TW201231690A - Copper alloy, and wrought copper, electric parts, and connector using thereof, and manufacturing method of copper alloy - Google Patents

Abstract

The present invention provides a titanium-copper, a wrought copper, electronic parts, and a connector having an excellent strength and bending processing property, and their manufacturing method. The copper alloy of the present invention contains 2.0 to 4.0 mass% of Ti, and contains 0 to 0.2 mass% of one or two or more elements selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B, and P as a third element, with the remainder portion being the copper alloy constituted by copper and inevitable impurity. Upon measuring the X-ray diffraction strength of the flattening plane, the ratio (I/I0) of the X-ray diffraction strength I of the flattening plane relative to the X-ray diffraction strength I0 of the pure copper powder in the plane (311) and plane (200) satisfies the following correlation: { I/I0 (311)}/ { I/I0 (200)} ≤ 2.54, and the ratio (I/I0) of the X-ray diffraction strength I of the flattening plane relative to the X-ray diffraction strength I0 of the pure copper powder in the plane (220) and plane (200) satisfies the following correlation: 15 ≤ { I/I0 (220)}/ { I/I0 (200)} ≤ 95.

Description

201231690 VI. [Technical Field] The present invention relates to a copper alloy containing titanium, which is suitable for use as a member for electronic parts such as connectors, and copper products, electronic parts and connectors using the same, and A method of manufacturing a copper alloy. [Prior Art] In recent years, the miniaturization of electronic devices represented by the end of the u-action has been progressing steadily. Therefore, the narrow pitch and low-profile (.L〇WPr〇file) of the connectors used therein are remarkable. The smaller the connector, the narrower the pin width (pin W1dth), and in order to be a folded shape, the member to be used is required to have high strength to obtain the necessary elasticity and to have an excellent ridge capable of withstanding severe bending. Flexibility. In this respect, since the copper alloy containing titanium (hereinafter referred to as "titanium copper") has a relatively high strength and the stress relaxation property is the most excellent in the copper alloy, it has been used as a signal line of particularly required strength since the prior art. Terminal member. Titanium copper type age hardening type copper alloy. Specifically, if a supersaturated solid solution of Ti as a solute atom is formed by solution treatment, and heat treatment is performed for a long period of time at a low temperature from this state, the mother may be decomposed by spinodal decomposition. The cyclical variation of the concentration of the phases is the expansion of the s-modulated structure and the increase in yield. We are developing various means to further improve the characteristics of titanium steel based on this reinforced structure. At this time, the problem lies in the fact that the strength is opposite to the bending workability. In other words, if the strength is increased, the bending workability is impaired. On the contrary, 3 201231690 If the bending workability is emphasized, the desired strength cannot be obtained. Therefore, research and development have been made to achieve a strong addition of titanium and copper from the following viewpoints. A third element such as Fe, Co, Ni, Si, and a previously unseen technique of bending workability (Patent Document 1); concentration of an impurity element group which is limited to solid solution in the matrix phase, and these are used as the second phase Particles (Cu—Ti—x-based particles are precipitated according to the distribution pattern specified in the patent document to improve the regularity of the modulation structure 2); the density of the trace additive element and the second phase particle which are effective to refine the crystal grains are specified (patent Document 3); refining crystal grains (Patent Document 4) and the like. Further, in Patent Document 5, there is proposed a technique of focusing on the crystal orientation 'and in order to prevent cracking in the bending process, and controlling the crystal orientation to satisfy the adjustment heat rolling condition to 1{42〇}/1〇{42〇} >1 〇, further adjust the cold rolling ratio to 1{22〇}/1〇{22〇}$3 〇, thereby improving strength, bending processability and stress relaxation resistance. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The rolling is performed by annealing and cold rolling, the final solution treatment, the calendering-aging treatment, and the improvement of the characteristics is basically achieved by this step. However, there is still room for further improvement in order to obtain titanium copper with better properties. VIII 4 201231690 Accordingly, the present invention is based on the characteristics of the present invention, thereby providing a manufacturing method having an excellent alloy and a copper-exposed product of the same. In view of the fact that the inventors have studied in order to solve the above problems, the present inventors have found that if they are after solution treatment, they have improved the strength and bending workability of copper parts and connectors, as well as copper alloys. Performing a suitable heat treatment (artifrical agi: g treatment) that does not generate or generate a part of the quasi-stationary phase or the stable phase of titanium, and causes a certain degree of phase-decomposition beforehand, and then performs cold rolling and aging. The strength of the beryllium copper that is processed and finally won # will be effectively improved. In other words, the conventional method for producing titanium copper is a heat treatment step that causes phase separation in one stage of aging treatment. On the other hand, the method for producing titanium copper of the invention is largely different in cold rolling. After the second stage, the phase separation is caused. Furthermore, it is also known that the amount of addition of the third element is adjusted to an optimum range, and the second solution treatment for the purpose of solid solution can be used in the past. At the stage of the treatment, it is known that solid solution and recrystallization are simultaneously performed in the solution treatment at one time, and titanium copper having excellent production efficiency and excellent balance of strength and curvature can be obtained. VIII. The present invention based on the above-mentioned findings is a copper: gold which contains 2.G to 4. G mass% of Ti, and contains a total of G to 〇2% by mass selected from Mn, Fe, Mg, Co. , Ni, Cr, v, Can, M〇,

In the group consisting of Zr, S"B and P, two or more elements are used as the third element, and the remainder is composed of copper and unavoidable impurities; when measuring the X-ray diffraction intensity of the calendering surface, χ ray diffraction intensity of the calendering surface ^ 20125690 The ratio of the χ ray diffraction intensity (1/1.) of the pure copper powder in the (3 11 ) plane and the (200 ) plane satisfies the following relationship (1: G/I〇( 311 ) } /{Ι/Ι〇(200)}$2.54· · · (1), and the radiant intensity of the radiant surface I is relative to the (220) plane and the (200) plane The ratio of the X-ray diffraction intensity of the pure copper powder to 1〇 (1/1〇) satisfies the following relation (2): 15${1/10 (220) }/{ΐ/ι〇(20〇) }$95· (2) In another aspect, the present invention is a copper alloy containing 2.0 to 4.0% by mass of Ti' and containing a total of 〇.01~〇.15 mass 〇/0 selected from Μη 'Fe, Mg One or two or more elements of the group consisting of Co, Ni, Cr, V, Nb, Mo, Zr, Si, Β, and 作为 are used as the third element, and the remainder is composed of copper and inevitable impurities. When measuring the diffraction intensity of the radiant rays of the calendering surface The ratio of the X-ray diffraction intensity of the calendering surface 〇 to the diffraction intensity of the χ-ray diffraction of the pure copper powder in the (3 丨丨) plane and the (200) plane (1〇) satisfies the following relation (1): (311 ) } / {1/1〇( 2〇〇) } -2·54 * * * ( 1 ), and the X-ray diffraction intensity I of the calendering surface is relative to the (2 2 0 ) plane and (2 0 0 ) The ratio of the χ-ray diffraction intensity of the pure copper powder in the surface (1/10) satisfies the following relation (3): 30$ {1/1〇( 220 ) } /{1/1〇( 200 ) }$95 According to still another aspect of the present invention, there is provided a steel product comprising the copper alloy. In still another aspect, the present invention provides an electronic component comprising the copper alloy. According to still another aspect of the invention, there is provided a connector comprising the copper alloy. In another aspect, the invention provides a method for producing the copper alloy, which comprises the following steps: ~4.0% by mass of Ti, and containing a mouth "10 0 to 0.2% by mass" selected from the group consisting of _, Fe, Mg, Co, Ni, Cr, V ' Nb ' M 〇 , Zr, Si, B and p i or 2 of them The 7L element is used as the third element, and the remaining part is made of a steel alloy material composed of copper and unavoidable impurities, and is heated to a solid solution having a solid solution limit of 73 〇 to 88 〇. The temperature is limited to 〇χ2〇χ: the temperature, and then the solution treatment is quenched; after the solution treatment, the heat treatment is performed, and after the heat treatment, the final cold rolling is performed at a processing rate of 5 to 4%; After cold rolling, aging treatment is performed. In a method of producing a copper alloy according to the present invention, the heat treatment package 3 is subjected to a heat treatment in which the titanium concentration (% by mass) is set to [It is a shape of [Ti], and the increase in conductivity C ( % IACS) satisfies the following relation (4). 0.5SCS ( - 〇.5〇[Ti]2 — 〇50[Ti]+ 14) · · · (4) The way 'increasing the conductivity. [Embodiment] <Ti content> When the Τι is less than 2% by mass, the strengthening mechanism caused by the formation of the original tuned structure of titanium copper cannot be sufficiently obtained, so that sufficient strength cannot be obtained, and if it exceeds When the amount is 4.0% by mass, the coarse TiCu3 tends to be precipitated, and the strength and the f-curvability tend to deteriorate. Therefore, the content of the oxime in the copper alloy of the present invention is 2 〇 to 4 〇 by mass, preferably 2 7 to 3 5 % by mass, and more preferably 2.9 to 3.3 % by mass. By optimizing the content of Ti, it is possible to simultaneously achieve excellent strength and bending processing suitable for use in electronic parts. <Third element> The third element contributes to the miniaturization of crystal grains. Therefore, a specific third element can be added. Specifically, even if the solution treatment is carried out at a relatively high temperature at which Ti is sufficiently solid-solved, the crystal grains are easily refined, and the strength is easily improved. The third element promotes the formation of a modulation structure. Further, 篦不 J 7L Jing also has the effect of suppressing the precipitation of TiCh. Therefore, the original age-hardening power of titanium steel can be obtained. Among the titanium copper, the highest effect is Fe. Moreover, Mn, Mg, c〇,

Ni, S!, Cr, V, Nb, Mo, Zr, B, and P can also be expected to have the same effect as Bu, and even if they are added alone, they can be expressed as Angu fruit, or two or more kinds can be added in combination. , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , : Health deterioration. At the same time, the coarse second phase particles will cause the bend to change: the raw sugar, and will promote the wear of the metal mold in the press working. Mn, Fe, MD °~〇_5 mass% are selected from the group consisting of Ni, Cr, v, Nb, Mo, Zr, Si, B&amp; P, which is composed of the third element group p. Kind or amount of %, more preferably A, more preferably contains 0~0.2 quality added more? It is preferably contained in an amount of 1.15% by mass. In contrast, it is broad, and although it is effective for the miniaturization of the titanium-copper crystal grain, the temperature is higher than the case where the temperature is not increased. Therefore, it is necessary to make the solid solution temperature in the case of solid solution of halogen. In the past, the solid solution was fully dissolved in 201231690, and after the first solution treatment at a high temperature for a relatively long period of time, the final @solution treatment was performed because the solution treatment was performed twice, resulting in a burden on the manufacturing steps. The situation of birth is low. In the present embodiment, the degree of (four) degrees in the steel is adjusted to 0 to 0.2% by mass, more preferably 〇.〇1 to 〇15% by mass, and the treatment temperature is lower than in the conventional state, once in the first time. The solution treatment simultaneously performs solid solution and recrystallization of the second element. Thereby, it is possible to realize a preferable process in which the amount of heat required for the production of titanium copper is less than that of the prior art, the processing time is short, the production efficiency is increased, and the mass production can be mass-produced. &lt;Integral intensity of X-ray diffraction&gt; Generally, the texture of the calendered surface after the solution treatment is higher in the group ratio of the (2〇〇) plane, and the rolling is caused by the rolling, and finally (22〇 The composition ratio of the surface becomes high. As a result of research by the present inventors, it has been found that in the manufacturing step of the present embodiment, that is, after the final solution treatment and the heat treatment before cold rolling, the previous step, that is, solution treatment-cold rolling-aging Since the modulation structure in the base material is expanded as compared with the manufacturing step of the treatment, the rotation of the (211) surface toward the (311) plane becomes difficult to occur. Therefore, the copper alloy of the present embodiment preferably has a X-ray diffraction intensity J of the calendering surface with respect to the (3 11 ) plane and the (200 ) plane when measuring the diffraction intensity (integral intensity) of the radiant ray of the calendering surface. The ratio of the χ-ray diffraction intensity of the pure copper powder (1/10) satisfies the following relation (1): {Ι/Ι〇(311) }/{Ι/Ι〇( 200 ) }$2·54· · (1) In the present invention, the 'pure copper standard powder system is defined as a copper powder having a purity of 99.5% of 325 mesh (JIS 28801). 9 201231690 {1/1〇(311)}/{1/ 10 ( 200 )} Better 〇5〇~2.〇〇, more preferably {I/I〇(311) }/{I/I 〇(2O0) } is 〇·8〇~1.75. When {Ι/Ι〇 ( 31 1 ) } / {Ι/ι〇 ( 200 ) } is larger than 2·54, there is a case where the strength (0.2% guaranteed stress) is weak and the bending workability is also deteriorated. The texture of beryllium copper is also affected by the processing rate of the final calendering step. In other words, if the rolling processing ratio is too large, the (220) surface is excessively expanded and the bending property is deteriorated. When the processing ratio is too low, the expansion of the (220) surface is insufficient and the strength is lowered. The titanium copper of the present embodiment is preferably subjected to a processing ratio of 5 to 40%, more preferably 1 to 30%. The texture of the calendering surface in this case is preferably a ratio of the X-ray diffraction intensity of the Χ-ray diffraction intensity I of the calendering surface to the pure copper powder of the (22 〇) plane and the (2 〇〇) plane (1). / 1〇) satisfies the following relation (2): 15$ Π〆1. ( 220 ) } / {1/ 10 ( 200 ) } $ 95 · · · ( 2). When {1/1 〇 ( 220 ) ( 200 ) } is less than 15, there is a case where the processing rate is lowered and the work hardening due to the rolling step becomes insufficient. It is found that when the solution treatment is performed twice, compared with the texture in the case where only one solution treatment is performed, the recrystallization texture ratio is subjected to the second solution treatment only when the solution treatment is performed once. The situation is weak, and (220) / (200) becomes larger than the value. In order to obtain a good balance between strength and flexibility, it is preferred to replace the relation (2) with the following relation (3) except for the relation (1): 30~(220)}/{1/1〇(200) 95 - · . (3) More preferably '{I/I〇( 220 ) ( 200 ) } is 40~70, more preferably {1/1. ( 220) }/〇/][〇( 200 ) } is 40~55. 10 201231690 &lt;Use&gt; The steel alloy of the present embodiment can be provided as various stretch plates, strips, tubes, rods, foils, and wires. Dreaming, β °σ 'fine processing of the copper alloy of the present embodiment, for example, a switch, a connector sub-part. Jack tweezers, relays, etc. <Production method> One of the characteristics of the steel alloy of the present embodiment is 'the final solution treatment 拽 ^ ^ ^ ± 枓, and the condition of the dish is subjected to a short time of heat ^ When the clams are over-traveled and the time is too long, in the subsequent aging treatment, the strong-yielding sputum, the tens of thousands of strengths, and the phase which causes the deterioration of the bending workability are easily precipitated. Moreover, the temperature of the material in the right heat treatment is too low. When the time is too short, it is easy to expand in the aging treatment. The modulation structure generated by the off-phase knife solution... The right heat treatment of the solid-cold titanium steel is performed, and the electrical conductivity increases with the expansion of the modulation structure. Therefore, the degree of annealing can be performed before and after annealing. The change in the rate is used as a standard. According to the research of the present inventors, it is preferable that the heat treatment is to increase the gamma concentration by 0.5 to 8% IACS, more preferably 1 to 4% I ACS. That is, it is preferable here that the heat treatment is carried out with a relative hardness of less than 90%. The specific heat treatment conditions corresponding to the increase in conductivity are 铋Μ dry horse 枓 temperature 300. (: Above, less than 70 (TC and heating for 0.001 to 12 hours. More specifically, Taiying...At heat treatment in the form of titanium in the case of titanium concentration (% by mass) is set to [Ti], The rising value of the isoelectric rate C (% I ACS ) satisfies the following relation (4): 11 201231690 〇·5 S CS ( - 0.50 [Ti] 2 - 0.50 [Ti] + 14 ) · · · (4). According to the above formula (4), for example, when the Ti concentration is 2.0 mass%, it is preferable to carry out the condition of increasing the conductivity by 0.5 to 丨1% IACs, and the concentration of Τι is 3.0% by mass. In the case of the case, it is preferable to carry out the condition that the conductivity is increased by 0.5 to 8% IACS, and in the case where the Ti concentration is 4 〇 mass%, it is preferable to increase the conductivity by 5 to 4% IACS. In the heat treatment of the present embodiment, when the titanium concentration (% by mass) is m], the increase in conductivity c (% IAcs) satisfies the following relation (5): K〇-C- ( °-25[Ti]2-3.75[Ti]+ 13) (5) If it is according to the above (5) &lt;, for example, when the concentration of cerium is 2.0% by mass, it is preferable to make it conductive. Rate rises i Q~ When the condition of the 6th heart is to enter the lamp at a temperature of 3 〇 mass%, it is preferable to carry out the condition of the electric conductivity at a rate of .G to 4% IACS, and the concentration of Ti is * 〇 mass%. In the case of the case, it is preferable to carry out the guide. &amp; Conductively increasing the i.Wcs strip in the heat treatment after the final solution treatment, when the hardness of the copper alloy is peaked, the lead ft / 〇 a4 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the final embodiment, the solid solution ACS is about the same, that is, the heat treatment after the u-energy treatment, and the aging of the value, the heat imparted to the steel alloy is extremely small. The hardness is the peak heat treatment, and the τ is the following. 2012 Any condition is carried out. 12 201231690 • Material temperature is above 300〇C, less than 40 (TC, heating for 0.5~3 hours • Material temperature is above 40 (TC, less than 5〇 (rc, heating 0.01~0) ·5 Material throwing is above 5〇〇C, less than 6〇〇〇c, plus 〇〇〇·〇·〇1 hour. Material, dish at 600 C The above is not reached. 〇 〇 〜 〇 〇〇 〇〇 〇〇 〇〇 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又Hour • Material temperature is above 40 (TC, less than 45 (rc, heating 0.2~0.5 heating 0.005 • Material temperature is 5 〇 (TC or more, less than 55 〇t, 〇·〇 1 hour). • The material temperature is above 55 (rc, less than rc, heating 〇〇〇1~ ϋ·0〇5 hours. • Material temperature is 60〇m, less than 65〇t, heating 〇〇〇25~ 〇·〇〇 5 hours. Hereinafter, a preferred embodiment of each step will be described. 1) Ingot manufacturing step * The manufacture of the anchoring by the dazzling and scale making is basically carried out in the true two or the emotional gas environment. The added elements remain in the 4 materials and do not effectively act to increase the strength. Therefore, in order to eliminate the dissolution residue, 13 201231690 must be thoroughly stirred after adding elements such as Fe and Cr, and then kept for a specific period of time. On the other hand, since Ti is relatively easily dissolved in Cu, it may be added after the third element group is melted. Therefore, it is added in a manner of containing 0 to 0.2 mass%/0 in Cu to be selected from Mn, Fe, and Mg. , Co, Ni,

An ingot or a mixture of two or more kinds of halogen, which is composed of Cr, V, Nb, Mo, Zr, Si, B, and p, is then added in an amount of 2 to 4% by mass to produce an ingot. 2) Homogenization annealing and hot rolling Here, it is preferred to eliminate (10) BB which is generated in solidification segregation or scale formation as much as possible. In the subsequent solution treatment, the first ruthenium phase particles are finely dispersed and uniformly dispersed, and also have an effect of preventing mixing. The car father Jia Wei in the town ^ 2A. ah. ffBst _ ^ after the installation step, heated to 900 ~ 970 ° C and 3 to 24 hours of clear servant ρ scooping annealing, and then hot rolling . In order to prevent the brittleness of the liquid metal, it is preferably set at 960 ° C for the mature rolling calender and hot rolling, and 3) after the first solution treatment, preferably the appropriate cost, or r ^ e ^ ^ _ The solution treatment is carried out after cold rolling and annealing. Specifically, 篦- °Γ » Η % - / combined processing system sets the heating temperature to 850~900 lines for 2~1 〇 minutes. ^ , , It is better to increase the temperature and the cold part at this time so that the amount of the first and the seventh is O.Oi'O b '笫兀素.•容处理,&lt;ϊή彳# 〇 ,1. In the case of the first solid solution treatment step, since the solid solution and recrystallization are carried out only at the final solid solution point Λ 4' ^ m. 4) Intermediate rolling 14 201231690 The second phase particles in the intermediate solution treatment before the final solution treatment will have a higher degree of processing. The final solidification improves the degree of processing, and the final solid, the contents are finely precipitated. However, if it is excessive, ^ A: m , it will sometimes cause the recrystallized texture to expand to produce plastic anisotropy. Therefore, the processing degree of the intermediate calendering is preferably 7 〇 曰 曰 曰 曰 & & & & & ^ ^ ^ ^ ^ ^ ^. The degree of processing is defined by ί ((thickness after rolling, thickness after rolling) / thickness of two 垫 pad I) xlOO%}. 5) Final solution treatment There is analysis (4) generated by the casting or intermediate seating process in the final solution treatment A + , copper δ gold material. Since the precipitate sometimes hinders the bending property and the mechanical property after the treatment is increased, it is preferable to heat the copper alloy material at a temperature at which the precipitate in the copper alloy material is completely dissolved in the final solution treatment. 'However', if heated to completely remove the precipitates, the pmnmg effect of the grain boundary formed by the precipitates disappears, and the crystal grains are greatly coarsened. If the crystal grains are greatly coarsened, the strength tends to decrease. Therefore, as the heating temperature, the copper alloy material before solid solution is heated to a temperature near the solid solution limit of the composition of the second phase particles. The amount of addition of Ti is in the range of 2.: 4.G mass%, and the solid solution limit of ruthenium is in the amount of addition. 5' (also referred to as "solid solubility limit temperature" in the present invention) is "Ο c = ', for example, when the amount of addition of Ti is mass%, it is about c. and the right is caught and heated to the temperature, and When the cooling rate is increased, the production of the coarse ginseng will be suppressed. Therefore, it is more typical to heat up to 730 ~ 8 8 0 ° Γ 丁 .. The solid solution limit becomes the same as the added amount, and The second type of ruthenium is heated to a temperature of 730 to 880 ° C. The solid solution limit becomes the same as the temperature at the temperature of G to 2 G ° C, preferably to a temperature of 0 to 1 〇. (: 15 201231690 In order to suppress the generation of coarse second phase particles in the final solution treatment, it is preferable to rapidly heat and cool the copper alloy material as much as possible. Specifically, the solid solution limit of the composition of the second phase particles is attached. (9) ~5 saki, preferably in the environment of W15G~5 sails, the alloy material can be used for rapid heating. Cooling can also be carried out by water cooling, etc. 6) The heat treatment heat treatment conditions are as above. After heat treatment, 7) final cold rolling β After the above annealing, the final cold rolling is performed. The final cold working can be carried out to: the strength of the high titanium copper. At this time, if the degree of processing is less than 5%, the effect of the charge cannot be obtained [therefore, it is preferable to set the workability to 5 % or more 'However, if π is added, the processing strain generated by the flatness of the crystal grains becomes larger than the lattice strain generated by the intragranular pulverization, and the bending workability is deteriorated. The aging treatment or strain relief annealing is likely to cause grain boundary analysis~30: addition: the degree is set to less than qing, preferably 5 to 4%%, more preferably 1 〇 0, and even more preferably 15 to 25%. Aging treatment, aging treatment after cold rolling. The usual conditions can be used for the treatment. In particular, the current treatment is preferably carried out with a material of 300 to 400 C for 3 to 12 hours of strips of 201231690 pieces. Furthermore, the aging time is short (unsuccessful) ” ... aging treatment up to 29 (TC: H hours), aging treatment temperature is low (not In the case of aging time, there is a case where the strength and the electrical conductivity are lowered. Moreover, in the case of a long time (above 13 hrs) or the case of aging (5 rc or more), there may be a case of ":" The power-saving hand is the same, but the strength reduction aging treatment is better under any of the following conditions. · The material temperature is above the gift, less than 36〇t, heating 5~8 small•Material temperature is above 360T: Not up to 38 (rc, heating b for 7 hours.

• The material temperature is 38 (TC or more, less than 4 〇 (rc, heating 3). J aging treatment is more preferably carried out under any of the following conditions. • The material temperature is above 3401, not up to 36 (rc, heating 6~) • Material temperature above 360 ° C, less than 3 thieves, heating 5 ~ 6 • Material temperature is 38 (TC or more, less than 4 〇 (rc, heating 4 to 6 hours. Furthermore, those skilled in the art should It is to be understood that steps such as grinding, polishing, bead blasting, and the like for removing surface rust scales may be performed in an appropriate manner between the above steps. [Examples] s 17 201231690 The following shows the practice of the present invention. The examples and the comparative examples are provided to enhance the understanding of the present invention and its advantages, and are not intended to limit the invention. When the copper alloy of the present invention is produced, since the active metal Ti is added as the second component, In the case of melting, a vacuum melting furnace is used. Further, in order to avoid the occurrence of unexpected side effects due to the incorporation of impurity elements other than the elements specified in the present invention, the raw materials are strictly selected for use with higher purity. Ingots are carried out at 95〇 c, after heating for 3 hours, homogenization annealing, hot rolling at 900~95 CTC, to obtain a hot rolled sheet having a thickness of 1 〇 mm, the cast bond system having: adding the third element of the table i as needed; Ti is added at the concentration of Table 1, and the remainder is composed of copper and unavoidable impurities. After the skin is removed by the end face cutting, cold rolling is performed to form the thickness of the strip (i 5_ ), as needed ( The first solution treatment in the strip state is carried out according to the amount of addition of the third element. The conditions of the first solution treatment are set to be heated for 75 minutes in the 85th generation. Then, in the middle of the cold rolling, The final plate thickness reaches Q25mm and the middle of the adjustment is 柘Lu尨, ^ ^ 7 ^ and...1 The final solution treatment is carried out in an annealing furnace that can be heated rapidly, and then the moxibustion water is cooled. The heating condition at this time is Sigh. The temperature of the material is Ti-degree (Tl desert is 3.2% by mass when the amount is about 0/. When it is about 73 (TC, Ti澶 Α Τ ι is 2.0 mass / 4 〇 mass%) At about 84 〇 ° c) in it! The solid solution limit of Ti becomes the basis of the addition of 40c) as a reference to the table in the form of W~ Articles Next n... Don't keep it for 1 minute.

^ According to the test piece to Table 1 斛 # speak A kg. • After the cold rolling is carried out under the conditions of the load, 18 201231690 is heat-treated under the conditions described in Table 1 in the Ar environment. After the derusting by pickling, the final cold rolling was carried out under the conditions shown in Table 1, and finally subjected to aging treatment under the respective heating conditions shown in Table 1, to prepare test pieces of the examples and the comparative examples. 19 201231690 [Table i] NO. Alloy composition manufacturing step Ti Element 3 First solution treatment Final solution treatment Heat treatment Cold pressure delay treatment (wt%) (wt%) Temperature (°C) Time (8) Temperature (°C) Time (h) EC difference before and after heat treatment (%IACS) Processability (%) Temperature (°C) Time (1) Comparative Example 1 3.2 0 - 800 1 — - 0 25 400 6 2 3.2 0.0 IFe — 805 1 A - 0 25 400 6 3 3.2 0.15Fe — 810 — — 0 25 400 6 4 3.2 0.17Fe ~ 815 - - 0 25 400 6 5 2.9 0.17Fe - 805 - - 0 25 400 6 6 3.2 0 850 〇C7.5 minutes 800 1 — - 0 25 400 6 7 3.2 0.04Fe 850 〇C7.5 minutes 805 - - 0 25 400 6 8 3.2 0.09Fe 850 °C 7.5. Minute 810 — — 0 25 400 6 9 3.2 0.13Fe 850 〇C7.5 minutes 815 — — 0 25 400 6 10 2.9 0.17Fe 850 〇C7.5 minutes 805 - - 0 25 400 6 11:: 3.2 0.06Fe — 805 500 0,01 4 1 350 6 12ί 3.2 0.06Fe — 805 1 500 0.01 4 50 350 6 3.2 : vo ! — n8Q5'. Ά1Λ: C:450/r .5 . • 9, 20 400 0.0167 Example 1 3.2 0 — 820 500 0.01 4 25 350 6 2 3.2 O.OlFe — 805 500 0.01 4 25 350 6 3 3.2 0.15Fe - 810 1 500 0.01 3 25 350 6 4 3.2 0.20Fe 850 &quot;C7.5 minutes 820 1 550 0.006 4 25 350 6 3.2 O.OSFe - 805 I 500 0.01 4 25 350 6 2.0 0.08Fe - 750 1 450 0.1 6 25 350 6 _丨4.0 0.08Fe — 850 1 600 0.003 4 25 350 6 3.2 0.08Fe — 805 1 500 0.01 4 5 350 6 Mine 3.2 0.08Fe — 805 500 0.01 4 40 350 6 _ m 3.2 O.OlCo O.OINi O.OlCr 0.01 V O.OlNb O.OlMo — 810 1 550 0.006 5 25 350 6 Climbing Φ Theory 3.2 O.OIMn O.OlZr O.OlSi O.OlMg 0.01B 0.01P — 810 1 550 0.006 4 25 350 6 Use the following conditions Each of the obtained test pieces was subjected to characteristic evaluation. 20 201231690 The results are shown in Table 2. <Strength> Made by a press machine in a manner in which the stretching direction is parallel to the rolling direction

Si : ί: 2: According to the claw-Z2241, the test piece was subjected to tensile measurement, and the 2·2% guaranteed stress (γδ) in the direction of the flattening direction was obtained. <Bending workability> According to m H 3U0, the ratio of the minimum radius (MBR) to the plate thickness (t) which is the ratio of the minimum radius (MBR) of the Badway (f-sleeve and the rolling direction in the same direction) without the crack is measured. /t value. <Electrical conductivity> According to JIS Η 0505, the conductivity (Ec · % IACS) 〇 * &lt; crystal orientation &gt; was measured by the 4-terminal method. For each test piece, an x-ray winding of Ultima 2000 model manufactured by Rigaku Electric Co., Ltd. was used. The diffraction intensity curve of the firing device on the following calendering surface, and the diffraction intensity (integral value) of the 结晶 ray of the crystal surface of the mi crystal surface, the lower surface, the (220) crystal surface, and the (3 丨丨) crystal surface h Under the same measurement conditions, the X-ray diffraction intensity for (iii) crystal plane, (2〇〇) crystal plane, (22〇) crystal plane, and (311) crystal plane was also determined for the pure copper powder standard sample. (Integral value) ^. Divide another J. Ten count I/IoOn)"/!〇() (311), and find 〇/!〇( 311 ) } / {工/1〇( 2〇〇) } and {]/Working (220) }/ {1/1〇( 200 ) }. • Target: Cu tube 21 201231690 min • Tube voltage: 40kV • Tube current: 40mA • Scanning speed: 5 ° / • Sampling width: 0.02 22 201231690 [Table 2] NO. U/I〇( 3 11)}/{l/I〇( 2〇〇)} {I/I〇( 220 )}/{I/I〇( 2〇〇) j Distortion comparison example* Example

&lt;Exploration&gt; Comparative Examples 1 to 5 show that the additive element of the third element is 〇~〇n s %, and the first solution treatment is not performed, and only the final solid solution is performed once, ' Winter solid solution treatment - cold calendering - the previous sequence of aging treatments is an example of the case of 劁 batch + also, ^. In Comparative Examples 1 to 5, the strength of the filling was not obtained. The knives of Examples 6 to 10 indicate that the additive element of the third element is 〇~ 〇·1 7 ..g 〇/() ' and the two-stage solution treatment (first solution treatment and # s solid solution) An example of the case where 彳^ _ to ) ' is manufactured by λ &amp; Jiu Shui in the order of the final solution treatment - cold calendering - aging treatment. In Comparative Example 5 to 1 ’, the viability of 寿t A increased, but sufficient strength could not be obtained. 23 201231690 Example 11 is shown in the case of the final solution treatment-heat treatment-cold calendering process, and the case where the cold press delay is too low is 4 Μ 7 . In Comparative Example 1, since the degree of processing was too low, sufficient strength could not be obtained. Comparative Example 12 shows an example in which (4) the processing of the time delay is too high in the case of being manufactured in the order of the final solution treatment-heat treatment-cold calendering-aging treatment. In Comparative Example 12, although sufficient strength was obtained, the degree of workability was too high, so that the flexibility was deteriorated. Comparative Example 13 shows that in the case of the final solution treatment-heat treatment-cold calendering-aging treatment, the final solution treatment is carried out in such a manner that the hardness of the titanium copper is close to the peak peak aging condition). An example of a situation in which final aging treatment is performed in a very short time. In Comparative Example U, since the heat treatment after solid solution was set to the vicinity of the peak, a coarse stable phase was precipitated, and "the bendability was deteriorated. As compared with the comparative example, it can be seen that the balance between the embodiment &quot;&amp; μ and bending workability is preferably improved. [Simple description of the diagram] None [Key component symbol description] None 24

Claims (1)

201231690 VII. Patent application scope: 1. A copper alloy containing 2.0 to 4.0% by mass of Ti and containing a total of 0 to 0.2% by mass selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, One or two or more elements of the group consisting of Mo, Zr, Si, B, and P are used as the third element 'the remainder is composed of copper and unavoidable impurities; and the X-ray diffraction intensity of the rolled surface is measured. The X-ray diffraction intensity I of the calendering surface satisfies the following relationship (1/1〇) with respect to the X-ray diffraction intensity (1/1〇) of the pure copper powder in the (3 11 ) plane and the (2〇〇) plane ( 1): {Ι/Ι〇(311) }/{Ι/Ι0 ( 200 ) }$2.54· · · (1) Moreover, the X-ray diffraction intensity I of the calendering surface is relative to the (220) plane and the (200) plane The ratio of the X-ray diffraction intensity I 〇 of the pure copper powder in the middle (I / I 〇) satisfies the following relation (2): 15${1/1〇( 220 )}/{1/1〇(20〇)} $95· · · (2). 2. A copper alloy which contains 2.0 to 4.0% by mass of Ti and contains 0.01 to 0.15 mass% in total selected from the group consisting of Mn, Fe, Mg, Co, Ni, Niobium, V, Nb, Mo, Zr, Si, One or two or more elements of the group consisting of B and P are used as the third element, and the remainder is composed of copper and unavoidable impurities. When measuring the X-ray diffraction intensity of the calendering surface, the X of the calendering surface The ratio of the X-ray diffraction intensity of the ray diffraction intensity I to the pure copper powder in the (3 丨丨) plane and the (2 〇〇) plane (〇 / 1()) satisfies the following relation (1): 1/1〇( 311 )}/{1/1〇( 200 ) 2.54 - · · (1) — 25 201231690 Moreover, the X-ray diffraction intensity I of the calendering surface is relative to the (220) plane and the (200) plane The X-ray diffraction intensity ratio of the pure copper powder (I〆") satisfies the following relation (3): 3〇SU/I0 (220 )}/{I/I0(20〇)}$95. · · ( 3) 3. A steel-stretching product consisting of a copper alloy of the first or second patent application scope. 4. An electronic component consisting of a copper alloy of claim 1 or 2. 5. A connector having There is a copper alloy of the second or second application of the patent scope. 6. A method for producing a copper alloy according to claim 1 or 2, which comprises the following steps: containing 2.0 to 4.0% by mass of Ti, and containing the total 〇~〇2% by mass of one or two or more elements selected from the group consisting of Mn, Fe, Mg, Co, Ni, Cr, V, Nb, Mo, Zr, Si, B, and P as the first 3 elements, the remaining part of the copper alloy material consisting of copper and unavoidable impurities, heated to a ratio of 730~88 (rCR Ti solid solution limit becomes the same as the solid solution limit temperature of the addition amount ~ 2 (rc The temperature is then subjected to quenching solution treatment; after the solution treatment, the heat treatment is performed; after the heat treatment, the final cold rolling is carried out at a processing rate of 5 to 4%; and after the final cold rolling, the aging treatment is carried out. According to the method for producing a copper alloy according to claim 6, the heat treatment 26 201231690 includes the following heat treatment: when the titanium concentration (% by mass) is set to [Ti], the rise value of the conductivity C ( % IACS ) satisfies the following relation (4): 0.5S CS ( - 0. 50[Ti]2- 0.50[Ti]+ 14) · · · (4) The way the conductivity is increased.