The present invention relates to steel members, steel plates, and methods for manufacturing them. Background technology [0002] 　In the field of steel sheets for automobiles, the application of steel sheets having high tensile strength is expanding in order to achieve both fuel efficiency and collision safety against the background of recent stricter environmental regulations and collision safety standards. However, as the strength increases, the press formability of the steel sheet decreases, which makes it difficult to manufacture a product having a complicated shape. [0003] 　Specifically, the decrease in ductility of the steel sheet due to the increase in strength causes a problem of fracture of a highly processed portion. In addition, residual stress after machining causes springback and wall warpage, which causes a problem that dimensional accuracy deteriorates. Therefore, it is not easy to press-mold a steel sheet having a high strength, particularly a tensile strength of 780 MPa or more, into a product having a complicated shape. It should be noted that roll forming rather than press forming makes it easy to process high-strength steel sheets, but its application is limited to parts having a uniform cross section in the longitudinal direction. [0004] 　Therefore, in recent years, for example, as disclosed in Patent Documents 1 to 3, a hot stamping technique has been adopted as a technique for press-molding a material that is difficult to form, such as a high-strength steel plate. The hot stamping technique is a hot stamping technique in which a material to be molded is heated and then molded. [0005] 　In this technique, since the material is heated and then molded, the steel material is soft and has good moldability at the time of molding. As a result, even a high-strength steel material can be accurately formed into a complicated shape. Further, in the hot stamping technique, since quenching is performed at the same time as molding by a press die, the steel material after molding has sufficient strength. Further, since the strain introduced by molding is eliminated by transformation during quenching, the steel material after molding is also excellent in toughness. [0006] 　For example, according to Patent Document 1, it is possible to impart a tensile strength of 1400 MPa or more to a steel material after forming by a hot stamping technique. Prior art literature Patent documents [0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-102980 Patent Document 2: Japanese Patent Application Laid-Open No. 2012-180594 Patent Document 3: Japanese Patent Application Laid-Open No. 2012-1802 Patent Document 4: Japanese Patent Application Laid-Open No. 2003-268489 Patent Document 5: Japanese Patent Application Laid-Open No. 2017-179589 JP Patent Document 6: JP 2015-113500 Patent Publication Patent Document 7: JP-T 2017-525849 Patent Publication Patent Document 8: JP 2011-122207 JP Patent Document 9: JP 2011-246801 JP Patent Document 10: Japanese Unexamined Patent Publication No. 2012-1816 Outline of the invention Problems to be solved by the invention [0008] 　Currently, with the setting of challenging fuel efficiency targets in each country, higher strength steel materials are required to reduce the weight of the vehicle body. Specifically, a high-strength steel material exceeding 1.5 GPa, which is a general strength for hot stamping, is required. [0009] 　By the way, when a high-strength steel plate having a strength of more than 1 GPa is applied to an automobile, not only the above-mentioned formability and toughness after molding but also hydrogen embrittlement resistance is required. If the high-strength steel sheet does not have sufficient hydrogen embrittlement resistance, the steel may corrode during use by general users after the automobile is shipped to the market, and hydrogen generated during the corrosion reaction may cause embrittlement cracking. [0010] 　In the region where the strength exceeds 1.5 GPa, the hydrogen embrittlement susceptibility of the steel material increases rapidly, so that there is a concern about hydrogen embrittlement cracking even in a portion where corrosion is slight. Therefore, in order to put a high-strength steel material exceeding 1.5 GPa into practical use as a vehicle body, a technique for providing a steel member having excellent hydrogen embrittlement resistance in a corrosive environment is required. [0011] 　Regarding high-strength steel materials exceeding 1.5 GPa, for example, Patent Document 2 discloses a press-molded product that is hot press-formed with excellent toughness and a tensile strength of 1.8 GPa or more. However, measures against hydrogen embrittlement in a corrosive environment are not sufficient, and it may not be possible to meet safer demands for use as an automobile member. [0012] 　Further, Patent Document 3 discloses a steel material having an extremely high tensile strength of 2.0 GPa or more and further having good toughness and ductility. However, measures against hydrogen embrittlement in a corrosive environment are not sufficient, and it may not be possible to meet safer demands for use as an automobile member. [0013] 　Regarding hydrogen embrittlement resistance, for example, Patent Documents 4, 5 and 6 show hot stamping materials having excellent hydrogen embrittlement resistance in a hydrochloric acid immersion environment. However, in an atmospheric corrosion environment when using an automobile, hydrogen embrittlement is more likely to occur than in a hydrochloric acid immersion environment due to pitting corrosion as described later, and it is not suitable for the use of a high-strength material exceeding 1.5 GPa as in the present invention. It is enough. [0014] 　Further, Patent Document 7 describes a hot stamping material in which Ni in a steel material is concentrated on the surface layer, and describes that it has an effect of suppressing hydrogen intrusion during heating in the hot stamping process. However, there is no description about hydrogen embrittlement resistance in a corrosive environment when using an automobile, and it is insufficient for the use of a vehicle body of a high-strength material exceeding 1.5 GPa. [0015] 　Further, Patent Documents 8, 9 and 10 indicate a hot stamping material in which Ni is diffused from a Ni-based plating layer to a steel sheet surface layer, and it is described that it has an effect of suppressing hydrogen intrusion in a corrosive environment. However, as will be described later, pitting corrosion, which is the starting point of hydrogen embrittlement cracking, cannot be reduced, and even if hydrogen intrusion is reduced, there is a high risk of hydrogen embrittlement cracking due to accumulation in the pitting corrosion portion. [0016] 　The present invention has been made to solve the above problems, and provides steel members, steel sheets, and methods for producing them, which have high tensile strength and toughness and excellent hydrogen embrittlement resistance in a corrosive environment. The purpose is. Means to solve problems [0017] 　The gist of the present invention is the following steel members, steel plates, and methods for manufacturing them. [0018] 　(1) The chemical composition is by mass%, C: 0.25 to 0.60%, Si: 0.25 to 2.00%, Mn: 0.30 to 3.00%, P: 0.050%. Hereinafter, S: 0.0100% or less, N: 0.010% or less, Ti: 0.010 to 0.100%, B: 0.0005 to 0.0100%, Cu: 0.15 to 1.00% , Mo: 0.10 to 1.00%, Cr: 0 to 1.00%, Ni: 0 to 1.00%, V: 0 to 1.00%, Ca: 0 to 0.010%, Al: 0 to 1.00%, Nb: 0 to 0.10%, Sn: 0 to 1.00%, W: 0 to 1.00%, Sb: 0 to 1.00%, REM: 0 to 0.30 %, Remaining: Fe and impurities, and the maximum value of the Cu content in the range of 0 to 30 μm from the surface is 1.4 times or more the Cu content in the depth of 200 μm. .. [0019] 　(2) The chemical composition is mass%, C: 0.25 to 0.60%, Si: 0.25 to 2.00%, Mn: 0.30 to 3.00%, P: 0.050%. Hereinafter, S: 0.0100% or less, N: 0.010% or less, Ti: 0.010 to 0.100%, B: 0.0005 to 0.0100%, Cu: 0.15 to 1.00% , Mo: 0.10 to 1.00%, Cr: 0 to 1.00%, Ni: 0 to 1.00%, V: 0 to 1.00%, Ca: 0 to 0.010%, Al: 0 to 1.00%, Nb: 0 to 0.10%, Sn: 0 to 1.00%, W: 0 to 1.00%, Sb: 0 to 1.00%, REM: 0 to 0.30 %, Remaining: Fe and impurities. The maximum Cu content in the range of 0 to 30 μm from the surface is 1.2 times or more the Cu content in the depth of 200 μm, and the average crystal grain size is 30 μm. A steel plate characterized by being as follows. [0020] 　(3) The time t1 (hr) from the end of rough rolling to the start of finish rolling by heating a slab having the component according to (2) above to 1100 to 1350 ° C. in the method for producing a steel sheet according to (2). When the average temperature of the rough bar from the end of rough rolling to the start of finish rolling is T1 (° C) , heating is performed under the condition that (T1 + 273) × (logt1 + 20) ≧ 20000 and the finish rolling end temperature is Ar 3 points to 1000 ° C. A step of hot-rolling the slab to obtain a hot-rolled steel sheet, a step of cooling the hot-rolled steel sheet at an average cooling rate of 10 ° C./s or more, and a step of winding the cooled steel sheet at 700 ° C. or lower, winding. A method for manufacturing a steel sheet, which comprises a step of pickling the steel sheet after rolling. [0021] 　(4) The pickling uses hydrochloric acid or sulfuric acid, the pickling temperature is 80 to 90 ° C., the acid concentration α (%), and the pickling time t (s) are 6 ≦ α <14, 0 For the 　obtained slab, Ar 3 points, Ac 3 points, Ms point and upper critical cooling rate were determined by the following method. The results are shown in Tables 1-1 to 1-2. [0119] 　A cylindrical test piece having a diameter of 3 mm and a length of 10 mm was cut out from the slab, and the test piece was heated to 1000 ° C. at an average heating rate of 10 ° C./sec in an air atmosphere, held at that temperature for 5 minutes, and then held at that temperature for 5 minutes. It was cooled to room temperature at various cooling rates. The cooling rate was set at intervals of 10 ° C./sec from 1 ° C./sec to 100 ° C./sec. By measuring the change in thermal expansion of the test piece during heating and cooling and observing the structure of the test piece after cooling, Ar 3 , Ac 3 , Ms, and the upper critical cooling rate were measured. [0120] 　The upper critical cooling rate was set to the minimum cooling rate at which the ferrite phase was not precipitated among the test pieces cooled at the above cooling rate. [0121] 　Next, using the obtained slab, the steel members and steel plates shown in Examples 1 to 4 below were produced. [0122] 　 　The slabs shown in Tables 1-1 to 1-2 above were hot-rolled to obtain a hot-rolled steel sheet having a thickness of 3.0 mm. In the hot rolling step, the slab heating temperature was set to 1250 ° C., the parameter S1 from rough rolling to the start of finish rolling was set to 22657, the finish rolling end temperature was set to 930 ° C., and cooling was performed at an average cooling rate of 20 ° C./s until winding. It was rolled up at 550 ° C. [0123] 　The parameter S1 was controlled to 22657 in the range of the time from the end of rough rolling to the start of finish rolling of 1 to 60 s and the average temperature of the rough bar from the end of rough rolling to the start of finish rolling of 950 to 1150 ° C. Then, the hot-rolled steel sheet was descaled for 30 seconds with hydrochloric acid having a concentration of 12% and a temperature of 90 ° C. Then, it was cold-rolled by a cold-rolling machine to obtain a cold-rolled steel sheet having a thickness of 1.4 mm. [0124] 　The cold-rolled steel sheet is heated to 920 ° C. at an average temperature rise rate of 10 ° C./s, the parameter S2 according to the reached temperature and the holding time is set to 21765, cooled to the Ms point at an average cooling rate of 50 ° C./s, and then 100 ° C. A steel member was obtained by performing a heat treatment for cooling at an average cooling rate of 30 ° C./s. The parameter S2 was controlled to 21581 in the range of the arrival temperature of the steel sheet from Ac 3 points to Ac 3 points + 300 ° C., and the time from reaching a temperature 10 ° C. lower than the ultimate temperature to the end of heating in the range of 1 to 600 s. [0125] 　After that, the obtained steel member was cut out and subjected to GDS (glow discharge emission analysis), tensile test, Charpy impact test, CCT (salt spray composite cycle test), and thiocyan acid immersion test by the following methods to enrich the surface of Cu. The degree, tensile strength, impact value, number of CCT limit cycles (hydrogen embrittlement resistance in corrosive environment), and limit hydrogen amount were evaluated. The evaluation results are shown in Table 2. [0126] 　 　The surface concentration of Cu was measured by the following procedure. [0127] 　GDS (glow discharge emission analysis) was performed from the surface of the steel member in the plate thickness direction to detect the Cu content. At this time, the maximum value of the Cu content in the range of 0 to 30 μm from the surface was divided by the Cu content in the depth of 200 μm from the surface to calculate the value, and the surface concentration of Cu was determined. The GDS was measured at 5 points at random in parallel with the rolling direction from the widthwise end of the steel member to the plate width (1/4), and the average was taken as the surface concentration of Cu. Here, the "surface" is set to a depth at which Fe is 80% or more by performing GDS from the surface of the steel member. [0128] 　 The 　tensile test was carried out in accordance with the regulations of ASTM Standard E8. After grinding the soaking part of the steel member to a thickness of 1.2 mm, a half-sized plate-shaped test piece of ASTM standard E8 (parallel part length: 32 mm, parallel part plate width:: 6.25 mm) was collected. [0129] 　Then, a strain gauge (gauge length: 5 mm) was attached to each test piece, and a room temperature tensile test was performed at a strain rate of 3 mm / min to measure the tensile strength (maximum strength). In this example, the case where the tensile strength exceeds 1500 MPa is evaluated as excellent in strength. [0130] 　 The 　Charpy impact test was carried out in accordance with JIS Z 2242: 2018. The soaking portion of the steel member is ground to a thickness of 1.2 mm, a test piece is cut out in parallel with the rolling direction, and three V-notch test pieces are laminated to prepare a Charpy test piece at a test temperature of -40 ° C. An impact test was performed to determine the impact value (absorbed energy). In this example, the obtained absorbed energy is divided by the cross-sectional area under the notch for three sheets, and a case having an impact value of 30 J / cm 2 or more is evaluated as having excellent toughness. [0131] 　 　CCT was carried out in accordance with the provisions of the neutral salt spray cycle test method described in JIS H8502: 1999. The surface scale of the heat equalizing portion of the steel member was removed by shot blasting to prepare a strip-shaped test piece having a width of 8 mm and a length of 68 mm. Then, a strain gauge (gauge length: 5 mm) similar to that in the tensile test was attached to the width and center of the surface of the test piece in the length direction, and the strain was bent with a jig indicated by four points to a strain equivalent to 1/2 of the tensile strength. A test piece bent at four points is placed in a CCT device together with a jig, and in the CCT described in JIS H8502: 1999, which comprises salt spray 2h, drying 4h, and wetting 2h as one cycle, every 3 cycles 24h. By observing, the presence or absence of cracks was confirmed up to 360 cycles, and the limit number of cycles at which cracks did not occur was determined. In this example, five tests were performed, and when hydrogen embrittlement cracking did not occur up to an average of 150 cycles, hydrogen embrittlement resistance in a corrosive environment was considered to be excellent. [0132] 　 The 　thiocyanate immersion was carried out by immersing the test piece bent at four points by the above method in an aqueous solution of ammonium thiocyanate together with a jig. An aqueous solution of ammonium thiocyanate is prepared by mixing 2 L of distilled water with an ammonium thiocyanate reagent, and after 72 hours from the start of immersion, it is taken out to observe the presence or absence of cracks, and at the same time, the amount of hydrogen is analyzed by a temperature desorption method up to 300 ° C. bottom. The test was carried out by changing the amount of hydrogen charged by changing the concentration of the ammonium thiocyanate aqueous solution, and the maximum amount of hydrogen that did not cause cracking was set as the limit hydrogen amount. In this example, the test was carried out five times, and the case where the average amount of hydrogen was 0.25 mass ppm or more was considered to be excellent in hydrogen embrittlement resistance. [0133] 　As shown in Table 2, Invention Examples B1 to B29 satisfying the scope of the present invention have good results in terms of structure and characteristics, but Comparative Examples b1 to b21 not satisfying the scope of the present invention have at least the structure and characteristics. The result was that one was not satisfied. [0134] [Table 2] [0135] 　 　The slabs shown in Tables 1-1 to 1-2 above were hot-rolled to obtain a hot-rolled steel sheet having a thickness of 3.0 mm. In the hot rolling process, the slab heating temperature is set to 1250 ° C, the parameter S1 from the end of rough rolling to the start of finish rolling is set to 22657, the finish rolling end temperature is set to 930 ° C, and the temperature is cooled at 20 ° C / s until winding at 550 ° C. I rolled it up with. The parameter S1 was controlled to 22657 in the range of the time from the end of rough rolling to the start of finish rolling of 1 to 60 s and the average temperature of the rough bar from the end of rough rolling to the start of finish rolling of 950 to 1150 ° C. Then, the hot-rolled steel sheet was descaled for 30 seconds with hydrochloric acid having a concentration of 12% and a temperature of 90 ° C. Then, it was cold-rolled by a cold-rolling tester to obtain a cold-rolled steel sheet having a thickness of 1.4 mm. [0136] 　With respect to the obtained cold-rolled steel sheet, the surface concentration of Cu was evaluated by the same method as that for the steel member. In addition, the average crystal grain size was determined in accordance with JIS G 0551: 2013. The evaluation results are shown in Table 3. [0137] [Table 3] [0138] 　Inventive Examples C1 to C29 satisfying the range of the present invention are the results showing good Cu surface density and average crystal grain size, but Comparative Examples c1 to c20 not satisfying the range of the present invention are Cu surface concentration. The result did not satisfy at least one of the degree of conversion and the average crystal grain size. [0139] 　 　Among the steel types shown in Table 1-1, the steel No. The slabs having the steel components of A28 and A29 are hot-rolled (partially heated using a bar heater) and pickled (hydrochloric acid or sulfuric acid) shown in Tables 4-1 and 4-2, and then hot-rolled. A steel plate (thickness 2.8 mm) was manufactured. The evaluation results of the structure of the obtained steel sheet are shown in Tables 4-1 and 4-2. In Tables 4-1 and 4-2, t1 (s) is the time from the end of rough rolling to the start of finish rolling, T1 (° C) is the average temperature of the rough bar from the end of rough rolling to the start of finish rolling, and S1 is. It is a value obtained by (T1 + 273) × (logt1 + 20). However, the unit of t1 in the equation of S1 is (hr). [0140] [Table 4-1] [0141] [Table 4-2] [0142] 　Inventive Examples D1 to D22 satisfying the range of the present invention are the results showing good Cu surface density and average crystal grain size, but Comparative Examples d1 to d18 not satisfying the range of the present invention are Cu surface concentration. The result did not satisfy at least one of the degree of conversion and the average crystal grain size. [0143] 　 　Among the steel types shown in Table 1-1, the steel No. A cold-rolled steel sheet (plate thickness 1.8 mm) having the steel components of A28 and A29, a Cu surface concentration of 1.2 or more and a crystal grain size of 30 μm or less, is subjected to the heat treatment shown in Table 5 to be steel. Manufactured the parts. [0144] 　Table 5 shows the evaluation results of the structure and characteristics of the obtained steel members. [0145] [Table 5] [0146] 　Examples E1 to E18 that satisfy the scope of the present invention have good results in terms of structure and characteristics, but Comparative Examples e1 to e14 that do not satisfy the scope of the present invention have results that do not satisfy at least one of the structure and characteristics. It became. Industrial applicability [0147] 　According to the present invention, it is possible to obtain a steel member and a steel plate having excellent hydrogen embrittlement resistance in a corrosive environment. The steel member according to the present invention is particularly suitable for use as a skeleton part of an automobile. The scope of the claims [Claim 1] 　Chemical composition is mass%, 　　C: 0.25 to 0.60%, 　　Si: 0.25 to 2.00%, 　　Mn: 0.30 to 3.00%, 　　P: 0.050% or less, 　　S : 0.0100% or less, 　　N: 0.010% or less, 　　Ti: 0.010 to 0.100%, 　　B: 0.0005 to 0.0100%, 　　Cu: 0.15 to 1.00%, 　　Mo: 0.10 to 1.00%, 　　Cr: 0 to 1.00%, 　　Ni: 0 to 1.00%, 　　V: 0 to 1.00%, 　　Ca: 0 to 0.010%, 　　Al: 0-1 .00%, 　　Nb: 0 to 0.10%, 　　Sn: 0 to 1.00%, 　　W: 0 to 1.00%, 　　Sb: 0 to 1.00%, 　　REM: 0 to 0.30%, 　　balance : Fe and impurities are, A steel member characterized in that 　the maximum value of the Cu content in the range of 0 to 30 μm from the surface is 1.4 times or more the Cu content in the depth of 200 μm . [Claim 2] 　Chemical composition is by mass%, 　　C: 0.25 to 0.60%, 　　Si: 0.25 to 2.00%, 　　Mn: 0.30 to 3.00%, 　　P: 0.050% or less, 　　S : 0.0100% or less, 　　N: 0.010% or less, 　　Ti: 0.010 to 0.100%, 　　B: 0.0005 to 0.0100%, 　　Cu: 0.15 to 1.00%, 　　Mo: 0.10 to 1.00%, 　　Cr: 0 to 1.00%, 　　Ni: 0 to 1.00%, 　　V: 0 to 1.00%, 　　Ca: 0 to 0.010%, 　　Al: 0-1 .00%, 　　Nb: 0 to 0.10%, 　　Sn: 0 to 1.00%, 　　W: 0 to 1.00%, 　　Sb: 0 to 1.00%, 　　REM: 0 to 0.30%, 　　balance : Fe and impurities are, A steel sheet characterized in that 　the maximum value of the Cu content in the range of 0 to 30 μm from the surface is 1.2 times or more the Cu content in the depth of 200 μm, and the 　average crystal grain size is 30 μm or less . [Claim 3] 　The method for producing a steel sheet according to 　claim 2, wherein the slab having the component according to claim 2 is heated to 1100 to 1350 ° C., 　and the time from the end of rough rolling to the start of finish rolling is t1 (hr), rough rolling. When the average temperature of the coarse bar from the end to the start of finish rolling is T1 (° C), the above is heated under the condition that (T1 + 273) × (logt1 + 20) ≧ 20000 and the finish rolling end temperature is Ar 3 points to 1000 ° C. A step of hot-rolling a slab to obtain a hot-rolled steel sheet, a step of 　cooling the hot-rolled steel sheet at an average cooling rate of 10 ° C./s or more, a step 　of winding the cooled steel sheet at 700 ° C. or lower, and a step 　after winding. A method for manufacturing a steel sheet, which comprises a step of pickling the steel sheet. [Claim 4] 　The pickling uses hydrochloric acid or sulfuric acid, the pickling temperature is 80 to 90 ° C., the acid concentration α (%), and the pickling time t (s) are 　　6 ≦ α <14, 　　0