, optimally 0.03-0.13 mass%) and Zn: 0.01-35 mass% (preferably 0.05 to 31 mass%, more preferably 0.3 to 27 mass%, optimally 4 to 15 mass%) and Ti: 0.002 to 0.049 mass% (preferred) 0.003-0.039 mass%, optimally 0.005-0.029 mass%), Hf: 0.002-0.049 mass% (preferably 0.003-0.039 mass%, optimally 0) 0.005 to 0.029 mass%), B: 0.001 to 0.03 mass% (preferably 0.0015 to 0.025 mass%, optimally 0.002 to 0.02 mass%), Mg: 0.001 to 0.3 mass% (preferably 0.005 to 0.2 mass%, optimally 0.01 to 0.1 mass%), Mn: 0.03 to 1 mass% (preferably 0.05 to 0.7 mass%, optimal 0.1 to 0.5 mass%) and Al: 0.01 to 1 mass% (preferably 0.02 to 0.8 mass%, more preferably 0.05 to 0.5 mass%) As: 0.02-0.2 mass% (preferably 0.025-0.15 mass%, optimally 0.03-0.1 mass%) and Sb: 0.02-0.2 mass% (preferably 0.00. One or more elements selected from 025 to 0.15 mass%, optimally 0.03 to 0.1 mass%) and Fe: 0.01 to 0.2 mass% (preferably 0.02 to 0.15 mass) %, Optimally 0.03-0.1 mass%), Co: 0.01-0.2 mass% (preferably 0.02-0.15 mass%, optimally 0.03-0.1 mass%) and From one or more elements selected from Si: 0.01 to 0.8 mass% (preferably 0.03 to 0.5 mass%, optimally 0.05 to 0.3 mass%), and Cu: the balance To make a composition.

(9) Regarding the content of Zr and P, the composition should satisfy the relationship of F1 = [P] / [Zr] = 0.6-36.8 ( optimally F1 = 2-30).

(10) In the case of containing Zn, there is a relationship of F2 = 3 [Sn] + [Zn] = 11.1 to 36.6 ( optimally F2 = 17.5 to 36) with respect to the contents of Sn and Zn. The composition must be established.

(11) In the case of containing at least one of Ti, Hf, B and Mg, F3 = ([P] + [Mg]) / ([Zr] +0.5 [Ti] +0.5 [Hf] + [ B]) = 0.6 to 36.8 ( optimally F3 = 2 to 30). Note that the element [a] not contained in F3 is set to [a] = 0.

(12) When Fe is contained, the relationship of F4 = ([P] −0.3 [Fe]) / [Zr] = 0.6-36.8 ( optimally F4 = 2-30) is established. The composition should be

  Thus, in the first to eighth plastic working materials, Cu is the main element of the copper alloy constituting the plastic working material or casting material, and when the content increases, the α phase can be easily obtained. The corrosion resistance (dezincification corrosion resistance, stress corrosion cracking resistance) and mechanical properties can be improved, but excessive Cu content hinders the refinement of crystal grains in the casting material. On the other hand, if the amount of Cu is too small, the primary crystal at the time of casting does not become the α phase, and many phases other than the α phase appear and hinder the refinement of crystal grains. Furthermore, although depending on the compounding ratio with Sn (Sn and Zn in the case of the fifth to eighth plastic working materials), the lower limit side of the range of Cu content is more stable corrosion resistance and erosion resistance. It is preferable to determine so as to be able to ensure, and it is also preferable to determine the upper limit side so as to ensure further strength and wear resistance. In addition, in order to refine the crystal grains, it is necessary to consider the relationship with other contained elements. From these points, the content of Cu was the balance.

In the first to eighth plastic working materials, Sn is used to refine crystal grains in the casting material, and the workpiece crystal is obtained by annealing (recrystallization annealing) in a recrystallization temperature range associated with hot working or cold working. It is intended to refine the grain. Furthermore, by containing Sn, the strength, spring limit value, corrosion resistance and wear resistance can be improved, and a plastic working material having an excellent balance between strength and ductility can be obtained. Sn alone has no significant effect, but effectively realizes refinement of crystal grains in the casting in the presence of Zr and P described later. Further, when hot working or annealing cold work is performed, Sn reduces the stacking fault energy of the copper alloy, and as a result, the number of recrystallization nucleation sites increases and the crystal grains are remarkably refined. Such an effect is exhibited by containing 0.2 mass% or more of Sn. In order to achieve finer crystal grains with Sn, it is better that the Sn content is large. However, since Sn is a low melting point metal, when Sn is contained in an amount exceeding 15 mass%, Sn content increases as the content increases. Segregation of the steel becomes remarkable, which causes a decrease in castability, hot workability, and cold workability. Even in the presence of Zr and P, ductility and castability are deteriorated, causing casting defects such as generation of cracks, shrinkage nests, and nests, and good plastic working cannot be performed. Further, Sn plays a role of expanding a composition range in which a peritectic reaction (an effective means for achieving the refinement of crystal grains at the time of melting and solidifying) occurs, and as the Sn content increases, a wide range of practical use. The peritectic reaction can be caused at a Cu concentration of 2%. Further, if Sn is contained in an amount exceeding 15 mass%, it depends on the blending ratio with Cu (Cu and Zn in the case of the fifth to eighth plastic working materials), but Sn from the parent phase (α phase). The γ phase, δ phase, and ε phase, which are hard phases having a high concentration, are excessively generated to cause selective corrosion of the phase, which may lower the corrosion resistance. Further, in the fifth to eighth plastic working materials, when the value of the relational expression F2 in (10) exceeds 30 (particularly when the Sn amount exceeds 10 mass%), the γ phase, δ phase, ε There is a possibility that a phase appears (precipitates) remarkably, and cracks are generated at the time of bending or the like starting from the precipitated portion. In order not to cause such a problem, the area ratio of the α phase is 94.5% or more (preferably 96% or more, more preferably 98% or more) in any of the first to eighth plastic working materials. 99.5% or more) and the total area ratio of the γ phase, δ phase and ε phase is 5% or less (preferably 3.5% or less, more preferably 1.5% or less, optimally 0.5 % Or less) is necessary. In consideration of these points comprehensively, in the first to fourth plastic workpiece, Sn content must be between 4.2 ~15mass%, it is kept as a 4.2 ~13mass% preferably, more preferably to keep the 4.2 ~12.5mass%, it is best to keep the 4.2 ~12mass%. In particular, in the fifth to eighth plastic working materials containing Zn, the Sn content needs to be 0.2 to 15 mass%, preferably 0.6 to 13 mass%, It is more preferable to set it to ˜12.5 mass%, and it is most preferable to set it to 2 to 12 mass%. In order to refine crystal grains of the casting material, the Sn content is taken into consideration in consideration of the relationship with Zn. Within the above range, it is necessary to determine that the relational expression F2 of (10) is established.

  In the first to eighth plastic working materials, Zr and P are co-added for the purpose of refining the crystal grains of the plastic working material, in particular, for refining the crystal grains at the time of melting and solidifying the casting material. is there. In other words, Zr and P, alone, as well as other general additive elements, can only slightly refine crystal grains, but have an extremely effective grain refinement function in the coexisting state. It is something that demonstrates.

  Such a crystal grain refining function is exhibited at 0.001 mass% or more for Zr, prominently exhibited at 0.0015 mass% or more, more prominently at 0.002 mass% or more, and 0.003 mass%. As described above, P is exhibited significantly at 0.01 mass% or more, P is exhibited significantly at 0.015 mass% or more, is exhibited more significantly at 0.02 mass% or more, and 0.03 mass. % Or more, it will be exhibited remarkably.

  On the other hand, when the Zr content reaches 0.049 mass% and the P content reaches 0.25 mass%, the crystal grains produced by co-addition of Zr and P are used regardless of the type and content of other constituent elements. However, there is a possibility that the refining function may be impaired, and it is difficult to obtain a plastic working material with fine crystal grains. Therefore, the contents of Zr and P necessary for effectively exhibiting the crystal grain refining function are required to be 0.049 mass% or less for Zr and 0.25 mass% or less for P. . In addition, Zr and P, if their content is a trace amount set in the above-described range, does not hinder the alloy characteristics exhibited by other constituent elements, but rather, by refining crystal grains, The segregated portion having a high Sn concentration can be distributed uniformly in the matrix, not continuously. As a result, it is possible to prevent casting cracks and to obtain a sound casting with little nest, shrinkage, blowhole and microporosity, and plastic workability after cold casting (cold drawing, cold drawing) Etc.) and the characteristics of the plastic working material can be further improved.

  Since Zr has a very strong affinity for oxygen, when it is melted in the atmosphere or when scrap material is used as a raw material, it is likely to be an oxide or sulfide of Zr, and Zr is added excessively. As a result, the viscosity of the molten metal is increased, and casting defects due to the inclusion of oxides and sulfides during casting occur. Blow holes and microporosity are likely to occur in the casting material, resulting in a high-quality plastic work material. It becomes difficult to obtain. In order to avoid this, melting and casting in a vacuum or a completely inert gas atmosphere can be considered. However, if this is done, the versatility is lost and the cost of copper alloys containing Zr exclusively as a refined element is greatly increased. It becomes. Considering this point, the amount of Zr that does not form an oxide or sulfide is preferably 0.039 mass% or less, more preferably 0.029 mass% or less, and 0.019 mass% or less. Is the best. Moreover, if the amount of Zr is set in such a range, even if the casting is dissolved in the air as a reusable material, the production of Zr oxides and sulfides is reduced, and the sound composed of fine crystal grains is again formed. It becomes possible to obtain the first to eighth plastic working materials.

  From these points, the Zr content needs to be 0.001 to 0.049 mass% in consideration of industrially adding a small amount of Zr, and 0.0015 to 0.039 mass%. It is preferable to set it as 0.002 to 0.029 mass%, and it is optimal to set it as 0.003 to 0.019 mass%.

Further, P is contained in order to exert the function of refining crystal grains by co-addition with Zr as described above, but also affects the corrosion resistance, castability and the like. P lowers the viscosity of the melt and lowers the interfacial energy and interfacial tension between the primary crystal and the melt (residual liquid) that crystallize in the process of solidification (solidification). In order to achieve such a state, the P amount needs to be 0.01 mass% or more, preferably 0.015 mass% or more, more preferably 0.02 mass% or more, and 0 It is optimal to set it to 0.03 mass% or more. On the other hand, even if P is contained exceeding 0.25 mass%, the effect is not only saturated, but rather, the ductility in the cold and the ductility in the hot are impaired. From this point of view, the P amount is optimally 0.14 mass% or less for the first to fourth plastic working materials, and 0.25 mass% or less for the fifth to eighth plastic working materials. Therefore, it is preferable to set it to 0.2 mass% or less, more preferably 0.18 mass% or less, and most preferably 0.14 mass% or less. Further, the crystal grains are refined in the melt-solidification stage because the crystal nucleation far exceeds the crystal growth by the function and interaction by the co-addition of P and Zr in the melt-solidified state as described above. When the value of the relational expression F1 (= [P] / [Zr]) in (9) exceeds 150 in an appropriate P and Zr content range, nucleation is not sufficiently performed and F1 <0.5. As the coalescence of crystal grains progresses, the crystal grains become network-like. From these points, it is necessary that the P amount be 0.01 to 0.14 mass% for the first to fourth plastic working materials on the condition that F1 satisfies the value of (9). It is preferably 0.015 to 0.14 mass%, more preferably 0.02 to 0.14 mass%, and most preferably 0.03 to 0.14 mass%. In the eighth plastic working material, it is necessary to be 0.01 to 0.25 mass%, preferably 0.015 to 0.2 mass%, and preferably 0.02 to 0.18 mass%. It is more preferable that 0.03 to 0.14 mass% be optimal.

  Further, the effect of refining crystal grains due to the co-addition of Zr and P is not exhibited only by individually determining the contents of Zr and P within the above-mentioned ranges, but the relationship of (9) above among these contents. It is necessary to satisfy Formula F1. Grain refinement is achieved by the fact that the nucleation rate of the primary α phase crystallized from the melt far exceeds the growth rate of the dendrite crystal. To generate such a phenomenon, Zr, It is not sufficient to determine the P content individually, and the co-addition ratio (F1 = [P] / [Zr]) needs to be considered. By determining the content of Zr and P so as to be an appropriate content ratio in an appropriate range, the crystal formation of the primary α phase can be significantly accelerated by the co-addition function or interaction of Zr and P. As a result, the nucleation of the α phase far exceeds the growth of the dendrite crystals. When the content of Zr and P is in the proper range and the blending ratio ([P] / [Zr]) is stoichiometric, the Zr and P content in the α-phase crystals can be reduced due to the small amount of Zr of about several tens of ppm. In addition, an intermetallic compound of Zr, P (for example, ZrP, ZrP1-x) may be generated, and the nucleation rate of the α phase is such that the value F1 of [P] / [Zr] is 0.5 to 150. The degree is further increased by F1 = 0.8 to 100, significantly increased by F1 = 1.2 to 60, and dramatically increased by F1 = 2 to 30. Will be enhanced. That is, the co-addition ratio F1 (= [P] / [Zr]) of Zr and P is an important factor in achieving finer crystal grains, and if F1 is in the above range, Crystal nucleation greatly exceeds crystal growth.

  In addition, when the casting material is manufactured, when solidification progresses and the proportion of the solid phase increases, crystal growth begins to occur frequently, and some of the crystal grains begin to coalesce. Grain grows larger. Here, if a peritectic reaction occurs in the process of solidification of the melt, the remaining melt without solidification reacts with the solid α phase, and a β phase is formed while eating the solid α phase. To do. As a result, the α phase is encapsulated in the β phase, the size of the α phase crystal grains themselves becomes smaller, and the shape of the α phase becomes an elliptical shape with a corner. If the solid phase becomes such a fine elliptical shape, the gas, Zr sulfide, and oxide are also likely to float, have resistance to cracking due to solidification shrinkage when solidified, and the shrinkage occurs smoothly, It also has a positive effect on various properties such as strength at normal temperature and corrosion resistance. Therefore, it is preferable that the primary crystal is the α phase when the cast material is melted and solidified, and a peritectic reaction occurs during the melt and solidification. Note that whether or not it affects the peritectic reaction generally occurs in a wider composition than the equilibrium state, unlike the equilibrium state in practice. Here, in the Cu—Sn—Zn alloy containing Zn, the relational expression F2 of the above (10) plays an important role, and the lower limit value of F2 mainly depends on the size of the crystal grains after melting and solidification. The upper limit value of F2 is mainly related to the size of the crystal after melt-solidification and the boundary value of whether the primary crystal is an α phase. As the value of F2 becomes the preferred range, the more preferred range, and the optimum range described in (10) above, the amount of the primary α phase increases, and the peritectic reaction that occurs in the non-equilibrium reaction occurs more actively. The crystal grains obtained at room temperature are getting smaller.

A series of these melt solidification phenomena naturally depends on the cooling rate. That is, when the cooling rate exceeds 10 ⁵ ° C / second, there is a risk that the crystal grains will not be refined because there is no time for nucleation of crystals, and conversely, less than 0.1 ° C / second. At this cooling rate, crystal growth is promoted, so that the crystal grains may not be refined. Further, since the equilibrium state is approached, the composition range that affects the peritectic reaction is also reduced. Therefore, in the manufacturing process (casting process) of the casting material, the casting cooling rate is 0.1 to 10 ⁵ ° C / second (preferably 0.5 to 10 ⁴ ° C / second, more preferably 5 to 10 ³ ° C / second. Seconds). Within such a range of cooling rates, the closer the cooling rate is to the upper limit, the wider the composition region in which crystal grains are refined, and the crystal grains are further refined.

  Zn contained in the fifth to eighth plastic working materials, like Sn, causes a peritectic reaction, which is an effective means for refining crystal grains when the cast material is melted and solidified. The stacking fault energy is reduced and the recrystallized grains are refined during recrystallization annealing in the plastic working process. Zn alone is not so effective, but in the presence of Zr and P, the crystal grains of the casting are further refined. Zn has a function of improving strength, spring limit value, corrosion resistance, wear resistance, and hot water flow, and is an alloy additive element having an excellent balance between strength and ductility. However, when Zn is added excessively, the primary crystal becomes β phase, the crystal grains of the casting are not refined and become brittle, and the susceptibility to stress corrosion cracking or dezincification corrosion increases. Considering these points, the Zn content needs to be 0.01 to 35 mass%, and although it depends on the Sn content, it is preferably 0.05 to 31 mass%. It is more preferable to set it to -27 mass%, and it is optimal to set it to 4-15 mass%. Further, in determining the Zn content in the above range, it is necessary to consider the relationship with the Sn content as described above in order to refine the crystal grains of the casting material. It is necessary to determine so that the relational expression F2 holds.

  Ti, Hf, and B have a function of substituting the crystal grain refining function and characteristics of Zr and P, or effectively maintaining Zr and P. The degree of crystal grain refinement effect as an alternative to Zr is equivalent to 1/2 of Zr for Hf and Ti, and is equivalent to Zr for B. However, an excessive content of Ti, Hf, and B leads to the formation of oxides and causes a problem in the soundness of the casting. In consideration of this point, when Ti, Hf, and B are contained, the content of Ti is 0 on the condition that the relational expression F3 of (11) is satisfied in relation to Zr and P. 0.002-0.049 mass% (preferably 0.003-0.039 mass%, optimally 0.005-0.029 mass%), and the Hf content is 0.002-0.049 mass% (preferably 0 0.003 to 0.039 mass%, optimally 0.005 to 0.029 mass%), and the content of B is 0.001 to 0.03 mass% (preferably 0.0015 to 0.025 mass%, optimally 0.002 to 0.02 mass%).

  Mg, Mn, and Al have a function of more effectively exerting the crystal grain refining function by Zr. That is, if Zr is in the form of sulfide and / or oxide, the function effective for refining the crystal grains cannot be sufficiently exhibited. However, Mg, Mn, and Al are not added before the addition of Zr during casting. In advance, the function of sufficiently desulfurizing or deoxidizing the molten metal is exhibited, and the amount of Zr necessary to exhibit the function of refining crystal grains is minimized. Although scrap materials (such as waste heat transfer tubes) are often used as a part of casting materials (raw materials for casting materials), such scrap materials often contain S components (sulfur components) When the S component is contained in the molten metal, Zr, which is a grain refinement element, may form a sulfide, and the effective grain refinement function due to Zr may be lost. , And casting defects due to blow holes, cracks, oxides, sulfides, etc. are likely to occur. In such a case, Mg or the like has a function of improving the hot water flow during casting even when a scrap material containing an S component is used as an alloy raw material. In addition, for example, Mg can remove S component in the form of harmless MgS, and this MgS is not in a form harmful to corrosion resistance even if it remains in the alloy, and the raw material contains S component. Therefore, it is possible to effectively prevent the corrosion resistance from being reduced. In addition, when the raw material contains an S component, S is likely to be present at the crystal grain boundaries, and there is a risk of causing grain boundary corrosion. However, inclusion of Mg can effectively prevent grain boundary corrosion. Moreover, there is a possibility that the S concentration of the molten metal becomes high and Zr is consumed by S. However, if the molten metal contains a certain amount or more of Mg before Zr charging, the S component in the molten metal will be reduced. Such a problem does not occur because it is removed or fixed in the form of MgS. However, if Mg is contained excessively, it is oxidized like Zr, the viscosity of the molten metal is increased, and there is a possibility that a casting defect due to oxide entrainment or the like may occur. Further, Mg also has a function of substituting part of the crystal grain refining function by P in the presence of Zr and P, and the degree of the crystal grain refining effect as an alternative to such P is P Is equivalent to Therefore, in the case of containing Mg, the Mg amount is set to 0.001 to 0.3 mass% (preferably 0) on condition that the relational expression F3 of (11) is satisfied in relation to Zr and P. 0.003 to 0.2 mass%, optimally 0.01 to 0.1 mass%). Al and Mn are also inferior to the above Mg, but have the effect of removing S component contained in the molten metal. Further, if the amount of oxygen in the molten metal is large, Zr may form an oxide and the function of refining crystal grains may be lost, but Al and Mn may also form such an oxide of Zr. The effect to prevent is also demonstrated. Considering this point and the above points, the Mn content is 0.03 to 1 mass% (preferably 0.05 to 0.7 mass%, optimally 0.1 to 0.5 mass%), and the Al content is Is 0.01 to 1 mass% (preferably 0.02 to 0.8 mass%, more preferably 0.05 to 0.5 mass%). In addition to the above-described functions, Al has the functions of improving the hot water flow and corrosion resistance, and further improving the erosion corrosion resistance, strength, and wear resistance as well as P. In order to exhibit it, the lower limit of the content range was made larger than Mg and Mn.

  As and Sb have the function of substituting part of the crystal grain refining function of P in the presence of Zr and P, and, like P, have the function of improving corrosion resistance and intergranular corrosion resistance. Have. However, excessive contents of As and Sb may reduce ductility, and further, toxic effects that adversely affect the human body are problematic. Considering this point, the contents of As and Sb are both 0.02 to 0.2 mass% (preferably 0.025 to 0.15 mass%, optimally 0.03 to 0.1 mass%). It was.

Fe has a function of suppressing crystal grain growth during recrystallization annealing performed after cold working. For example, if Fe is contained in excess of 0.25 mass%, the refinement of crystal grains in the casting is inhibited. However, if the amount of Fe is 0.2 mass% or less, the refinement of crystal grains in the casting is reduced. There is almost no effect, and the crystal grains of the casting are sufficiently refined. On the other hand, recrystallization by heat treatment does not occur simultaneously in all parts of the object to be processed, and there may be a time lag due to the number of nucleation sites microscopically. ) Is likely to cause crystal grain growth in the meantime. By avoiding this, crystal grain refinement in the workpiece (work material) can be realized. Fe has a function of suppressing grain growth during recrystallization annealing even if its content is 0.2 mass% or less, which cannot affect the grain refinement in the casting as described above. By containing Fe in the range, it can contribute to refinement of crystal grains in the casting and the processed product. The suppression of the growth of recrystallized grains by Fe is caused by the fact that Fe combines with a part of P in a Cu—Sn alloy or Cu—Zn—Sn alloy to produce a fine compound (Fe ₂ P) and the pin of the precipitated particles The stopping effect effectively suppresses the growth of recrystallized grains. Such a function by Fe is hardly exhibited when the Fe amount is less than 0.01 mass%, and conversely, even if the Fe content exceeds 0.2 mass%, the above-described effect of suppressing the growth of recrystallized grains by Fe. Will be saturated, and on the contrary, it will hinder the refinement of crystal grains at the casting stage as described above. Therefore, from these points, it is appropriate that the Fe content is 0.01 to 0.2 mass%. In addition, if further refinement of crystal grains in the casting is taken into consideration, the upper limit of the amount of Fe is preferably set to 0.15 mass% or less, more preferably 0.1 mass% or less, and crystals in the plastic work material. In view of the effect of suppressing grain growth, the lower limit of the amount of Fe is preferably set to 0.02 mass% or more, and more preferably set to 0.03 mass% or more. Thus, when Fe is contained, P is consumed by forming a compound (Fe ₂ P) with P as described above. Is 0.01 to 0.2 mass% (preferably 0.02 to 0.15 mass%, optimally 0.03 to 0.1 mass%) on condition that the relational expression F4 of (12) is satisfied. It is good to leave as.

Co and Si, like Fe, have a function of suppressing crystal grain growth during recrystallization annealing performed after cold working. In particular, when Co and Si are added together, Co ₂ Si is added. It has the function of forming and suppressing the growth of recrystallized grains more effectively like Fe ₂ P. Further, Si is effective in improving the strength, and, like Sn and Zn, reduces the stacking fault energy and contributes to the refinement of crystal grains. Furthermore, Si also has a function of improving the spring limit value and stress relaxation characteristics. From these points, the Co content is 0.01-0.2 mass% (preferably 0.02-0.15 mass%, optimally 0.03-0.1 mass%), and the Si content is 0.01 To 0.8 mass% (preferably 0.03 to 0.5 mass%, optimally 0.05 to 0.3 mass%).

  By the way, since the crystal grain of the casting is coarse, if the stress is locally concentrated during the plastic working, it becomes easy to crack. Further, when alloyed, concentration segregation occurs. In particular, when a large amount of a low melting point metal such as Sn is contained, the degree of segregation becomes further remarkable. This concentration segregation also becomes macroscopic (large and wide) when the crystal grains are coarsened, coupled with the coarsening phenomenon of the crystal grains, and further increases the susceptibility to cracking during plastic working (high Sn concentration). (Since the hard part and the soft part exist in a wide area, it is easy to crack if stress concentration occurs at the boundary.) If the crystal grain of the casting is fine, even if stress is concentrated, it can be mitigated by the effect of miniaturization. Even if elements such as Sn are contained, the segregation is only microscopic, and the stress concentration source It is hard to become. That is, when the crystal grains are large at the casting stage, cracks occur early during plastic processing such as rolling and wire drawing, but if the crystal grains of the casting are fine, even if the content of elements such as Sn is large, Increased resistance to processing cracks. When a product is manufactured by light plastic processing once, naturally, if the crystal grain of the casting is large, it is brittle, the strength is low, and there is a problem in corrosion resistance and the like. Regarding the corrosion resistance, when the second phase and the third phase are present, they are long and continuous, and this is also a problem.

  In the recrystallization annealing performed after the plastic working, if the original crystal grain is large, the recrystallization nucleation site is recrystallized at a portion centering on the grain boundary. Although depending on the processing rate by plastic working and the temperature condition of annealing, the grains are in an unrecrystallized state or are coarse recrystallized grains even if recrystallized. And since the segregation of alloy elements such as Sn is originally macroscopic segregation due to coarsening, element segregation will be eliminated together with recrystallization, but it is not sufficient, although it is improved from the casting stage, The plastic workability is still poor. Furthermore, when there is a large amount of Sn or the like or when the value of F2 (= 3 [Sn] + [Zn]) is large, the second phase other than the α phase (γ phase, δ phase, etc.) is generated excessively from the equilibrium state. Although it is easy, if the crystal grains are large at the casting stage, the second phase remains without being reduced or disappeared even after annealing (recrystallization annealing). As a result, cracks starting from the second phase are likely to occur during plastic working. Such a problem is conspicuous particularly during plastic processing where stress due to bending or the like tends to concentrate. When the annealing temperature is increased, element segregation is considerably eliminated, but the size of the obtained crystal grain is coarse and naturally the energy cost is also increased. If it is commercialized at this stage (there may be final processing), it is improved from the casting stage, but the strength is low, the ductility such as bending workability is inferior, and the corrosion resistance still has a problem.

  In the preferred embodiment, the first to eighth plastic working materials are subjected to cold working and / or hot working one or more times on the casting material and at the same time annealing in the recrystallization temperature range (recrystallization annealing). It is a plate material, strip material, wire material, bar material or pipe material that is applied more than once. The cold working includes cold working such as finishing and straightening performed after the last recrystallization annealing (hereinafter referred to as “simple cold working”) as necessary. By subjecting the workpiece (including cast material) to cold working and then performing recrystallization annealing, or by subjecting the workpiece to hot working that is plastic working in the recrystallization temperature range. The crystal grains of the material are reduced. The degree of grain refinement increases as the working rate of cold working or hot working before recrystallization annealing increases. On the other hand, the casting material has the above-described composition, so that the crystal grains are refined (the average crystal grain size D2 is 300 μm or less (preferably D2 ≦ 150 μm, more preferably D2 ≦ 100 μm, optimally D2 ≦ 60 μm)). Therefore, the crystal grain of the workpiece is further refined by subjecting the casting material to cold processing (recrystallization annealing is performed after that) and / or hot processing. As a result, a plastic work material having fine crystals (average crystal grain size of 150 μm or less) is obtained. The degree of refinement of crystal grains in the plastic working material increases as the overall processing rate P described later increases and / or as the crystal grains of the casting material become finer. In simple cold working, the crystal grains of the workpiece are only deformed, and the crystal grains cannot be reduced.

  By the way, the degree of crystal grain refinement by plastic working increases / decreases depending on the type of plastic working (cold working (after which recrystallization annealing is performed) or hot working), the working rate by plastic working, and the number of plastic workings. However, in order to grasp these relationships, it is convenient to use an overall processing rate P (%) defined as follows.

  That is, assuming that three recrystallization annealings are performed, all the cold workings performed between the last recrystallization annealing and the intermediate recrystallization annealing (hereinafter referred to as “first cold working”). By the processing rate (hereinafter referred to as “first processing rate”) P1 and all cold processing (hereinafter referred to as “second cold processing”) performed between the first recrystallization annealing and the intermediate recrystallization annealing. The processing rate (hereinafter referred to as “second processing rate”) P2 and the processing rate (hereinafter referred to as “third processing rate”) of all cold processing (hereinafter referred to as “third cold processing”) performed before the first recrystallization annealing. )) P3 and the processing rate by hot processing (hereinafter referred to as “hot processing rate”) P4, the total processing rate is P = P1 + 0.4 × (P2 + P3) + 0.2 × P4. In addition, in the calculation of the overall processing rate P, when there are two or more intermediate recrystallization annealings, the sum of the processing rates by cold working performed between each recrystallization annealing is the second processing rate. In addition, when the first, second, or third cold working or hot working is performed a plurality of times, the processing rate is the cross-sectional area of the workpiece to be subjected to the first processing (the cross-sectional area or (Plate thickness) and a cross-sectional area (including a cross-sectional area or a plate thickness for a plate material) of a workpiece (including a plastic processed material that is a final processed material) subjected to the last processing. When the intermediate recrystallization annealing is not performed (when the recrystallization annealing is performed twice), the second processing rate is set to P2 = 0, and the first recrystallization annealing and the intermediate recrystallization annealing are not performed. When the recrystallization annealing is performed once, the second and third processing rates are P2 = P3 = 0, and when the hot processing is not performed, the hot processing rate is P4 = 0. Needless to say, the processing rate by the simple cold working is not included in the total processing rate P because the simple cold working does not contribute to the refinement of crystal grains.

  Thus, although the crystal grains in the plastic work material are remarkably refined as compared with the crystal grains of the cast material, the degree of refinement becomes higher as the value of the overall work rate P increases. In a preferred embodiment, when the average crystal grain size D2 of the casting material is 300 μm or less (preferably D2 ≦ 150 μm, more preferably D2 ≦ 100 μm, optimally D2 ≦ 60 μm), P <30% By performing plastic working, a plastic working material having an average crystal grain size D1 ≦ 150 μm (preferably D1 ≦ 100 μm, more preferably D1 ≦ 60 μm, optimally D1 ≦ 50 μm) can be obtained, and 30% ≦ P < By applying 50% plastic working, a plastic working material having an average crystal grain size D1 ≦ 60 μm (preferably D1 ≦ 50 μm, more preferably D1 ≦ 40 μm, optimally D1 ≦ 30 μm) can be obtained. Further, by performing plastic working with P ≧ 50%, a plastic working material having an average grain size D ≦ 45 μm (preferably D1 ≦ 40 μm, more preferably D1 ≦ 30 μm, optimally D1 ≦ 25 μm) can be obtained. Further, a plastic working material having an average grain size D1 ≦ 4 μm (preferably D1 ≦ 3 μm, more preferably D1 ≦ 2.5 μm, optimally D1 ≦ 2 μm) is obtained by performing plastic working with P ≧ 70%. be able to. In order to effectively refine the crystal grains of the plastic working material, it is preferable that the working rate (first working rate P1) of the cold working performed before the last recrystallization annealing is 30% or more. .

  The number of plastic working steps for obtaining a plastic working material having such an average crystal diameter D1 decreases as the average crystal grain diameter D2 of the casting material decreases. On the other hand, the crystal grains of the casting material are refined by having the above-described composition, and the average crystal grain size D2 is D2 ≦ 300 μm (preferably D2 ≦ 150 μm, more preferably D2 ≦ 100 μm, optimally D2 ≦ 60 μm). Can be made. Therefore, by using a casting material in which crystal grains are refined in this way, the number of plastic working steps for obtaining a plastic working material having the above-mentioned average crystal diameter D1 can be reduced as will be understood from the examples described later. Can be minimal.

  In addition, the first to eighth plastic working materials have the above-described crystal structure (D1 ≦ 150 μm) and phase structure (α ≧ 94.5%, γ + δ + ε ≦ 5%), so that strength, elongation, bending workability, etc. It will be excellent. When the average grain size D of the plastic workpiece is large, when the plastic workpiece is processed (for example, deep drawing), in addition to the appearance defects such as rough skin and wrinkles on the product surface, it also affects the product function. Although adverse effects are caused, such a problem can be avoided if D1 ≦ 150 μm. For example, if D1 ≦ 30 μm, there is almost no problem in any product processing. Also, if the crystal grain of the casting material is coarse, if the processing rate for obtaining the plastic work material is low, it is not possible to obtain a fine recrystallized grain, suppose that a fine recrystallized grain was obtained However, since the recrystallization is performed around the grain boundary of the casting material, the crystal grains in the plastic working material are not uniform. Even when the average crystal grain size is small, if the crystal grains are uneven in size, rough skin occurs due to the local presence of the large-diameter grains. Moreover, the fact that coarse crystal grains remain means that the elements that segregate at the time of casting (such as Sn) are not sufficiently uniform, and the strength of the segregation varies depending on the degree of segregation. Sometimes cracks tend to occur. That is, when coarse grains and small recrystallized grains exist, stress is concentrated between them and cracks are likely to occur. These two factors overlap to cause a problem in the workability of the product, and naturally a problem remains in the corrosion resistance. However, in the first to eighth plastic working materials, since the crystal grains of the casting material are miniaturized, the size of the crystal grains in the plastic working material is uniform, and the above problems do not occur. Since the strength is inherently dependent on the crystal grains, the larger the crystal grains or the larger the coarse grains, the lower the strength. However, according to the present invention, the strength, ductility, and workability are reduced. An excellent plastic working material can be provided.

  Moreover, in order to ensure sufficient strength, corrosion resistance, etc. for the first to eighth plastic working materials, the content of α phase as a matrix in the area ratio is 94.5% or more (preferably 96% or more, more Preferably it is 98% or more, optimally 99.5% or more) and the total area ratio of γ phase, δ phase and ε phase is 5% or less (preferably 3.5% or less, more preferably 1.5% or less) It is necessary to form a metal structure (phase structure) that is 0.5% or less optimally). That is, if the content of the δ phase or the like is excessive, selective corrosion of the phase occurs, the corrosion resistance is lowered, and the ductility is lowered. When the crystal grains are refined, the δ phase and the like are small, and the crystal grains are divided, subdivided, and uniformly distributed in the matrix, so that mechanical characteristics are greatly improved.

  Therefore, the first to eighth plastic working materials having fine crystal grains and having the phase structure described above require high strength, elongation, workability, etc., springs, switches, connectors, bellows for electronic and electrical equipment. , Fuse clip, bush, relay, gear, cam, joint, flange, machine screw, bolt, nut, eyelet, washer, bearing, coil spring, spiral spring, snap button, header, lead terminal, transistor terminal, lead frame, rotary Switch sliding piece, switch contact piece, bearing frame, hydraulic cap, packing, clutch plate, papermaking blade material, diaphragm, spring for cable attachment / detachment, movable spring for timer relay, heat exchanger, tube plate for heat exchanger, Heat exchanger, wire net, marine net, aquaculture net, fish net, seawater condenser pipe, ship parts shaft, ginger Frame, tumbler, wiring devices, sockets, pins, welded pipe gas pipe, intake ship seawater, can be suitably used as a constituent material, such as marine fish preserve frame (frame).

  In addition, when manufacturing the 1st-8th plastic working material, a scrap material may be used for the raw material of a casting raw material, However, When using this scrap material, an impurity may inevitably contain. Yes, practically acceptable. However, when the scrap material is a nickel-plated material or the like, when Ni is contained as an inevitable impurity, the content is preferably limited. That is, if the content of the impurity Ni is large, Zr and P useful for refining crystal grains are consumed by Ni, and there is an inconvenience that inhibits the refining action of crystal grains. Therefore, in the first to eighth plastic working materials, when Ni is contained as an impurity during the production of the casting material, the content is 0.25 mass% or less (preferably 0.2 mass% or less, optimally Is preferably limited to 0.1 mass% or less). In such a range, it is also meaningful to contain Ni as an impurity, provided that Fe is co-added. That is, if the Ni content is 0.1 mass% or less, there is almost no adverse effect on the refinement of the crystal grains of the casting material, and the effect of co-addition with Fe causes crystals during recrystallization annealing after plastic working. Effectively suppress grain growth.

  The third aspect of the present invention is a method for producing the first to eighth plastic working materials, wherein the average crystal grain size D2 is 300 μm or less (preferably D2 ≦ 150 μm, more preferably D2 ≦ 100 μm, optimally Is a casting process for producing a casting material of D2 ≦ 60 μm), and a recrystallization annealing which is performed at least once in the recrystallization temperature range while subjecting the casting material obtained in the casting process to cold working and / or hot working at least once. The manufacturing method of the copper alloy-made plastic working material which comprises the plastic working process which performs this more than once is proposed.

  In this manufacturing method, as described above, the working rate (first working rate) P1 of cold working (first cold working) performed before the last recrystallization annealing in the plastic working step is set to 30% or more. It is preferable to keep.

  In the final recrystallization annealing, the average cooling rate in the temperature range of 300 ° C. to 450 ° C. (especially 300 to 400 ° C.) is 0.5 ° C./second or more (preferably 1 ° C./second or more, more preferably 3 C./second or more, optimally 10 ° C./second or more). That is, the cooling rate in the temperature range (300 ° C. to 450 ° C.) where the second phase (δ phase etc.) other than the matrix phase (α phase) is generated is increased (the average cooling rate is 0.5 ° C./second or more). Thus, the appearance of the second phase is avoided as much as possible, and the phase structure in the first to eighth plastic working materials is made appropriate as described above. In addition, recrystallization obtained by recrystallization annealing by high-speed cooling and short-time annealing at a higher temperature (specifically, 450 ° C or higher, more preferably 475 ° C or higher) avoiding the brittle temperature range. The grains become finer. That is, if the high temperature state continues for a long time, the crystal grains grow, but if it is a short time, recrystallization nuclei are generated at the same time without causing a time lag in more places. Becomes finer. And naturally, if the cooling rate after annealing is high, the growth of recrystallized grains in the cooling process is suppressed. In particular, if a small amount of Fe or the like that exerts the effect of suppressing recrystallized grains as described above is contained, the recrystallization temperature is hardly increased and the growth of recrystallized grains is effectively suppressed. A material suitable for the conditions at a high annealing temperature can be obtained.

  In the casting process, as described above, it is preferable that the primary crystal at the time of melting and solidifying the casting forms an α phase and / or that a peritectic reaction is caused at the time of melting and solidifying the casting.

  In the casting process, Zr (containing for the purpose of further refinement of crystal grains and stable refinement of crystal grains) is cast in the form of a copper alloy containing the same. It is preferable that Zr is not contained in the form of an oxide and / or sulfide at the time of casting by adding it immediately before or at the final stage of raw material dissolution. The copper alloy containing Zr includes a Cu—Zr alloy, a Cu—Zn—Zr alloy, or one or more elements selected from P, Mg, Al, Sn, Mn, and B based on these alloys. What was contained is suitable.

  That is, in the casting process of casting the raw material (casting material) of the first to eighth plastic working materials, an intermediate alloy (copper alloy) in which Zr is in the form of a granular material, a thin plate material, a rod material, or a linear material. ) In the form of Z), the loss during addition of Zr is reduced as much as possible, and Zr is contained in the form of an oxide and / or sulfide during casting to produce crystal grains. Therefore, it is possible to prevent a situation in which a Zr amount necessary and sufficient for exhibiting the micronization effect cannot be secured. When Zr is added just before casting as described above, the melting point of Zr is 800 to 1000 ° C. higher than the melting point of the copper alloy, so that the granular material (particle size: about 2 to 50 mm), the thin plate (thickness: 1) A low melting point alloy material (for example, about 0.1 mm to about 0.1 mm), a rod-shaped material (diameter: about 2 to 50 mm) or a linear material, which is close to the melting point of the copper alloy and contains many necessary components. One or more elements selected from P, Mg, Al, Sn, Mn and B based on Cu-Zr alloy or Cu-Zn-Zr alloy containing 5 to 65 mass% Zr or these alloys as a base (each element It is preferable to use it in the form of an alloy) containing 0.1-5 mass%). In particular, a Cu-Zn-Zr alloy containing 0.5 to 35 mass% Zr and 5 to 50 mass% Zn (more It is preferably used in the form of an alloy based on a Cu-Zn-Zr alloy containing 1-15 mass% Zr and 5-45 mass% Zn. Zr is an element that hinders electrical and thermal conductivity, which is an essential characteristic of copper alloys, although it depends on the blending ratio of P and co-added with Zr, but does not form oxides or sulfides. If the amount of Zr is 0.039 mass% or less, particularly 0.019 mass% or less, there is almost no decrease in electrical / thermal conductivity due to the inclusion of Zr, even if the electrical / thermal conductivity is reduced, The rate of decrease is negligible compared to the case where Zr is not contained.

  Further, in producing (casting) a casting material suitable for obtaining the first to eighth plastic working materials, it is desirable that the casting conditions, particularly the casting temperature and the cooling rate, be appropriate. That is, the casting temperature is preferably determined so as to be 20 to 250 ° C. high temperature (more preferably 25 to 150 ° C. high temperature) with respect to the liquidus temperature of the copper alloy. That is, the casting temperature is preferably determined in the range of (liquidus temperature + 20 ° C.) ≦ casting temperature ≦ (liquidus temperature + 250 ° C.), and (liquidus temperature + 25 ° C.) ≦ casting temperature ≦ ( It is more preferable to determine within the range of (liquidus temperature + 150 ° C.). Generally, the casting temperature is 1200 ° C. or lower, preferably 1150 ° C. or lower. The lower limit side of the casting temperature is not particularly limited as long as the molten metal is filled in every corner of the mold, but as the casting is performed at a lower temperature, the crystal grains tend to become finer. It should be understood that these temperature conditions vary depending on the alloying amount.

  The plastic work material made of the Cu-Sn copper alloy or Cu-Sn-Zn copper alloy of the present invention has achieved significant improvements in strength, ductility, corrosion resistance, workability, etc. by realizing finer crystal grains. The final product can be obtained easily and with high quality. It can be suitably used as a component of electrical and electronic equipment parts (connectors, etc.) that are required to be further reduced in strength, thickness, etc., and its use can be greatly expanded. It can be done.

  Moreover, according to the manufacturing method of this invention, such a plastic working material can be manufactured efficiently and easily.

As Example 1, a plastic working material No. 1 obtained by plastic working a casting material having the composition shown in Tables 1 and 2 was used. 1- No. 8 and no. 10- No. 40 was obtained by the following casting process and plastic working process.

Casting process:
The copper alloy materials having the compositions shown in Tables 1 and 2 were cast into molds at a casting temperature of the liquidus temperature + 100 ° C., respectively, and a rectangular ingot (thickness: 30 mm, width: 70 mm, length) : 250 mm), and the ingot was subjected to surface chamfering to obtain a rectangular casting material E1 having a thickness of 24 mm, a width of 70 mm, and a length of 250 mm.

Plastic working process:
Each cast material E1 was cold-rolled (third cold work) to obtain a primary work material E2 having a thickness of 6 mm (third work rate P3: 75%), and annealed in a recrystallization temperature range. (First recrystallization annealing). Next, the primary work material E2 was cold-rolled (first cold work) to obtain a secondary work material E3 having a thickness of 0.9 mm (first work rate P1: 85%), and the recrystallization temperature. Annealed in the zone (final recrystallization annealing). Thereafter, the secondary work material E3 is pickled and then cold-rolled (simple cold work) to obtain a plastic work material (thin plate material) No. 7 having a thickness of 0.7 mm. 3-No. 37 (No. 8 , No. 10 , No. 13 to No. 19, No. 22, and No. 28) were obtained. In addition, No. 1, no. 2, N
o. 8 , no . 10, no. 13, no. 17-No. 19, no. 22 and no. For No. 28, the plastic working step was completed when a step (cold rolling) for obtaining the primary work material E2 necessary for evaluating the cold rolling property described later was performed. No. 14-No. 16 and no. No. 38-No. For No. 40, only the casting material E1 for investigating the average crystal grain size of the casting material was obtained, and the plastic working process of the casting material E1 was not performed.

  The overall processing rate P in this plastic processing step was obtained by P = P1 + 0.4 × P3, and P = 115% as shown in Tables 5 and 6.

Plastic working material No. 3-No. 37 (No. 8 , No. 10 , No. 13 to No. 19, No. 22, and No. 28 are excluded), the primary work material E2 is annealed (intermediate annealing) at 500 ° C. for 60 minutes. This was carried out by holding and cooling. This cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  Also, plastic working material No. 3, no. 11, no. 12, no. 20-No. 23, no. 29-No. 31, no. 36, no. Regarding No. 37, the secondary processed material E3 was annealed (final annealing) by holding it at 400 ° C. for 30 minutes and then cooling it. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 400 ° C. was 5 ° C./second.

  Also, plastic working material No. 4, no. 24 and no. For No. 32, the secondary processed material E3 was annealed (final annealing) by holding at 450 to 475 ° C. for 1000 seconds and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 2 ° C./second.

  Also, plastic working material No. 5, no. 25 and no. Regarding No. 33, the secondary work material E3 was annealed (final annealing) by holding at 475 to 500 ° C. for 120 seconds and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  Also, plastic working material No. 6, no. 26 and no. For No. 34, the secondary processed material E3 was annealed (final annealing) by holding at 500 to 525 ° C. for 30 seconds and then cooling. The cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 15 ° C./second.

  Also, plastic working material No. 7, no. 27 and no. Regarding No. 35, the secondary work material E3 was annealed (final annealing) by holding at 525 to 550 ° C. for 10 seconds and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 0.7 ° C./second.

  As Example 2, a plastic working material No. 2 formed by plastic working a casting material having the composition shown in Tables 2 and 3 was used. 41-No. 59 was obtained by the following casting process and plastic working process.

Casting process:
The copper alloy materials having the compositions shown in Table 2 and Table 3 were cast into molds at a casting temperature of the liquidus temperature + 100 ° C., respectively, and a rectangular ingot (thickness: 30 mm, width: 70 mm, length) : 250 mm), and the surface of the ingot was chamfered to obtain a rectangular casting material F1 having a thickness of 24 mm, a width of 70 mm, and a length of 250 mm.

Plastic working process:
Each cast material F1 was hot-rolled (hot work) to obtain a primary work material F2 having a thickness of 6 mm (hot work rate P4: 75%). Next, the primary work material F2 was cold-rolled (first cold work) to obtain a secondary work material F3 having a thickness of 0.9 mm (first work rate P1: 85%), and recrystallized. Annealing was performed in the temperature range (final recrystallization annealing). Thereafter, the secondary work material F3 is pickled and then cold-rolled (simple cold work) to obtain a plastic work material (thin plate material) No. 7 having a thickness of 0.7 mm. 42-No. 55 (excluding No. 45, No. 46 and No. 50) were obtained. In addition, No. 41, no. 45, no. 46, no. 50 and no. 56-No. For 59, the plastic working process was completed when a process (hot rolling) for obtaining the primary work material F2 necessary for evaluating the hot rollability described later was performed.

  The overall processing rate P in this plastic processing step was obtained by P = P1 + 0.2 × P4, and P = 100% as shown in Tables 6 and 7.

  Plastic working material No. 41-No. 51 and no. 56-No. For No. 59, the secondary work material F3 was annealed (final recrystallization annealing) by holding at 400 ° C. for 30 minutes and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 400 ° C. was 5 ° C./second.

  Also, plastic working material No. Regarding No. 52, the secondary work material F3 was annealed (final recrystallization annealing) by holding at 450 to 475 ° C. for 1000 seconds and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 2 ° C./second.

  Also, plastic working material No. For 53, the secondary work material F3 was annealed (final recrystallization annealing) by holding at 475 to 500 ° C. for 120 seconds and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  Also, plastic working material No. For No. 54, the secondary work material F3 was annealed (final recrystallization annealing) at 500 to 525 ° C. for 30 seconds and then cooled. The cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 15 ° C./second.

  Also, plastic working material No. About 55, it carried out by cooling after hold | maintaining (second recrystallization annealing) of the secondary processed material F3 at 525-550 degreeC for 10 second. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 0.7 ° C./second.

  As Example 3, a plastic working material No. obtained by plastic working a casting material having the composition shown in Table 3 was used. 60-No. 62 was obtained by the following casting process and plastic working process.

Casting process:
Each of the copper alloy materials having the composition shown in Table 3 was cast into a mold at a casting temperature of the liquidus temperature + 100 ° C. to form a rectangular ingot (thickness: 30 mm, width: 70 mm, length: 250 mm) Then, the surface of the ingot was chamfered to obtain a rectangular casting material G1 having a thickness of 22.5 mm, a width of 70 mm, and a length of 250 mm.

Plastic working process:
Plastic working material No. 60 and no. Each of the casting materials G1 for 61 was cold-rolled (first cold working) to obtain a primary processed material G2 having a thickness of 20 mm (first working rate P1: 11%), and this was recrystallized temperature range Annealing (last recrystallization annealing). Further, the primary work material G2 was cold-rolled (simple cold work), and a plastic work material (thick plate material) No. 18 having a thickness of 18 mm was obtained. 60 and no. 61 was obtained.

  Also, plastic working material No. Each of the casting materials G1 for 62 was cold-rolled (first cold working) to obtain a primary processed material G3 having a thickness of 11 mm (first working rate P1: 51%), and this was recrystallized temperature range Annealing (last recrystallization annealing). Furthermore, the primary work material G3 was cold-rolled (simple cold work), and a plastic work material (thick plate material) No. 10 having a thickness of 10 mm was obtained. 62 was obtained.

  The overall working rate P in this plastic working process is obtained by P = P1, and as shown in Table 7, the plastic working material No. 60 and no. For P61, P = 11%. For 62, P = 51%.

  The primary processed materials G2 and G3 were annealed (final annealing) by holding them at 500 ° C. for 60 minutes and then cooling them. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  As Example 4, a plastic working material No. obtained by plastic working a casting material having the composition shown in Table 3. 63-No. 73 was obtained by the following casting process and plastic working process.

Casting process:
A round bar-shaped casting (diameter: 10 mm) was obtained from each of the copper alloy materials having the compositions shown in Table 3 by using a graphite mold with a horizontal continuous casting machine. Casting was performed under the conditions of casting temperature: liquidus temperature + 100 ° C. and casting speed: 200 mm / min. Then, the round bar-shaped casting was subjected to surface chamfering to obtain a round bar-shaped casting material H1 having a diameter of 9.5 mm.

Plastic working process:
Each of the cast materials H1 was cold-drawn (first cold working) to obtain a primary processed material H2 having a diameter of 5 mm (first working rate P1: 72%), which was then annealed in the recrystallization temperature range. (Final recrystallization annealing). Further, the primary work material H2 was pickled and then cold-drawn (simple cold work) to obtain a plastic work material (wire) No. 4 having a diameter of 4.45 mm. 63-No. 72 (excluding No. 70) was obtained. In addition, No. 70 and no. For 73, the plastic working step was completed when a step (cold drawing) for obtaining the primary work material H2 necessary for evaluating the cold drawing property described later was performed.

  The overall processing rate P in this plastic processing step was obtained with P = P1, and as shown in Table 7, P = 72%.

  Plastic working material No. 63 and no. 68-No. For 73, the primary work material H2 was annealed (final recrystallization annealing) by holding at 400 ° C. for 30 minutes and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 400 ° C. was 5 ° C./second.

  Also, plastic working material No. For No. 64, annealing (final recrystallization annealing) of the primary work material H2 was held at 450 to 475 ° C. for 1000 seconds and then cooled. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 2 ° C./second.

  Also, plastic working material No. For No. 65, the primary work material H2 was annealed (final recrystallization annealing) at 475 to 500 ° C. for 120 seconds and then cooled. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  Also, plastic working material No. For No. 66, the primary work material H2 was annealed (final recrystallization annealing) at 500 to 525 ° C. for 30 seconds and then cooled. The cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 15 ° C./second.

  Also, plastic working material No. For No. 67, the primary work material H2 was annealed (final recrystallization annealing) at 525 to 550 ° C. for 10 seconds and then cooled. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 0.7 ° C./second.

  As Example 5, a plastic work material No. obtained by plastic working a cast material having the composition shown in Table 3 was used. 74-No. 78 was obtained by the following casting process and plastic working process.

Casting process:
A round bar-shaped casting (diameter: 20 mm) was obtained from each of the copper alloy materials having the compositions shown in Table 3 using a graphite mold by a horizontal continuous casting machine. Casting was performed under the conditions of casting temperature: liquidus temperature + 100 ° C. and casting speed: 150 mm / min. Then, the round bar-shaped casting was subjected to surface chamfering to obtain a round bar-shaped casting material I1 having a diameter of 19.5 mm.

Plastic working process:
Plastic working material No. 74-No. Each of the casting materials I1 for 77 was subjected to cold drawing (first cold working) to obtain a primary processed material I2 having a diameter of 18 mm (first working rate P1: 15%). Annealing (last recrystallization annealing). Thereafter, the primary work material I2 is pickled and then cold-drawn (simple cold work) to obtain a plastic work material (wire) No. 17 having a diameter of 17 mm. 74-No. 77 was obtained.

Also, plastic working material No. Cast material I1 for 78 was cold-drawn (first cold working) to obtain a primary work material I3 having a diameter of 15.5 mm (first working rate P1: 37%), and this was recrystallized temperature Annealed in the zone. Thereafter, the primary work material I3 is pickled and then cold-drawn (simple cold work) to obtain a plastic work material (wire material) No. 1 with a diameter of 14.7 mm. 78 was obtained.

  The overall working rate P in this plastic working process is obtained by P = P1, and as shown in Table 7, the plastic working material No. 74-No. 77, P = 15%. For 78, P = 37%.

Plastic working material No. 74-No. In each of 78, the primary processed materials I2 and I3 were annealed (final recrystallization annealing) by holding at 500 ° C. for 60 minutes and then cooling. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  As Example 6, plastic working material No. obtained by plastic working a casting material having the composition shown in Table 3. 79 and no. 80 was obtained by the following casting process and plastic working process.

Casting process:
Each of the copper alloy materials having the compositions shown in Table 3 was obtained by using a graphite mold with a horizontal continuous casting machine to obtain a tubular casting (outer diameter: 61 mm, inner diameter: 50 mm). Casting was performed under the conditions of casting temperature: liquidus temperature + 100 ° C. and casting speed: 150 mm / min. Then, the surface of this tubular casting was chamfered to obtain a tubular casting material J1 having an outer diameter of 60 mm and an inner diameter of 50 mm.

Plastic working process:
Each cast material J1 was subjected to cold drawing (first cold working) to obtain a primary work material J2 having an outer diameter of 58 mm and an inner diameter of 50 mm (first working rate P1: 21%). This was annealed in the recrystallization temperature range (final recrystallization annealing). Thereafter, the primary work material J2 is pickled and then cold-drawn (simple cold work) to obtain a plastic work material (tube material) No. 5 having an outer diameter of 57.2 mm and an inner diameter of 50. 79 and no. 80 was obtained.

  The overall processing rate P in this plastic processing step was obtained with P = P1, and as shown in Table 7, P = 21%.

  The primary processed material J2 was annealed (final recrystallization annealing) by holding it at 500 ° C. for 60 minutes and then cooling it. Cooling was performed under the condition that the average cooling rate in the temperature range of 300 to 450 ° C. was 5 ° C./second.

  As Comparative Example 1, the plastic working material No. 1 in Example 1 was used. In the same casting process and plastic working process as in the case of obtaining 1 101-No. 107 was obtained, but the plastic working process could not be performed as follows.

That is, a casting material e1 having the same shape as the casting material E1 was obtained from the copper alloy material having the composition shown in Table 4 by the same casting process as in Example 1. In addition, No. 104, no. 106 and no. For 107, the casting material e1 for investigating the average crystal grain size of the casting material was stopped, and the plastic working process of the casting material e1 was not performed.

Then, each casting material e1, underwent the same cold rolling as in Example 1 to produce a primary processed member e2 of the primary processed material E2 the same shape. However, no. 101-No. In any of No. 105 (excluding No. 104), the primary work material e2 was cracked so that the subsequent plastic working process could not be performed, and the final plastic work material could not be obtained.

  As Comparative Example 2, the plastic working material No. 1 in Example 2 was used. No. 41 is obtained by the same casting process and plastic working process as in the case of obtaining No. 41. 108-No. 112 was obtained, but the plastic working process could not be performed as follows.

  That is, a casting material f1 having the same shape as the casting material F1 was obtained from the copper alloy material having the composition shown in Table 4 by the same casting process as in Example 2.

And each casting raw material f1 was subjected to the same hot rolling as in Example 2 to obtain a primary processed material f2 having the same shape as the primary processed material F2 . However, no. 108-No. In all of 112, since the primary work material f2 was cracked greatly, the plastic working process after the cracking could not be performed, and the final plastic work material could not be obtained.

  As Comparative Example 3, the plastic working material No. 1 in Example 3 was used. 60 or No. No. 62 is obtained by the same casting process and plastic working process as in the case of obtaining No. 62. 113-No. 118 was obtained.

  That is, a casting material g1 having the same shape as the casting material G1 was obtained from the copper alloy material having the composition shown in Table 4 by the same casting process as in Example 3.

  And plastic working material No. 113-No. Each of the casting materials g1 for 117 was subjected to the same plastic working process as in Example 3 to obtain a plastic working material No. By performing the same plastic working as in the case of obtaining 60, the plastic working material No. No. 60 plastic work material No. 113-No. 117 was obtained. In addition, No. 113-No. For each of 117, the primary work material g2 having the same shape as the primary work material G2 was obtained by subjecting each casting material g1 to the same cold rolling as when the primary work material G2 was obtained. The work material g2 was cracked. However, since the cold working after brazing is performed at a low working rate, the plastic working process is not finished when the primary work material g2 is obtained, and the plastic working process is continued as it is to obtain the final plastic working material. No. 113-No. 117 was obtained.

  Also, plastic working material No. Each of the casting materials g1 for 118 was subjected to the same plastic working process as in Example 3 to produce a plastic working material No. By performing the same plastic working as in the case of obtaining No. 62, the plastic working material No. No. 62 plastic work material No. 118 was obtained. In addition, No. For 118, a primary work material g3 having the same shape as the primary work material G3 was obtained by subjecting the casting material g1 to the same cold rolling as when the primary work material G3 was obtained. Cracks occurred. However, since the cold working after brazing is performed at a low working rate, the plastic working process is not finished when the primary work material g3 is obtained, and the plastic working process is continued as it is to obtain the final plastic working material. No. 118 was obtained.

  As Comparative Example 4, the plastic working material No. 1 in Example 4 was used. No. 63 is obtained by the same casting process and plastic working process as in the case of obtaining No. 63. 119 and No. 120 was obtained, but the plastic working process could not be performed as follows.

  That is, a casting material h1 having the same shape as the casting material H1 was obtained from the copper alloy material having the composition shown in Table 4 by the same casting process as in Example 4.

Then, the same cold drawing as in Example 4 was performed on each casting material h1 to obtain a primary processing material h2 having the same shape as the primary processing material H2 . However, no. 119 and No. For all of 120, since the wire was disconnected at the stage of obtaining the primary work material h2 , the subsequent plastic working process could not be performed, and the final plastic work material could not be obtained.

  Further, as Comparative Example 5, the plastic working material No. 74 or No. No. 78 is obtained by the same casting process and plastic working process as in the case of obtaining No. 78. 121-No. 125 was obtained.

  That is, a casting material i1 having the same shape as the casting material I1 was obtained from the copper alloy material having the composition shown in Table 4 by the same casting process as in Example 5.

  And plastic working material No. 121-No. Each of the casting materials i1 for No. 124 is subjected to the same plastic working process as in Example 5 to produce a plastic working material No. 74, the same plastic working material No. 74 is obtained. No. 74 plastic work material No. 121-No. 124 was obtained.

  Also, plastic working material No. Each of the casting materials i1 for 125 is subjected to the plastic working material No. 1 by the same plastic working process as in the fifth embodiment. 78, the same plastic working as in the case of obtaining No. 78 is performed. No. 78 plastic work material No. 125 was obtained.

  Further, as Comparative Example 6, plastic working material No. 1 was obtained by the same casting process and plastic working process as in Example 6. 126-No. 128 was obtained.

  That is, a casting material j1 having the same shape as the casting material J1 was obtained from the copper alloy material having the composition shown in Table 4 by the same casting process as in Example 6.

  Then, each cast material j1 was subjected to the same plastic working process as in Example 6 with a plastic working material No. 79, the same plastic working as in the case of obtaining No. 79 is performed. No. 79 plastic working material No. 126-No. 128 was obtained.

  Thus, the average crystal grain size D1 of the plastic working materials of Examples and Comparative Examples and the average crystal grain size D2 of the casting material were measured. The average crystal grain diameters D1 and D2 are obtained by cutting a plastic working material or casting material, etching the cut surface with nitric acid, and measuring the grain size of the crystal grains in the macro structure appearing on the etched surface. The diameter is calculated. This measurement was carried out based on the comparison method of the grain size test of JIS H0501 for copper products. After etching the cut surface with nitric acid, the crystal grain size exceeding 0.5 mm was observed with the naked eye. .5 mm or less is observed at a magnification of 7.5 times, and those smaller than about 0.1 mm are etched with a mixed solution of hydrogen peroxide and ammonia water and then magnified by a magnification of 75 with an optical microscope. And observed. The results were as shown in Tables 5-8. In Table 8, what is described as “mixed grain” in the average grain size column indicates that the grain size is not uniform and the grain size varies greatly.

  As apparent from the average crystal grain size D1 of the plastic working material and the average crystal grain size D2 of the casting material shown in Tables 5 to 8, the plastic working material of the comparative example is not refined of crystal grains. On the other hand, in the plastic working material of the example, the crystal grains are greatly refined according to the crystal grain size and the overall processing rate P of the casting material.

  Further, the phase structures of the plastic working materials of Examples and Comparative Examples were confirmed, and the area ratio (%) of the α phase and the total area ratio (%) of the γ phase, δ phase, and ε phase were measured by image analysis. That is, the area ratio of each phase was determined by binarizing a 200-fold optical microscope texture with image processing software “WinROOF”. The area ratio was measured in three fields, and the average value was used as the phase ratio of each phase. The results are as shown in Tables 5 to 8, and it was confirmed that all of the plastic working materials of the examples had the above-described preferred crystal structure.

  Moreover, the plastic workability of the plastic working materials of the examples and comparative examples was evaluated as follows.

  That is, the primary processed material obtained by cold-rolling the casting materials E1, G1, e1, and g1 of the plastic processed materials (excluding some) of Example 1, Example 3, Comparative Example 1, and Comparative Example 3. Cold workability was evaluated by visually confirming whether or not cracks occurred in E2, G2, G3, e2, g2, and g3. The results were as shown in Tables 5-8. In Tables 5 to 8, those having no cracks are indicated by “◯” as being excellent in cold rollability (cold workability), and those having significant cracks are inferior in cold rollability. “X” is indicated as (practical difficulty), and “N” is indicated as “Δ” indicating that it has general cold rolling.

  About the plastic work material of Example 2 and Comparative Example 2, it is hot by visually confirming whether the primary work materials F2 and f2 obtained by hot rolling the casting materials F1 and f1 are cracked. Processability was evaluated. The results were as shown in Tables 6-8. In Tables 6 to 8, those having no cracks are indicated by “◯” as being excellent in hot rollability, and those having significant cracks are indicated as being inferior in hot workability (practical difficulty) as “ A symbol “x” indicates that none of them (which can be practically used although there are some problems) is indicated by “Δ” as having general hot workability.

  Whether or not the plastic working materials of Example 4, Example 5, Comparative Example 4 and Comparative Example 5 are disconnected at the stage of cold drawing the casting materials H1 and h1 to obtain the primary working materials H2 and h2. The cold drawing property was evaluated by visually confirming whether or not the obtained primary processed material was cracked. The results were as shown in Table 7 and Table 8. In Tables 7 and 8, those with no cracks or wire breakage are indicated with “◯” as being excellent in cold drawability, and those with wire breakage or noticeable cracking are inferior in cold wire drawability (practical difficulty) ) Is indicated by “x”, and none of these (which is practical although there are some problems) is indicated by “Δ” as having a general cold drawing property. In addition, No. 78 and no. For 125, by obtaining the same casting material as the casting material T1 by the same casting process as in Example 4, the same cold drawing as in the case of obtaining the primary work material H2 in Example 4 was performed. The primary processed material (drawn wire) having the same shape as the primary processed material H2 was obtained, and the cold drawn property was evaluated depending on whether cracks or breakage occurred in this (No. 125 is a stage for obtaining the primary processed material) Was disconnected).

  As can be understood from the evaluation results of plastic workability shown in Tables 5 to 8, the plastic work materials of the examples are plastic work materials No. 1 having a large average crystal grain size D2 of 150 to 200 μm of the cast material. 1, no. 13, no. 56 and No. No final plastic working material was obtained. Except for 41 having general cold rolling properties and hot rolling properties, it was excellent in cold rolling properties, hot rolling properties, and cold wire drawing properties. On the other hand, the plastic working materials of the comparative examples were all inferior in cold rollability, hot rollability, and cold wire drawing. Therefore, it was confirmed that the plastic work material obtained from the casting material specified in the present invention is excellent in plastic workability (cold rollability, hot rollability, cold drawability).

In addition, test pieces were collected from the plastic working materials of Examples and Comparative Examples, and the test pieces were subjected to a tensile test using an Amsler type universal testing machine to measure tensile strength (N / mm ² ) and elongation (%). .

That is, a No. 5 test piece defined in JIS Z 2201 was collected from the plastic working materials of Examples 1 to 3 and Comparative Example 3, and a tensile test was performed on the test piece using an Amsler type universal testing machine to obtain a tensile strength. The thickness (N / mm ² ) and elongation (%) were measured. In addition, No. 4 test piece defined in JIS Z 2201 was collected from the plastic working materials of Example 4 and Comparative Example 4, and the test piece was subjected to a tensile test using an Amsler type universal testing machine, and the tensile strength (N / mm ² ) and elongation (%) were measured. Further, a No. 9 B test piece defined in JIS Z 2201 was collected from the plastic working materials of Example 5 and Comparative Example 5, and this test piece was subjected to a tensile test using an Amsler type universal testing machine to obtain a tensile strength (N / Mm ² ) and elongation (%). Furthermore, No. 12 B test piece defined in JIS Z 2201 was collected from the plastic working materials of Example 6 and Comparative Example 6, and the test piece was subjected to a tensile test using an Amsler type universal testing machine to obtain a tensile strength (N / Mm ² ) and elongation (%). These test results were as shown in Tables 5 to 8.

  From the results of the tensile tests shown in Tables 5 to 8, it was confirmed that the plastic working materials of the examples were excellent in tensile strength and elongation.

  Moreover, the following evaluation was performed about the plastic work material of an Example, and the bending workability of a plastic work material.

  That is, with respect to the plastic working material of Example 1 and Example 2 which is a thin plate material, a test piece cut out perpendicularly to the rolling direction from the plastic working material is bent 180 ° into a U shape, and a crack occurs. The bending workability was evaluated based on the bending degree R / t (R: radius of curvature (mm) on the inner peripheral side in the bent portion, t: plate thickness (mm) of the test piece). The results are as shown in Tables 5 and 6. In these tables, those in which no cracks occurred when R / t = 1 were indicated by “◯” as being excellent in bending workability, and R / t No crack was generated at 2.5, but a crack was generated at R / t = 1, which was indicated by “Δ” as having good bending workability (no practical problem), and R / t A crack that occurred at = 2.5 was shown by “x” as being inferior in bending workability (practical difficulty).

  Moreover, about the plastic working material of Example 3 which is a thick plate material, and the comparative example 3, the test piece cut out perpendicularly | vertically with respect to the rolling direction from the plastic working material is bent 90 degrees in L shape, and a crack arises. The bending workability was evaluated based on the bending degree R / t (R: radius of curvature (mm) on the inner peripheral side in the bent portion, t: plate thickness (mm) of the test piece). The results are as shown in Tables 7 and 8. In these tables, those that did not crack at R / t = 0.5 are indicated by “◯” as being excellent in bending workability, and R No cracking occurred at / t = 1, but cracking at R / t = 0.5 was indicated by “Δ” as having good bending workability (no practical problem), and R Those having cracks at / t = 1 are indicated by “x” as being inferior in bending workability (practical difficulty).

  Moreover, about the plastic working material of Example 4 (drawing material), Example 5 (drawing material), Comparative Example 4 (drawing material), and Comparative Example 5 (drawing material), which are wire materials, the plastic working material is cut in the longitudinal direction. The test specimen collected in this way was bent 90 degrees into an L shape, and the bending degree R / D when the crack occurred (R: radius of curvature (mm) on the inner periphery side in the bent portion, D: test) The bending workability was evaluated by the diameter (mm) of the piece. The results are as shown in Tables 7 and 8. In these tables, those in which cracks did not occur at R / D = 0.5 are indicated by “◯” as being excellent in bending workability, and R When / D = 1, no cracking occurred, but when R / D = 0.5, cracking was indicated by “Δ” as having good bending workability (no practical problem). Those having cracks at / D = 1 are indicated by “x” as being inferior in bending workability (practical difficulty).

  Further, for the plastic working material of Example 6 and Comparative Example 6 which are pipe materials, the test piece taken by cutting the plastic working material in the longitudinal direction is bent so that the axis thereof is U-shaped, and bent. The bending workability was evaluated based on the presence or absence of cracks occurring in the bent portion when the flat state was in close contact with a plate having a thickness of 4 mm and a width of 30 mm sandwiched between the portions. The results are as shown in Tables 7 and 8. In these tables, those that did not cause cracking are indicated by “◯” as being excellent in bending workability, and those that are cracked are bent. Indicated as “x” as inferior (practical difficulty).

  From the evaluation results of the bending workability shown in Tables 5 to 8, it was confirmed that the plastic working material of the example was excellent in bending workability as compared with the plastic working material of the comparative example.

  Moreover, in order to confirm the corrosion resistance, the following erosion / corrosion test and the dezincification corrosion test specified in “ISO 6509” were performed on the plastic working materials of Examples and Comparative Examples.

That is, in the erosion / corrosion test, samples collected from the plastic working materials of Examples and Comparative Examples were subjected to 3% saline (30 ° C.) from a nozzle having a diameter of 1.9 mm in a direction perpendicular to the rolling direction or the axial direction. ) Was collided at a flow rate of 11 m / sec, and an erosion / corrosion test was conducted. After 96 hours, the corrosion loss (mg / cm ² ) was measured. Corrosion weight loss is the difference per 1 cm ² (mg / cm ² ) from the sample weight before the start of the test to the sample weight after colliding with 3% saline for 96 hours. The results of the erosion / corrosion test were as shown in Tables 7 and 8.

In addition, in the “ISO 6509” dezincification corrosion test, samples taken from the plastic working materials of Examples and Comparative Examples were seated in a phenolic resin so that the exposed sample surface was perpendicular to the stretching direction. After the surface was polished to number 1200 with emery paper, this was ultrasonically washed in pure water and dried. After the corrosion test sample thus obtained was immersed in an aqueous solution of 1.0% cupric chloride dihydrate (CuCl ₂ .2H ₂ O) and kept at 75 ° C. for 24 hours, The sample was taken out from the aqueous solution, and the maximum value of the dezincification corrosion depth, that is, the maximum dezincification corrosion depth (μm) was measured. The results were as shown in Table 7 and Table 8.

  From the results of the erosion / corrosion test and the dezincification corrosion test shown in Table 7 and Table 8, it was confirmed that the plastic working material of the example was excellent in corrosion resistance as compared with the plastic working material of the comparative example.

  As described above, the plastic working material of the example has a mechanical structure (tensile strength, elongation), cold rollability, hot rollability, cold drawability by forming the metal structure confirmed as described above. It was confirmed that the film was excellent both in bending workability and corrosion resistance. In general, it is considered that the elongation is lowered by the refinement of crystal grains. However, as understood from the results of the tensile test described above, in the plastic working material of the present invention, the elongation is reduced by the refinement of crystal grains. Rather, it has improved.

  The plastic working material of the present invention includes springs, switches, connectors, bellows, fuse clips, bushes, relays, gears, cams, joints, flanges, machine screws, bolts, nuts, eyelets, washers, bearings, coils for electronic and electrical equipment. Spring, spiral spring, snap button, header, lead terminal, transistor terminal, lead frame, rotary switch sliding piece, switch contact piece, bearing frame, hydraulic cap, packing, clutch plate, paper blade material, diaphragm, cable attachment / detachment Springs, movable relays for timer relays, heat exchangers, tube plates for heat exchangers, heat exchangers, wire nets, marine nets, aquaculture nets, fish nets, seawater condenser tubes, ship parts shafts, ginger frames, tumblers , Wiring equipment, sockets, pins, welded pipes for gas piping, ship seawater intake, marine ginger frame It is suitably used as a constituent material of the frame), and the like.

Claims (14)

Sn: 4.2 to 15 mass%, Zr: 0.001 to 0.049 mass%, P: 0.01 to 0.14 mass%, Cu: remainder, and [P] / [Zr] = 0.6 to Plasticity formed by hot and / or cold plastic processing of a casting material having an average crystal grain size of 300 μm or less that has a composition satisfying the relationship 36.8 (the content of element a is [a] mass%) Processing material,
It has a metal structure in which the area ratio of α phase is 94.5% or more and the total area ratio of γ phase, δ phase and ε phase is 5% or less, and the average crystal grain size is 150 μm or less. Copper alloy plastic working material. Sn: 0.2-15 mass%, Zr: 0.001-0.049 mass%, P: 0.01-0.25 mass%, Zn: 0.01-35 mass%, Cu: balance, and [P] /[Zr]=0.6-36.8 and 3 [Sn] + [Zn] = 11.1-36.6 (the content of the element a is [a] mass%) A plastic working material obtained by plastic working hot and / or cold casting material having an average crystal grain size of 300 μm or less ,
It has a metal structure in which the area ratio of α phase is 94.5% or more and the total area ratio of γ phase, δ phase and ε phase is 5% or less, and the average crystal grain size is 150 μm or less. Copper alloy plastic working material. Ti: 0.002-0.049 mass%, Hf: 0.002-0.049 mass%, B: 0.001-0.03 mass%, Mg: 0.001-0.3 mass%, Mn: 0.03- 1 element%, Al: 0.01-1 mass%, As: 0.02-0.2 mass%, and Sb: 0.02-0.2 mass% and further containing one or more elements selected as the element When at least one element is selected from Ti, Hf, B, and Mg, ([P] + [Mg]) / ([Zr] +0.5 [Ti] +0.5 [Hf] + [B ]) = Average crystal grain size having a composition satisfying a relationship of 0.6 to 36.8 (the content of the element a is [a] mass%, and the element a that is not contained is [a] = 0) the following casting material 300μm and plastic working Characterized in that it is a shall, copper alloy plastic working material according to any one of claims 1 and 2. Fe: 0.01-0.2 mass%, Co: 0.01-0.2 mass%, and Si: 0.01-0.8 mass%. Is selected, ([P] −0.3 [Fe]) / [Zr] = 0.6 to 36.8 (the content of the element a is [a] mass%) The copper alloy plastic working material according to any one of claims 1 to 3, wherein the copper alloy plastic working material is formed by plastic working a cast material having an average crystal grain size of 300 µm or less that has a composition to be established. When Ni is contained as an unavoidable impurity, it is obtained by plastic working a casting material having an average crystal grain size of 300 μm or less and having a composition in which the Ni content is 0.25 mass% or less. The copper alloy plastic working material according to any one of claims 1 to 4.   It is a plate, strip, wire, rod, or pipe that is subjected to cold processing and / or hot processing at least once on the casting material and at least one recrystallization annealing that is annealing in the recrystallization temperature range. A copper alloy plastic working material according to any one of claims 1 to 5, characterized in that:   Assuming that the recrystallization annealing is performed three times, the processing rate P1 by all the cold work performed between the last recrystallization annealing and the intermediate recrystallization annealing, and the first recrystallization annealing and the intermediate recrystallization annealing are performed. The processing rate P2 by all cold working performed during recrystallization annealing, the processing rate P3 by all cold processing performed before the first recrystallization annealing, and the processing rate P4 by hot working. , P = P1 + 0.4 × (P2 + P3) + 0.2 × P4 (P2 = 0 when intermediate recrystallization annealing is not performed, and the first recrystallization annealing and intermediate recrystallization annealing are not performed P2 = P3 = 0, and when hot working is not performed, P4 = 0), and the plastic working with the overall working rate P defined in this way being less than 30% is used as the casting material. A plastic working material, The copper alloy plastic working material according to claim 6, which has a crystal structure having an average crystal grain size of 150 μm or less.   It is a plastic working material obtained by subjecting a casting material to plastic working so that the total working rate P is 30% or more and less than 50%, and has an average crystal grain size of 60 μm or less. The copper alloy plastic working material according to claim 6, wherein:   A plastic working material obtained by subjecting a casting material to plastic working with an overall processing rate P of 50% or more, and having a crystal structure having an average crystal grain size of 45 μm or less, The copper alloy plastic working material according to claim 6.   A plastic working material obtained by subjecting a casting material to plastic working with an overall processing rate P of 70% or more, and having a crystal structure with an average crystal grain size of 4 μm or less, The copper alloy plastic working material according to claim 6.   Springs for electronic and electrical equipment, switches, connectors, bellows, fuse clips, bushes, relays, gears, cams, joints, flanges, machine screws, bolts, nuts, eyelets, washers, bearings, coil springs, spiral springs, snap buttons, Header, lead terminal, transistor terminal, lead frame, rotary switch sliding piece, switch contact piece, bearing frame, hydraulic cap, packing, clutch plate, paper blade material, diaphragm, spring for cable attachment / detachment, timer relay movable Spring, heat exchanger, heat exchanger tube plate, heat exchanger, wire mesh, marine net, aquaculture net, fish net, seawater condenser tube, ship parts shaft, ginger frame, tumbler, wiring device, socket, pin, Constituent materials such as welded pipes for gas piping, marine seawater intakes, marine ginger frames To characterized in that it is intended to use a copper alloy plastic working material according to any one of claims 7 to claim 10.   A method for producing a copper alloy plastic working material according to any one of claims 1 to 11, obtained by a casting process for producing a casting material having an average crystal grain size of 300 µm or less, and a casting process. A copper alloy plasticity characterized by comprising a plastic working step of performing at least one cold working and / or hot working on a casting material and at least one recrystallization annealing which is annealing in a recrystallization temperature range. Manufacturing method of processed material.   The method for producing a plastic work material made of copper alloy according to claim 12, wherein a processing rate by cold working performed before the last recrystallization annealing is set to 30% or more.   14. The copper alloy plastic working according to claim 13, wherein the final recrystallization annealing is performed under a condition that an average cooling rate in a temperature range of 300 ° C. to 450 ° C. is 0.5 ° C./second or more. A method of manufacturing the material.