CN102719741A - Hot-galvanized high-strength steel with 220MPa-level yield strength and production method thereof - Google Patents

Hot-galvanized high-strength steel with 220MPa-level yield strength and production method thereof Download PDF

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Publication number
CN102719741A
CN102719741A CN201210202281XA CN201210202281A CN102719741A CN 102719741 A CN102719741 A CN 102719741A CN 201210202281X A CN201210202281X A CN 201210202281XA CN 201210202281 A CN201210202281 A CN 201210202281A CN 102719741 A CN102719741 A CN 102719741A
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steel
hot
strength
yield strength
dip galvanized
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胡宽辉
田德新
谭运刚
周长青
张小红
谷继刚
孙方义
冯冠文
刘祥东
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Wuhan Iron and Steel Group Corp
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Wuhan Iron and Steel Group Corp
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Abstract

The invention provides hot-galvanized high-strength steel with 220MPa-level yield strength. The steel comprises the following chemical components in percentage by weight: 0.0008-0.003% of C, 0.07-0.10% of Si, 0.35-0.50% of Mn, 0.04%-0.06% of P, 0.015-0.040% of Al, 0.02-0.04% of Ti, 0.020-0.035% of Nb, 0.0005-0.002% of B, smaller than or equal to 0.005% of S, smaller than or equal to 0.004% of N, smaller than or equal to 0.0030% of O and the balance of Fe and inevitable impurities. The invention also provides a production method of the hot-galvanized high-strength steel with 220MPa-level yield strength. The hot-galvanized high-strength steel developed by the invention has high strength, meets the requirements on the strength and rigidity of a complex structural part of a vehicle body caused by the automobile industry, is good in deep drawing performance, and can implement complex deformation successfully, and meanwhile, according to the hot-galvanized high-strength steel provided by the invention, the secondary work brittleness resisting capability is good, the secondary work brittleness temperature is minus 60 DEG C, the demand that a vehicle can work at low-temperature environment is met, and the corrosion resistance is good.

Description

Yield strength 220 MPa hot-dip galvanized high-strength steel and working method thereof
Technical field
The present invention relates to automotive body structure spare and use steel, relate in particular to a kind of yield strength 220 MPa body of a motor car complex structural member with hot-dip galvanized high-strength steel and working method thereof.
Background technology
The important development direction of Hyundai Motor structure, performance and technology be loss of weight, energy-conservation, reduce discharging and improve security.The weight and the energy consumption of automobile are linear.According to statistics, 1% burnup of the every reduction of vehicle weight can reduce by 0.6~1.0%.One of approach of automobile loss of weight is exactly the attenuate of vehicle body with material.But, must at first improve the intensity of material, guarantee the safety of product.This needs of auto-producing have been satisfied in the production application of high tensile steel plate.It is quite general that external body of a motor car is used high tensile steel plate, accounts for vehicle body with 30% of steel plate total mass, mainly is used in the stamping parts such as car door, hood, luggage-boot lid, collision bumper, vehicle frame; Simultaneously, along with automobile resists corrosive requirement, heat zinc coating plate is more and more widely the inside and outside plate that is used for automobile body covering piece also.Therefore, both had HS, had again on pot galvanize high tensile steel plate each parts that are applied to body of a motor car more and more widely of good corrosion resistance.
And yield strength 220 MPa deep-draw pot galvanize plow-steel has higher intensity and good deep drawability concurrently; And excellent solidity to corrosion and anti-collision property; Complicated, the higher parts of requirement of strength of distortion such as the therefore increasing inner and outer plates that is used for vehicle body, structural part become the main flow of body of a motor car with steel gradually.The yield strength 220 MPa automobile with the performance requriements of pot galvanize plow-steel is: ys Rp0.2:220~280MPa, tensile strength Rm:340~420MPa, unit elongation A80mm >=32%, r value >=1.5, n value >=0.17.
To of mechanical property and plasticity, anti-secondary processing brittleness and the corrosion proof requirement of yield strength 220 MPa automobile with the pot galvanize plow-steel; The technical problem that needs to solve is: (1) is on the chemical composition design of steel grade; Should guarantee that product has higher-strength, guarantee to have good deep drawability again.(2) in the technological design, need to adopt suitable rolling and annealing and hot dip galvanizing process, thereby guarantee that product has good solidity to corrosion and anti-suitability for secondary processing.
Iron and steel enterprises more both domestic and external and research institution are also carrying out the research work of these type of analogous products, to satisfy the needs of automotive industry.
Application number is 200610030716.1 Chinese patent " a kind of bell furnace is produced cold rolling high-strength ultra-deep-drawing steel plate and method of manufacture thereof ", and its chemistry becomes: C≤0.006, Si≤0.30; Mn 0.15~1.40, P≤0.08, S≤0.02; N 0.001~0.005, Al0.03~0.06, and B 0.0003~0.002; Its add-on of Ti and Nb is respectively: Ti-(48/14) N=(0.005~0.015), Nb-(93/12) C=(0~0.03), surplus Fe and inevitable impurity; Press mentioned component smelting, strand; Rolling after 1100~1250 ℃ of heating, at A R3The single-phase austenitic area finish to gauge of above temperature; Cold rolling, cold rolling draft is more than 73%; Annealing, perhydro or the cover annealing of nitrogen hydrogen, temperature 690-730 ℃; The annealing back is smooth.This invention armor plate strength rank reaches 390MPa, has the ability of high-elongation and r value and high anti-secondary processing brittleness, and ductile-brittle transition temperature is less than-40 ℃.Yet this steel adopts bell-type annealing technology, and cost is higher, and ductile-brittle transition temperature is higher, can not satisfy the anti-secondary processing brittleness of vehicle body under low temperature environment.And this steel belongs to no coating product, and solidity to corrosion is relatively poor.
Application number be JP621461121 Japanese Patent " method of manufacture of the cold rolling gap-free atom steel plate of a kind of deep-draw ", its main chemical compositions is: C≤0.005, Mn 0.001~0.5, Si≤0.02, N≤0.007, aluminium≤0.1 and an amount of Zr and Ti are dissolved in acid.Above-mentioned steel is 1000 ℃ of hot rollings,>=A 1Transition point≤720 ℃ finish to gauge, cold roller and deformed rate are 60~95%, and this steel is heated to recrystallization temperature~A C3Transition point carries out continuous annealing.This steel has added this valuable alloy of Zr, and cost is higher; Cold roller and deformed rate has reached 95%, and so big deformation rate is given the cold rolling difficulty that causes, and causes energy dissipation; In addition, this steel also is no coating product, so solidity to corrosion is relatively poor, can not satisfy the requirement of vehicle body to corrosion resisting property.
Summary of the invention
The objective of the invention is to provides yield strength 220 MPa hot-dip galvanized high-strength steel and the working method thereof that a kind of cost is low, deep drawability is good, anti-secondary processing brittleness is good, solidity to corrosion is good to the deficiency that prior art exists.
The present invention solves the problems of the technologies described above the technical scheme of being taked to be:
The yield strength 220 MPa hot-dip galvanized high-strength steel, its chemical ingredients consists of by weight percentage: C:0.0008~0.003%, Si:0.07~0.10%, Mn:0.35~0.50%; P:0.04~0.06%, Al:0.015~0.040%, Ti:0.02~0.04%; Nb:0.02~0.035%, B:0.0005~0.002%, S ≦ 0.005%; N ≦ 0.004%, O ≦ 0.0030%, surplus Fe and inevitable impurity.
In the such scheme, the thickness of said yield strength 220 MPa hot-dip galvanized high-strength steel is 0.60~2.0mm.
In the such scheme, Si:0.082~0.088%.
In the such scheme, Mn:0.35~0.45%.
In the such scheme, P:0.042~0.055%.
In the such scheme, said yield strength 220 MPa hot-dip galvanized high-strength steel comprises steel plate and is arranged at the corrosion-resistant zinc coating of steel plate upper surface and lower surface respectively that said coating weight is 80~275g/m 2
The working method of above-mentioned yield strength 220 MPa hot-dip galvanized high-strength steel, it may further comprise the steps:
1) adopts desulphurised hot metal, slab is smelted, is cast as to product by predetermined composition;
2) hot continuous rolling is carried out in single-phase austenitic area in slab heating back; The laminar flow cooling of rolling back, high temperature batches then, and said slab heating temperature is: 1260~1290 ℃; The roughing temperature out of said hot continuous rolling is: 1070~1090 ℃; Finishing temperature is: 910~940 ℃, laminar flow refrigerative speed of cooling is: 55~65 ℃/s, coiling temperature is: 710~740 ℃;
3) pickling and cold rolling, said cold rolling draft is: 67~82%;
4) continuous annealing, control annealing Heating temperature is: 815~825 ℃, speed of cooling is: 45~50 ℃/s;
5) pot galvanize, control band steel is gone into zinc pot temperature and is: 460~485 ℃, zinc liquid temperature is: 454~466 ℃, total aluminium quality percentage composition of hot galvanizing liquid is controlled at 0.17~0.25%;
6) polishing, control polishing unit elongation is: 1.2~1.4%;
7) finishing.
Carbon is cheap solution strengthening element, but the carbon content height in the steel is totally unfavorable to deep drawability.So its content is limited to 0.0008~0.003% scope.
Silicon has stronger solid solution strengthening effect, can improve the intensity of steel, but it is unfavorable to deep drawability to add too much element silicon in the steel, simultaneously, influences the surface quality after the pot galvanize.So, its content is limited to 0.07~0.10% scope.Preferred 0.082~0.088%, be beneficial to belt steel surface and carry out pot galvanize.
Manganese also is the solution strengthening element; Can improve the intensity of steel; But higher manganese content is unfavorable to deep drawability, especially the solid solution carbon in the steel, nitrogen-atoms more for a long time, manganese is owing to the interaction between manganese and the interstitial atom causes to the heavy damage of deep drawability.In steel of the present invention, owing to carbon, nitrogen-atoms are fixed fully, so the detrimentally affect of manganese reduces.Consider practical situation, so, its content is limited to 0.35~0.50% scope.Preferred 0.35~0.45%, be beneficial to belt steel surface and carry out pot galvanize.
Phosphorus is the solution strengthening element, compares with other displaced type alloying element, and it is to improve the highest element of ferritic intensity.Add an amount of phosphoric in the steel, can not only improve the intensity of steel, and not reduce the deep drawability of steel.But higher phosphoric causes the secondary processing embrittlement easily, and favorable texture is weakened, and reduces the r value of steel, and its content should be controlled at below 0.1%.Take all factors into consideration the contribution of phosphoric, it is limited in 0.04~0.06% scope intensity.Preferred 0.042~0.055%, be beneficial to belt steel surface and carry out pot galvanize.
Aluminium adds as reductor, is mainly used in to remove to be dissolved in the oxygen in the molten steel when oxygen blast is smelted.Aluminium suppresses the solid solution of nitrogen in ferritic as deciding the oxygen agent simultaneously, eliminates strain aging, improves cold plasticity.But too much aluminium content can make the inclusion in the steel increase, and influences the mechanical property of steel.The Als content of taking all factors into consideration in the steel is controlled between 0.015~0.040%.
Titanium, niobium are strong C, Nization thing forming element, and the purpose that adds titanium and niobium in the steel is fixing interstitial atom C and the N in the steel, the purification ferrite matrix, thus make steel grade of the present invention have good deep drawability.Simultaneously, the adding of niobium, titanium can be played the effect of separating out precipitation strength and crystal grain thinning, and the compound interpolation of niobium, titanium is beneficial to the pot galvanize of surface of steel plate.So, its content is limited to titanium: 0.02~0.04%; Niobium: 0.02~0.035%.
The effect that boron adds in the steel is to hinder phosphorus at grain boundary segregation, thereby improves the anti-secondary processing brittleness ability of steel.So, its content is limited to 0.0005~0.002% scope.
Sulphur is very deleterious element.Sulphur in the steel often exists with the oxide morphology of manganese, and this sulfide inclusion can worsen the toughness of steel, and causes the anisotropy of performance, therefore, needs to control sulphur content in the steel low more good more.So sulphur content in the steel is controlled at below 0.005%.
Nitrogen is harmful element in steel, influences the deep drawability of steel.So its content is controlled at below 0.004%.
Oxygen also is the detrimental impurity element in steel; The quantity that how much has reflected nonmetallic inclusionsin steel of oxygen content in steel; Be that oxygen content in steel is many more, then wherein non-metallic inclusion is also many, and it not only influences the punching performance of steel plate; And influence the surface quality of steel plate, so the present invention with the Control for Oxygen Content in the steel below 0.003%.
Product after the pot galvanize is processed into 80mm gauge length tension specimen (original gauge length L by GB 0=80mm b=20mm), and carries out tension test by GB, and the mechanical property requirements of product is as shown in table 1.
The mechanical property of table 1 product delivery
The invention has the beneficial effects as follows: the yield strength 220 MPa body of a motor car complex structural member that the present invention develops is compared with existing 220MPa level hot-dip galvanized high-strength steel with the pot galvanize plow-steel; Product of the present invention had both had higher-strength; Satisfy the requirement of automotive industry, have good deep drawability again, can accomplish complex deformation smoothly vehicle body complex structural member strength and stiffness; Simultaneously; Product of the present invention has anti-preferably secondary processing brittleness ability, and its secondary processing embrittlement temperature reaches below-60 ℃, can satisfy automobile requirements of one's work under low temperature environment; And this product has good solidity to corrosion.And existing 220MPa level pot galvanize plow-steel plasticity and anti-secondary processing brittleness ability are relatively poor.
Description of drawings
Fig. 1 is the metallographic structure figure of yield strength 220 MPa hot-dip galvanized high-strength steel of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further description, certain following embodiment should not be construed as limitation of the present invention.
The yield strength 220 MPa hot-dip galvanized high-strength steel, its chemical ingredients consists of by weight percentage: C:0.0008~0.003%, Si:0.07~0.10%, Mn:0.35~0.50%; P:0.04~0.06%, Al:0.015~0.040%, Ti:0.02~0.04%; Nb:0.02~0.035%, B:0.0005~0.002%, S ≦ 0.005%; N ≦ 0.004%, O ≦ 0.0030%, surplus Fe and inevitable impurity.
Table 2 has been listed and can be used for producing the chemical ingredients of yield strength 220 MPa body of a motor car complex structural member with six kinds of embodiment of pot galvanize plow-steel.
Chemical ingredients (the unit: wt.%) of table 2 embodiment of the invention 1 to embodiment 6 and Comparative Examples 1 to Comparative Examples 2
Embodiment C Si Mn P S Als Nb Ti B N O
1 0.0018 0.070 0.40 0.060 0.004 0.040 0.029 0.035 0.0008 0.003 0.0022
2 0.0022 0.081 0.35 0.050 0.005 0.015 0.020 0.040 0.0005 0.002 0.0030
3 0.0030 0.079 0.39 0.046 0.004 0.033 0.035 0.038 0.0015 0.002 0.0025
4 0.0008 0.100 0.45 0.040 0.005 0.033 0.028 0.025 0.0008 0.004 0.0018
5 0.0013 0.077 0.50 0.047 0.003 0.029 0.031 0.020 0.0010 0.003 0.0022
6 0.0025 0.084 0.40 0.048 0.004 0.034 0.025 0.028 0.002 0.003 0.0026
Comparative Examples 1 0.006 0.30 1.20 0.07 0.01 0.04 0.056 0.020 0.0005 0.003 ?
Comparative Examples 2 0.004 0.25 1.00 0.06 0.008 0.045 0.060 0.025 0.0006 0.004 ?
The working method of the pot galvanize plow-steel of embodiment 1 to embodiment 6 is following:
1) adopts desulphurised hot metal, steel billet is smelted, is cast as to product by predetermined composition;
Concrete steps are: in 90 tons of converters of steelworks, carry out top bottom blowing, adopt the desulfurizing iron technology, make S≤0.002% in the molten iron; Tapping began to add iron alloy at 1/3 o'clock behind the stove, tapped to add in 2/3 o'clock to finish alloying order: ferro-aluminum → ferrosilicon → ferromanganese; Carry out vacuum-treat then, and carry out trimming, trimming alloy addition sequence: aluminum shot → manganese metal → ferrosilicon → ferromanganese → ferrophosphorus → ferro-niobium.Add ferrotianium and ferro-boron at last.Make chemical ingredients in the steel satisfy the requirement of table 2, surplus is Fe and inevitably is mingled with.Again the pouring molten steel of composition shown in the table 2 is become the steel billet of 210~250mm * 700~1550mm section.
2) hot continuous rolling is carried out in single-phase austenitic area in slab heating back; The laminar flow cooling of rolling back, high temperature batches then, and said slab heating temperature is: 1260~1290 ℃; The roughing temperature out of said hot continuous rolling is: 1070~1090 ℃; Finishing temperature is: 910~940 ℃, laminar flow refrigerative speed of cooling is: 55~65 ℃/s, coiling temperature is: 710~740 ℃.
3) pickling and cold rolling, said cold rolling draft is: 67~82%.
4) continuous annealing, control annealing Heating temperature is: 815~825 ℃, speed of cooling is: 45~50 ℃/s.
5) pot galvanize, control band steel is gone into zinc pot temperature and is: 460~485 ℃, zinc liquid temperature is: 454~466 ℃, total aluminium quality percentage composition of hot galvanizing liquid is controlled at 0.17~0.25%.
6) polishing, control polishing unit elongation is: 1.2~1.4%.
7) finishing, the yield strength 220 MPa hot-dip galvanized high-strength steel that promptly obtains 0.60~2.0mm thickness specification is rolled up.
The working method of Comparative Examples 1 and Comparative Examples 2 cold rolling high-strength ultra-deep-drawing steels is following:
Slab is smelted, poured into to composition by Comparative Examples in the table 21 and Comparative Examples 2; Strand is rolling after 1100~1250 ℃ of heating, at A R3The single-phase austenitic area finish to gauge of above temperature; Carry out cold rollingly then, cold rolling draft is more than 73%; Perhydro or the cover annealing of nitrogen hydrogen, temperature 690-730 ℃ are adopted in annealing; The annealing back is smooth.
The mechanical property test result of the hot-dip galvanized high-strength steel of the embodiment of the invention 1 to embodiment 6 and Comparative Examples 1, Comparative Examples 2 lists in table 3; From the performance that table 3 reflects, thickness of the present invention is that the product of 0.60~2.0 each composition of mm can both satisfy automotive industry to HS, good deep drawing quality, anti-secondary processing brittleness and corrosion proof requirement.And the deep drawability and the anti-secondary processing brittleness ability of Comparative Examples 1 and Comparative Examples 2 are all poor than product of the present invention, and its no coating in surface, and corrosion resisting property is relatively poor.The microstructure of the finished product of the present invention is a ferritic, sees Fig. 1 for details.
Table 3 performance of products
Yield strength 220 MPa hot-dip galvanized high-strength steel of the present invention is mainly used in the higher part of the more complicated requirement of strength of distortion such as pulls in the A column reinforcement plate of making body of a motor car, passage, floor, the wheel cover.

Claims (7)

1. yield strength 220 MPa hot-dip galvanized high-strength steel, its chemical ingredients consists of by weight percentage: C:0.0008~0.003%, Si:0.07~0.10%, Mn:0.35~0.50%; P:0.04~0.06%, Al:0.015~0.040%, Ti:0.02~0.04%; Nb:0.020~0.035%, B:0.0005~0.002%, S ≦ 0.005%; N ≦ 0.004%, O ≦ 0.0030%, surplus Fe and inevitable impurity.
2. yield strength 220 MPa hot-dip galvanized high-strength steel as claimed in claim 1 is characterized in that, the thickness of said yield strength 220 MPa hot-dip galvanized high-strength steel is 0.60~2.0mm.
3. yield strength 220 MPa hot-dip galvanized high-strength steel as claimed in claim 1 is characterized in that: Si:0.082~0.088%.
4. yield strength 220 MPa hot-dip galvanized high-strength steel as claimed in claim 1 is characterized in that: Mn:0.35~0.45%.
5. yield strength 220 MPa hot-dip galvanized high-strength steel as claimed in claim 1 is characterized in that: P:0.042~0.055%.
6. yield strength 220 MPa hot-dip galvanized high-strength steel as claimed in claim 1; It is characterized in that; Said yield strength 220 MPa hot-dip galvanized high-strength steel comprises steel plate and is arranged at the corrosion-resistant zinc coating of steel plate upper surface and lower surface respectively that said coating weight is 80~275g/m 2
7. the working method of yield strength 220 MPa hot-dip galvanized high-strength steel as claimed in claim 1, it may further comprise the steps:
1) adopts desulphurised hot metal, slab is smelted, is cast as to product by predetermined composition;
2) hot continuous rolling is carried out in single-phase austenitic area in slab heating back; The laminar flow cooling of rolling back, high temperature batches then, and said slab heating temperature is: 1260~1290 ℃; The roughing temperature out of said hot continuous rolling is: 1070~1090 ℃; Finishing temperature is: 910~940 ℃, laminar flow refrigerative speed of cooling is: 55~65 ℃/s, coiling temperature is: 710~740 ℃;
3) pickling and cold rolling, said cold rolling draft is: 67~82%;
4) continuous annealing, control annealing Heating temperature is: 815~825 ℃, speed of cooling is: 45~50 ℃/s;
5) pot galvanize, control band steel is gone into zinc pot temperature and is: 460~485 ℃, zinc liquid temperature is: 454~466 ℃, total aluminium quality percentage composition of hot galvanizing liquid is controlled at 0.17~0.25%;
6) polishing, control polishing unit elongation is: 1.2~1.4%;
7) finishing.
CN201210202281XA 2012-06-19 2012-06-19 Hot-galvanized high-strength steel with 220MPa-level yield strength and production method thereof Pending CN102719741A (en)

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CN104213026A (en) * 2014-09-22 2014-12-17 武汉钢铁(集团)公司 Hot galvanizing high-strength steel with tensile strength of 370 MPa for car outer covering piece and production method thereof
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CN105970105A (en) * 2016-06-08 2016-09-28 攀钢集团攀枝花钢铁研究院有限公司 Hot-dip aluminum-zinc plate/strip used for highly deep drawing and preparation method thereof
CN106834938A (en) * 2017-01-17 2017-06-13 唐山钢铁集团有限责任公司 The high-strength galvanized steel of 400MPa grade ultra-low-carbons and its production method
CN107587089A (en) * 2017-07-19 2018-01-16 宝钢集团新疆八钢铁有限公司 A kind of technique for eliminating zinc-plated door-plate steel surface straightening line
CN110804715A (en) * 2019-12-10 2020-02-18 马鞍山钢铁股份有限公司 255 MPa-grade boron-containing high-strength and high-toughness hot-dip galvanized structural steel and production method thereof
CN112048662A (en) * 2020-08-03 2020-12-08 河钢股份有限公司 Age-resistant bake-hardening steel plate, galvanized plate thereof and production method

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Publication number Priority date Publication date Assignee Title
CN103627957A (en) * 2013-10-14 2014-03-12 首钢总公司 Steel for CR4 hot dip galvanized automobile sheets and production method thereof
CN104213026A (en) * 2014-09-22 2014-12-17 武汉钢铁(集团)公司 Hot galvanizing high-strength steel with tensile strength of 370 MPa for car outer covering piece and production method thereof
CN104328340A (en) * 2014-10-25 2015-02-04 河北钢铁股份有限公司唐山分公司 Cold-rolled galvanized phosphorated high-strength steel band and preparation method thereof
CN104593674A (en) * 2015-01-21 2015-05-06 首钢总公司 Hot-dip galvanized ultra-low carbon bake-hardening steel and production method thereof
CN104962809A (en) * 2015-07-07 2015-10-07 武汉钢铁(集团)公司 Niobium-containing alloying hot-galvanizing steel for automobile outer cover part and manufacturing method of steel
CN105970105A (en) * 2016-06-08 2016-09-28 攀钢集团攀枝花钢铁研究院有限公司 Hot-dip aluminum-zinc plate/strip used for highly deep drawing and preparation method thereof
CN106834938A (en) * 2017-01-17 2017-06-13 唐山钢铁集团有限责任公司 The high-strength galvanized steel of 400MPa grade ultra-low-carbons and its production method
CN107587089A (en) * 2017-07-19 2018-01-16 宝钢集团新疆八钢铁有限公司 A kind of technique for eliminating zinc-plated door-plate steel surface straightening line
CN107587089B (en) * 2017-07-19 2021-05-28 新疆八一钢铁股份有限公司 Process for eliminating withdrawal and straightening lines on surface of galvanized door sheet steel
CN110804715A (en) * 2019-12-10 2020-02-18 马鞍山钢铁股份有限公司 255 MPa-grade boron-containing high-strength and high-toughness hot-dip galvanized structural steel and production method thereof
CN112048662A (en) * 2020-08-03 2020-12-08 河钢股份有限公司 Age-resistant bake-hardening steel plate, galvanized plate thereof and production method

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