CN109072447A - The manufacturing method of surface-treated steel strips and surface-treated steel strips - Google Patents

The manufacturing method of surface-treated steel strips and surface-treated steel strips Download PDF

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Publication number
CN109072447A
CN109072447A CN201780023567.2A CN201780023567A CN109072447A CN 109072447 A CN109072447 A CN 109072447A CN 201780023567 A CN201780023567 A CN 201780023567A CN 109072447 A CN109072447 A CN 109072447A
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China
Prior art keywords
zinc phosphate
trbasic zinc
steel plate
film coated
lubricating film
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CN201780023567.2A
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CN109072447B (en
Inventor
安井淳
佐藤宏
佐藤一宏
西谷宗刚
川西義博
嶋谷佳祐
勅使河原智哉
藤脇健史
田口宽树
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Nihon Parkerizing Co Ltd
Nippon Steel Corp
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Nihon Parkerizing Co Ltd
Nippon Steel Corp
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Publication of CN109072447A publication Critical patent/CN109072447A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10M2205/024—Propene
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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    • C10N2020/04—Molecular weight; Molecular weight distribution
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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  • Chemical & Material Sciences (AREA)
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  • Mechanical Engineering (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Chemical Treatment Of Metals (AREA)
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  • Paints Or Removers (AREA)

Abstract

Surface-treated steel strips of the invention have: matrix steel plate；Trbasic zinc phosphate coating layer is formed in the surface of aforementioned substrates steel plate with island and by acicular trbasic zinc phosphate Crystallization；With, lubricating film coated layer, covers the surface of aforementioned substrates steel plate and a part of aforementioned phosphate zinc coating layer and include at least Lubrication Composition, aforementioned phosphate zinc crystal is 25%~90% in the area ratio that the surface of aforementioned lubricating film coated layer is exposed.

Description

The manufacturing method of surface-treated steel strips and surface-treated steel strips
Technical field
The present invention relates to the manufacturing methods of surface-treated steel strips and surface-treated steel strips.
Background technique
In the plastic processing of steel plate, in the processing of automobile transmission component for needing the multistep under high surface pressure to be press-formed etc., Steel plate and seizure or sticking to mould in order to prevent have carried out following phosphate soap processing: having made the phosphate based on trbasic zinc phosphate Crystal is precipitated in surface of steel plate and forms phosphate overlay film, is the response type soap of principal component to odium stearate (alkali soap) then Overlay film is covered as the upper layer of phosphate overlay film.However, in the processing of phosphate soap, phosphate overlay film and response type soap overlay film Formation need longer chemical time, therefore, production cost can be got higher.In addition, unreacted soap ingredient pressurization at It is adhered to mold as pressurization dregs when type, therefore, the frequent cleaning of mold becomes important.
Therefore, the multistep extrusion forming without needing the processing of prolonged response type soap, under high surface pressure It is killed in order to prevent in such multistep plastic processing or sticking to mould, discloses to form the lubricating film coated comprising Lubrication Composition as phosphorus The technology (referring for example to patent document 1 below) on the upper layer of hydrochlorate overlay film
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-104125 bulletin
Summary of the invention
Problems to be solved by the invention
Herein, processing disclosed in above-mentioned patent document 1 is implemented in the state of steel band mostly in practical.Process object In the case where for steel band, in the cutting process of the preceding step of multistep plastic processing, it is necessary to send out steel from steel band by pinch roller Plate.In addition, resistent mucous membrane when in order to ensure multistep extrusion forming, the confficient of static friction for reducing the steel plate sent out from steel band become It is important, but when excessive reduction confficient of static friction, steel plate slides on pinch roller, and the probability that blanking (blanking) occurs can become It is high.In this way, the resistent mucous membrane when multistep under roller transporting (skid-resistant roller) and high surface pressure is press-formed is anti-in back each other The performance of relationship.In order to continuously implement multistep plastic processing while sending out steel plate from steel band, start to require to take into account above-mentioned Skid-resistant roller and resistent mucous membrane.
Therefore, the present invention has been made in view of the above problems, and the object of the present invention is to provide can be achieved at the same time as back The skid-resistant roller of reflexive energy and resistent mucous membrane, surface-treated steel strips and surface-treated steel strips manufacturing method.
The solution to the problem
The present inventor has made intensive studies in order to solve the above problems, as a result obtains opinion below.
(A) before forming lubricating film coated layer as the surface of the matrix steel plate of base material, make trbasic zinc phosphate crystal in matrix steel plate Surface be precipitated with island.At this point, in such a way that a part of trbasic zinc phosphate crystal exposes (protrusion) from the surface of lubricating film coated layer, Control the shape of trbasic zinc phosphate crystal.Bumps caused by trbasic zinc phosphate crystal are finally obtained as a result, to reveal from the surface of lubricating film coated layer The surface-treated steel strips of the form of (protrusion) out.
(B) trbasic zinc phosphate crystal does not have lubricity, and therefore, bumps caused by trbasic zinc phosphate crystal are formed in lubricating film coated layer Surface surface-treated steel strips confficient of static friction be greater than the individual confficient of static friction of lubricating film coated layer.Surface-treated steel strips The area ratio of confficient of static friction and the trbasic zinc phosphate crystal exposed from the surface of lubricating film coated layer is (hereinafter, sometimes referred to as expose area Rate) it is in correlativity.That is, can control the quiet of surface-treated steel strips by the exposing the area ratio of control trbasic zinc phosphate crystal and rub Wipe coefficient.
(C) when being conveyed surface-treated steel strips with the state being held between a pair of of pinch roller, by pinch roller to table Surface treatment steel band applies pressure (face pressure), but the pressure does not crush the trbasic zinc phosphate crystal exposed from lubricating film coated layer up to.It changes The bumps of Yan Zhi, the surface of lubricating film coated layer will not be planarized by pinch roller.Therefore, the surface-treated steel strips under pinch roller is quiet Coefficient of friction can maintain the larger value constant.As a result, the sliding of the surface-treated steel strips under pinch roller is suppressed, and therefore, folder The skid-resistant roller of (bottom surface pressure) is sent under roller to improve.
(D) on the other hand, multistep is implemented to surface-treated steel strips using the pressurizing device in the downstream side for being set to pinch roller When extrusion forming, due to applying very big pressure (face pressure) to surface-treated steel strips, the phosphorus exposed from lubricating film coated layer Sour zinc crystal is crushed, and makes the concave-convex planarization on the surface of lubricating film coated layer.Surface-treated steel strips under pressurizing device as a result, Confficient of static friction becomes lubricating film coated layer possessed confficient of static friction originally.As a result, table can be played under pressurizing device The original lubricity (sliding property) of surface treatment steel band, therefore, the resistent mucous membrane under pressurizing device (under high surface pressure) improve.
The present invention is completed based on above-mentioned opinion, and purport is as described below.
[1]
A kind of surface-treated steel strips, have:
Matrix steel plate；
Trbasic zinc phosphate coating layer is formed in the surface of aforementioned substrates steel plate with island and by acicular trbasic zinc phosphate crystal shape At；With,
Lubricating film coated layer covers the surface of aforementioned substrates steel plate and a part and at least of aforementioned phosphate zinc coating layer Comprising Lubrication Composition,
Aforementioned phosphate zinc crystal is 25%~90% in the area ratio that the surface of aforementioned lubricating film coated layer is exposed.
[2]
The surface-treated steel strips according to [1], wherein the average grain diameter of the long axis direction of aforementioned phosphate zinc crystal is 25 μm~70 μm, the average grain diameter of short-axis direction be 3 μm~10 μm.
[3]
The surface-treated steel strips according to any one of [1] or [2], wherein the adhesion amount of aforementioned phosphate zinc coating layer For every single side 1.5g/m2~15.0g/m2。
[4]
The surface-treated steel strips according to any one of [1]~[3], wherein the adhesion amount of aforementioned lubricating film coated layer is Every single side 1.0g/m2~12.0g/m2。
[5]
The surface-treated steel strips according to any one of [1]~[4], aforementioned lubricating film coated layer includes: SiO2/M2(M is O Alkali metal) shown in molar ratio be 2~5 silicic acid alkali metal salt；With the polyethylene wax for being 0.1 μm~3.0 μm by average grain diameter Or the macromolecule wax that at least either in polypropylene wax is formed,
Relative to all solids composition quality of aforementioned lubricating film coated layer, the solid component content of aforementioned silicic acid alkali metal salt For 60 mass of mass %~90 %, the solid component content of aforementioned macromolecule wax is 5 mass of mass %~40 %.
[6]
A kind of manufacturing method of surface-treated steel strips comprising following steps:
Quenched step carries out the quenched of the surface of matrix steel plate using the surface conditioner comprising colloidal titanium；
Trbasic zinc phosphate coating layer forming step makes the needle of trbasic zinc phosphate on the surface for the aforementioned substrates steel plate for implementing surface tempering Shape crystal growth is island, forms trbasic zinc phosphate coating layer on the surface of the matrix steel plate；With,
Lubricating film coated layer forming step, by the lubricated agent for including at least Lubrication Composition with adhesion amount for every single side 1.0g/m2~12.0g/m2Mode be coated on the surface of aforementioned substrates steel plate and aforementioned phosphate zinc coating layer, form lubricating film coated Layer, the area ratio 25%~90% for exposing aforementioned phosphate zinc crystal on the surface of aforementioned lubricating film coated layer.
[7]
The manufacturing method of the surface-treated steel strips according to [6], wherein in aforementioned phosphate zinc coating layer forming step In, aforementioned substrates steel plate is heated.
[8]
The manufacturing method of the surface-treated steel strips according to [7], wherein aforementioned substrates steel plate is made to contact progress with steam Heating.
The effect of invention
According to the present invention it is possible to be embodied as simultaneously resistance to viscous under the skid-resistant roller and high surface pressure of carrying on the back the bottom surface pressure of reflexive energy Mould.
Detailed description of the invention
Fig. 1 is the explanatory diagram of the surface-treated steel strips of one embodiment of the present invention.
(A) of Fig. 2 schematically shows the explanatory diagram of the composition of the surface-treated steel strips of same embodiment.
(B) of Fig. 2 is the explanatory diagram for schematically showing the composition of surface-treated steel strips of same embodiment.
(A) of Fig. 3 is to show to form the front of an example of the trbasic zinc phosphate processing bath of trbasic zinc phosphate coating layer on the surface of steel band Figure.(B) of Fig. 3 is to show to form the plan view of an example of the trbasic zinc phosphate processing bath of trbasic zinc phosphate coating layer on the surface of steel band.
Fig. 4 is the flow chart for showing an example of manufacturing method process of the surface-treated steel strips of same embodiment.
Fig. 5 is the explanatory diagram for schematically showing the test method of resistent mucous membrane.
Fig. 6 is the explanatory diagram for schematically showing the test method of skid-resistant roller.
Fig. 7 is the enlarged photograph of the surface-treated steel strips of comparative example.
Fig. 8 is the enlarged photograph of the surface-treated steel strips of comparative example.
Fig. 9 is the enlarged photograph of the surface-treated steel strips of example of the present invention.
Figure 10 is the enlarged photograph of the surface-treated steel strips of example of the present invention.
Specific embodiment
To be illustrated below referring to an example of attached drawing side to embodiments of the present invention.It should be noted that this explanation In book and attached drawing, for the constituent element substantially constituted with same function, mark same symbol is to omit repeated explanation.
(about surface-treated steel strips)
Firstly, being said in detail in referring to Fig.1~Fig. 2 B to the surface-treated steel strips of one embodiment of the present invention It is bright.Fig. 1 is the explanatory diagram being illustrated for the surface-treated steel strips to present embodiment, and the B of the A and Fig. 2 of Fig. 2 are schematic The explanatory diagram of the composition of the surface-treated steel strips of present embodiment is shown.
The surface-treated steel strips 10 of present embodiment like that, implement at high lubrication matrix steel plate 101 as detailed below Reason.Above-mentioned surface-treated steel strips 10 are as being schematically shown Fig. 1, in the cutting process of the preceding step of multistep plastic processing, Uncoiling is carried out using pinch roller 1 from the state batched as web-like, logical plate is continuously carried out along defined logical plate direction X.Logical plate Surface-treated steel strips 10 are processed into target manufacture object by the multistep pressure processing using the mold 2 for meeting target manufacture object.
As described above like that, lead to the surface-treated steel strips 10 (matrix steel plate 101) of plate and stinging for mold 2 in order to prevent Extremely, sticking to mould, it is important that the confficient of static friction of surface-treated steel strips 10 is reduced, on the other hand, in order to by surface-treated steel strips 10 Using pinch roller 1 from the in stable condition ground uncoiling batched as web-like, it is important that surface-treated steel strips 10 have a degree of Confficient of static friction.Therefore, for the surface-treated steel strips of present embodiment 10, as shown in the B of the A of Fig. 2 and Fig. 2, for Surface treatment described below is implemented on the surface of matrix steel plate 101 as base material, forms the surface treatment being made of 2 layers Layer.
The surface-treated steel strips 10 of present embodiment include the matrix as base material as shown in the B of the A of Fig. 2 and Fig. 2 Steel plate 101；The trbasic zinc phosphate coating layer 103 being formed on matrix steel plate 101；With the lubrication being formed on trbasic zinc phosphate coating layer 103 Coating layer 105.It should be noted that trbasic zinc phosphate coating layer 103 and lubricating film coated layer 105 be as shown in the A of Fig. 2, it can be only A surface for being formed in matrix steel plate 101 can also be formed in the right each other of matrix steel plate 101 as shown in the B of Fig. 2 Two surfaces set.
[about matrix steel plate 101]
Matrix steel plate 101 is used as the base material of surface-treated steel strips 10.Do not have for the matrix steel plate 101 of present embodiment It is particularly limited to, characteristic required by the object for being able to achieve the plastic processing of the multistep through walking later processing manufacture can be used Well known steel plate.Manufacturing method, the material of above-mentioned well known steel plate are also not particularly limited, it can be from common slab system Making process is suitable for manufacturing by various processes well known to hot rolling, pickling, cold rolling, annealing, temper rolling or the like.In addition, Certain above-mentioned matrix steel plate 101 not only can be carbon steel sheet, but also can be the special steels such as stainless-steel sheet, high alloy steel plate Plate.
As an example of such matrix steel plate 101, for example, the hot rolled steel plate with chemical component below.
The hot rolled steel plate of an example as matrix steel plate 101 contains C:0.070%~0.080%, Si in terms of quality %: 0.030%~0.080%, Mn:1.15%~1.30%, P:0.015%~0.028%, S:0.000%~0.040%, surplus It is made of Fe and impurity.
By using such hot rolled steel plate as matrix steel plate 101, the intensity of the object of manufacture can be improved.
[about trbasic zinc phosphate coating layer 103]
Trbasic zinc phosphate coating layer 103 undertakes the effect for improving the adaptation of matrix steel plate 101 and lubricating film coated layer 105.The phosphorus Sour zinc coating layer 103 be by the surface of matrix steel plate 101 by chemical reaction precipitation trbasic zinc phosphate acicular crystal constitute, The aggregate of acicular trbasic zinc phosphate crystal.The B of the A and Fig. 2 of the acicular crystal of the trbasic zinc phosphate of precipitation such as Fig. 2 schematically show that Sample is not the surface of matrix steel plate 101 to be completely covered, and become a part on the surface of matrix steel plate 101 not by trbasic zinc phosphate Crystal covering and remaining state.As a result, the acicular crystal of trbasic zinc phosphate becomes on the surface of matrix steel plate 101 with island point The surface of cloth, the matrix steel plate 101 that the acicular crystal of trbasic zinc phosphate is not present exists as flat part.It should be noted that phosphoric acid Zinc coating layer 103 is divided into multiple positions on the surface of matrix steel plate 101, with state independent of each other presentation.It, will in the present invention So it is divided into multiple positions, on the surface of matrix steel plate 101 with the trbasic zinc phosphate coating layer 103 of state independent of each other presentation State is known as " island ".
The trbasic zinc phosphate coating layer 103 of present embodiment as be described hereinafter, is formed in and has carried out table using specific surface conditioner On the quenched matrix steel plate 101 in face, in turn, formed in the trbasic zinc phosphate coating layer forming step of trbasic zinc phosphate coating layer 103, due to inciting somebody to action Matrix steel plate 101 is heated, so by the acicular crystal of the bigger trbasic zinc phosphate of the partial size ratio of long axis direction and short-axis direction It constitutes.The adhesion amount of above-mentioned trbasic zinc phosphate coating layer 103 is preferably set to every single side 1.5g/m2~15.0g/m2.Trbasic zinc phosphate coating layer 103 adhesion amount is more preferably every single side 3.0g/m2~15.0g/m2.By keeping the adhesion amount of trbasic zinc phosphate coating layer 103 above-mentioned Range, lubricating film coated layer 105 can be made more reliably closely sealed on matrix steel plate 101, phosphorus in the processing and forming under high surface pressure Sour zinc coating layer 103 will not disappear, and can more reliably keep lubricating film coated layer 105 up to the final process of processing and forming.
It should be noted that the acicular crystal for constituting the trbasic zinc phosphate of the trbasic zinc phosphate coating layer 103 of present embodiment is preferred It is that the average grain diameter of long axis direction is 25 μm~70 μm, the average grain diameter of short-axis direction is 3 μm~10 μm.Trbasic zinc phosphate it is needle-shaped The average grain diameter of crystal is it is further preferred that being 25 μm~50 μm on long axis direction, on short-axis direction being 3 μm~5 μm.Constitute phosphoric acid The trbasic zinc phosphate crystal of zinc coating layer 103 is by can more reliably realize above-mentioned adaptation with above-mentioned average grain diameter.
In addition, the acicular crystal for constituting the trbasic zinc phosphate of the trbasic zinc phosphate coating layer 103 of present embodiment is preferably, long axis side To the acicular crystal for being 2.5 or more with the average grain diameter ratio of short-axis direction.Pass through the phosphoric acid for making that there is such average grain diameter The acicular crystal of zinc is precipitated, and can more reliably realize the adaptation of matrix steel plate 101 Yu lubricating film coated layer 105.
The trbasic zinc phosphate coating layer 103 can be used comprising trbasic zinc phosphate and can make known in the acicular crystal precipitation of trbasic zinc phosphate Treatment fluid and formed.For such treatment fluid, it is not particularly limited, for example: the plastic processing of response type is used Trbasic zinc phosphate treatment fluid (use by the plastic processing for the response type that more specifically, the processing time for being completely covered is 20 seconds or more Trbasic zinc phosphate treatment fluid).When the formation of trbasic zinc phosphate coating layer 103, spray coating method can use, infusion process makes above-mentioned trbasic zinc phosphate treatment fluid It is contacted with matrix steel plate 101, also can use the reactive tank comprising above-mentioned trbasic zinc phosphate treatment fluid and carry out electrolysis processing.
In order to which trbasic zinc phosphate crystal is precipitated on matrix steel plate 101 with island, base can be completely covered in trbasic zinc phosphate crystal Before the entire surface of body steel plate 101, making trbasic zinc phosphate, processing terminate.For this purpose, can be by matrix steel plate 101 and trbasic zinc phosphate treatment fluid Time of contact, electrolysis time are limited to the short period.I.e., it is possible to using commercially available plastic processing trbasic zinc phosphate treatment fluid, with than The processing time of instruction it is also short time completion processing.About the specific processing time, electrolytic condition, handled by investigation in advance The corresponding relationship of time (or electrolytic condition) and adhesion amount specific can be able to achieve the processing time of above-mentioned preferred adhesion amount (electrolytic condition).In addition, forming trbasic zinc phosphate coating layer 103 in order to which trbasic zinc phosphate crystal is precipitated on matrix steel plate 101 with island Trbasic zinc phosphate coating layer forming step in, it is also effective that matrix steel plate 101, which is carried out heating,.
It whether is island about the trbasic zinc phosphate crystal being precipitated by above-mentioned processing, it can be to trbasic zinc phosphate treated matrix The surface of steel plate 101 carries out micro- sem observation and judges.Specifically, with scanning electron microscope (Scanning Electron Microscope:SEM) observation trbasic zinc phosphate treated matrix steel plate 101 surface, can will pass through two images The situation that the area for handling the flat part found out is 30% or more is judged as that trbasic zinc phosphate crystal is formed with island.Above-mentioned trbasic zinc phosphate is brilliant It carries out, can also be carried out before the lubricating film coated layer 105 that the observation of body can be stated after its formation after its formation.But form lubrication In the case where being observed after coating layer 105, in order to observe trbasic zinc phosphate crystal through lubricating film coated layer 105, high acceleration electricity is carried out The SEM of pressure is observed.Specifically, by making acceleration voltage 20kV or more phosphoric acid can be observed across lubricating film coated layer 105 The crystal of zinc can find out the area ratio of flat part.It should be noted that formed in the observation before lubricating film coated layer 105, even if Trbasic zinc phosphate crystal can also be observed under lower acceleration voltage.
Herein, it when forming trbasic zinc phosphate coating layer 103 on matrix steel plate 101, is handled prior to above-mentioned trbasic zinc phosphate, utilizes packet Surface conditioner containing colloidal titanium carries out the modifier treatment on the surface of matrix steel plate 101.Trbasic zinc phosphate crystal never attaching surface tune The surface for saving the matrix steel plate 101 of the ingredient of agent is precipitated, but since colloidal titanium is coarse colloidal solid, the base of exposing The area on the surface of body steel plate 101 is suppressed.As a result, by carrying out surface tempering using the surface conditioner comprising colloidal titanium Processing, can be such that the acicular crystal of the trbasic zinc phosphate for the preferred average grain diameter ratio for having above-mentioned is more reliably precipitated.
[about lubricating film coated layer 105]
Lubricating film coated layer 105 is positioned at the surface of matrix steel plate 101 as being schematically shown the B of the A of Fig. 2 and Fig. 2 At least one of at least part of upper, covering matrix steel plate 101 surface and trbasic zinc phosphate coating layer 103 and trbasic zinc phosphate crystal Divide the layer exposed on surface.The lubricating film coated layer 105 is the layer including at least Lubrication Composition, preferably by Binder Composition and lubrication Ingredient is formed.
In the surface-treated steel strips 10 of present embodiment, by forming the trbasic zinc phosphate crystal of above explained island, lubrication Lubrication Composition contained in coating layer 105, Binder Composition are held in island as being schematically shown the B of the A of Fig. 2 and Fig. 2 Trbasic zinc phosphate crystal between.When multistep plastic processing (such as when multistep pressure processing), the surface of surface-treated steel strips 10 is applied When the face pressure increased, it is held in the Lubrication Composition between the trbasic zinc phosphate crystal of island and is flowed out between matrix steel plate 101 and mold. As a result, the confficient of static friction of lubricating film coated layer 105 reduces, to embody greasy property, resistent mucous membrane is realized.
The adhesion amount of above-mentioned lubricating film coated layer 105 is every single side 1.0g/m2~12.0g/m2, trbasic zinc phosphate crystal covers in lubrication The area ratio (the area ratio of per unit area) that the surface of film layer 105 is exposed is 25%~90%.By making lubricating film coated layer 105 Adhesion amount and the area ratio of the trbasic zinc phosphate crystal exposed on the surface of lubricating film coated layer 105 be above range, can be real together Existing above-mentioned resistent mucous membrane and skid-resistant roller.
The adhesion amount of lubricating film coated layer 105 is lower than 1.0g/m2In the case where, the lubrication as the holding of lubricating film coated layer 105 The amount of ingredient is insufficient, cannot achieve sufficient resistent mucous membrane, it is not preferable.In addition, the adhesion amount of lubricating film coated layer 105 is more than 12.0g/m2In the case where, the amount of the Lubrication Composition as the holding of lubricating film coated layer 105 becomes excessive, cannot achieve skid-resistant roller Property, it is not preferable.The more preferable 2.0g/m of adhesion amount of every single side of lubricating film coated layer 1052~9.0g/m2。
It should be noted that adhesion amount of the adhesion amount of lubricating film coated layer 105 also by trbasic zinc phosphate coating layer 103 is influenced. That is, the amount of retainable lubricating film coated layer 105 also tails off in the case that the adhesion amount of trbasic zinc phosphate coating layer 103 is few, on the contrary, In the case that the adhesion amount of trbasic zinc phosphate coating layer 103 is more, the amount of retainable lubricating film coated layer 105 also becomes more.For example, trbasic zinc phosphate The adhesion amount of coating layer 103 is 1.5g/m2~8.0g/m2In the case where, the preferred 1.0g/m of the adhesion amount of lubricating film coated layer 1052~ 6.0g/m2Left and right, the adhesion amount of trbasic zinc phosphate coating layer 103 is more than 8.0g/m2It and is 15.0g/m2In situation below, lubrication is covered The adhesion amount of film layer 105 is preferably greater than 6.0g/m2It and is 12.0g/m2Left and right below.
The adhesion amount of trbasic zinc phosphate coating layer 103 is if it is single side 1.5g/m2~8.0g/m2, then can make adhesion amount 1.0g/m2~6.0g/m2The lubricating film coated layer 105 of left and right is compatibly closely sealed on matrix steel plate 101, and the molding under high surface pressure adds Trbasic zinc phosphate coating layer 103 does not also disappear in work, and lubricating film coated layer 105 can be kept up to the final process of processing and forming.
On the other hand, it in the automobile components such as direct clutch, is shaped to by around after the molding of the cylinder of multistep, existing The component of dentation.These components under more high surface pressure due to by duplicate sliding form, trbasic zinc phosphate coating layer 103 Adhesion amount is every single side 8.0g/m2When following, molding midway process makes trbasic zinc phosphate coating layer 103 disappear due to sliding, has The worry that the dimensional accuracy of finished goods reduces, the crackle in molding midway process occurs.Under above situation, it is preferred that phosphorus The adhesion amount of sour zinc coating layer 103 is more than 8.0g/m2It and is 15.0g/m2Below, the adhesion amount of lubricating film coated layer 105 is more than 6.0g/m2It and is 12.0g/m2Left and right below.
Herein, the lubricating film coated layer 105 of present embodiment is preferably, and includes SiO as above-mentioned Binder Composition2/M2O The silicic acid alkali metal salt that molar ratio shown in (M be alkali metal) in Li, Na, K etc. is 2~5, as above-mentioned lubrication at Point, include the macromolecule formed by average grain diameter for at least either in 0.1 μm~3.0 μm of polyethylene wax or polypropylene wax Wax.
By using above-mentioned silicic acid alkali metal salt as Binder Composition, Lubrication Composition can be appropriately held in It, can be in the firm continuous overlay film of steel strip surface formation excellent heat resistance on the basis of in overlay film.As a result, can embody anti- What only the surface-treated steel strips of present embodiment and the metal of mold directly contacted resistance to kill sexual function, covers from fine and close alkalinity Antirust sexual function of the barrier property of film etc..Herein, it in the case that above-mentioned molar ratio is lower than 2, is unable to fully obtain film intensity, mould Property processing performance deteriorate, it is not preferable.In addition, plastic deformation ability deteriorates, and covers in the case that above-mentioned molar ratio is more than 5 The stability of the silicic acid aqueous solution of alkali metal salt utilized when film formation deteriorates, and lacks practicability, it is not preferable.Silicic acid alkali metal salt In SiO2/M2Molar ratio shown in O more preferable 3~4.
By using above-mentioned macromolecule wax as Lubrication Composition, the expansion of lubricating film coated layer 105, Ke Yijin can be inhibited The plastic deformation ability of one step raising lubricating film coated layer 105.Herein, in the case that the average grain diameter of macromolecule wax is lower than 0.1 μm, Oil becomes apparent from diffusion of the interface of macromolecule wax into overlay film, and the oil resistivity of overlay film deteriorates, and it is not preferable, and macromolecule wax is put down In the case that equal partial size is more than 3.0 μm, the dispersion of the macromolecule wax in chemical solution is deteriorated, it is difficult to uniform overlay film is formed, therefore Not preferably.More preferable 0.5 μm~1.5 μm of the average grain diameter of macromolecule wax.By using the high score with above-mentioned average grain diameter As Lubrication Composition, Lubrication Composition is easy to fill to the recess portion of the convex-concave of trbasic zinc phosphate crystal, as a result, trbasic zinc phosphate crystal wax It is easy to expose from the surface of lubricating film coated layer 105.
The solid component content of above-mentioned silicic acid alkali metal salt is excellent relative to all solids composition quality of lubricating film coated layer 105 Select 60 mass of mass %~90 %, all solids of the solid component content of above-mentioned macromolecule wax relative to lubricating film coated layer 105 Composition quality preferably 5 mass of mass %~40 %.
The solid component content of silicic acid alkali metal salt is lower than the glass in the case where 60 mass %, formed by silicic acid alkali metal salt A possibility that continuity of glass shape overlay film lacks, and obtains the film intensity for being resistant to plastic processing reduction, it is not preferable.In addition, In the case that the solid component content of silicic acid alkali metal salt is more than 90 mass %, gained film intensity is saturated, and is become not in cost Benefit, it is not preferable.All solids of the solid component content of above-mentioned silicic acid alkali metal salt more preferably relative to lubricating film coated layer 105 Composition quality is 70 mass of mass %~80 %.
In the case that the solid component content of macromolecule wax is lower than 5 mass %, the Lubrication Composition of the holding of lubricating film coated layer 105 Amount it is insufficient, a possibility that embodying sufficient greasy property, reduces, and it is not preferable.In addition, the solid component content of macromolecule wax In the case where 40 mass %, the amount for the Lubrication Composition that lubricating film coated layer 105 is kept becomes excessive, embodies sufficient skid-resistant roller A possibility that property, reduces, and it is not preferable.The solid component content of above-mentioned macromolecule wax is more preferably relative to lubricating film coated layer 105 All solids composition quality is 3 mass of mass %~10 %.
The lubricating film coated layer 105 of present embodiment can use to be mixed in the solution or dispersion liquid of above-mentioned Binder Composition There is the lubricated agent of above-mentioned Lubrication Composition, formed by coating.It herein, can be water, organic as the solvent used Solvent, they mixture any one, it is preferable to use water solvent (water or the water miscibilities such as water and alcohol on operating environment The mixed solvent of organic solvent).For above-mentioned solvent, adding relative to all solids composition quality of lubricated agent is 60 matter The Binder Composition (such as silicic acid alkali metal salt) and all solids ingredient relative to lubricated agent for measuring the mass of %~90 % Quality is the Lubrication Composition (such as macromolecule wax) of 5 mass of mass %~40 %, is suitably coated drying, so as to Form the lubricating film coated layer 105 of above-mentioned solid component content.
It should be noted that in order to improve the dispersibility of Lubrication Composition, it can be for known in above-mentioned lubricated agent addition Surfactant.In addition, in order to adjust the viscosity of above-mentioned lubricated agent, in the film intensity not to lubricating film coated layer 105 Viscous regulator can be added in the range of impacting.As above-mentioned viscous regulator, the substance generally used can be used, For example, hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylamide, Sodium Polyacrylate, polyvinylpyrrolidone, poly- The organic polymers such as vinyl alcohol system thickener etc..In the case where using above-mentioned viscous regulator, content is relative to lubricating film coated The all solids composition quality of layer 105 is preferably shorter than 10 mass %.
When above-mentioned lubricated agent is coated on blank substrate 3 and trbasic zinc phosphate coating layer 103, it can use at dipping Method well known to reason, spray lantern ring (shower ringer treatment) processing, roller coating process etc..As long as in addition, coating The surface of blank substrate 3 and trbasic zinc phosphate coating layer 103 is adequately coated just to the temperature of lubricated agent with above-mentioned lubricated agent Degree, coating duration are not particularly limited.In addition, the drying temperature for lubricated agent is it is not also specifically limited, can basis Ingredient contained in lubricated agent and be suitable for setting.
[the area ratio (25%~90%) exposed about trbasic zinc phosphate crystal on the surface of lubricating film coated layer 105]
In the lubricating film coated layer 105 of present embodiment, as shown in the B of the A of Fig. 2 and Fig. 2, pass through trbasic zinc phosphate crystal The a part of a part of (trbasic zinc phosphate coating layer 103) on the surface of lubricating film coated layer 105 is exposed, and can inhibit to lubricate well The reduction of the confficient of static friction of coating layer 105.As a result, skid-resistant roller when also may be implemented steel plate from steel band uncoiling.
Trbasic zinc phosphate crystal is in the case where the area ratio that the surface of lubricating film coated layer 105 is exposed is lower than 25%, lubricating film coated The reduced inhibition level of the confficient of static friction of layer 105 becomes inadequate, and cannot achieve sufficient skid-resistant roller, it is not preferable. In addition, trbasic zinc phosphate crystal lubricating film coated layer 105 surface expose the area ratio be more than 90% in the case where, lubricating film coated layer The reduced inhibition level of 105 confficient of static friction becomes over, and cannot achieve sufficient resistent mucous membrane, it is not preferable.Phosphoric acid The area ratio more preferable 30%~60% that zinc crystal exposes on the surface of lubricating film coated layer 105.
The face exposed by the adhesion amount and trbasic zinc phosphate crystal that make lubricating film coated layer 105 on the surface of lubricating film coated layer 105 Product rate becomes above-mentioned range, and the confficient of static friction of the lubricating film coated layer 105 of present embodiment becomes 0.10~0.20.Lubrication is covered The confficient of static friction of film layer 105 more preferable 0.12~0.15.
It should be noted that by the preferred range for keeping the adhesion amount of trbasic zinc phosphate coating layer 103 above-mentioned, it can more really Make trbasic zinc phosphate crystal in the area ratio above range that lubricating film coated layer 105 exposes on the spot.
In addition, for the area for exposing trbasic zinc phosphate crystal (trbasic zinc phosphate coating layer 103) on the surface of lubricating film coated layer 105 Rate is 25%~90%, it is necessary to make every single side 1.5g/m2~15.0g/m2Trbasic zinc phosphate coating layer 103 be island, for this purpose, consider The temperature for handling trbasic zinc phosphate rises or makes to handle the method extended etc the time.However, for the temperature of trbasic zinc phosphate processing bath Degree, since water is solvent, substantially it is difficult to for treatment temperature to be increased to 100 DEG C or more, on the other hand, if at extension The time is managed, then the crystal for the trbasic zinc phosphate overlay film being precipitated densely is generated in steel strip surface, and trbasic zinc phosphate coating layer 103 not will become island Shape.In addition, the rising of the temperature of trbasic zinc phosphate processing bath must increase the whole temperature of processing bath, accordingly, there exist make cost of energy The problem of increase.In turn, in the case where carrying out trbasic zinc phosphate processing in handling the trbasic zinc phosphate processing bath that the time extends certain time, The problem of there is also productivity reductions.
Therefore, every single side 1.5g/m is formed as with island2~15.0g/m2Trbasic zinc phosphate coating layer 103 method one Example, proposes following method: for the temperature of trbasic zinc phosphate processing bath, locally increasing temperature with steam.According to the above method, On the basis of the adhesion amount for increasing trbasic zinc phosphate crystal, making trbasic zinc phosphate crystal further is needle-shaped (sharp keen shape), thus phosphoric acid The fluffy degree of zinc crystal improves, and the head of trbasic zinc phosphate crystal more exposes from lubricating film coated layer.Trbasic zinc phosphate crystal itself does not have The sliding property of bottom surface pressure, therefore, confficient of static friction becomes larger.On the other hand, trbasic zinc phosphate crystal is crushed under high surface pressure, with profit Sliding coating layer facilitates sliding property together, therefore, can with equally maintained in the past high surface pressure mouldability=resistent mucous membrane (with L font extrusion forming simulation).
Herein, it will be used to form every single side 1.5g/m with island2~15.0g/m2Trbasic zinc phosphate coating layer 103 device One is illustrated in A, B of Fig. 3.It in device shown in A, B of the Fig. 3, is constructed as follows: leading to the base of plate in trbasic zinc phosphate processing bath 20 The steam generated in the surface of body steel plate 101 and heater 21 contacts.In trbasic zinc phosphate processing bath 20, produced by the heating of heater 21 Raw steam is stirred with blender 22, and is contacted with the surface of matrix steel plate 101.When forming trbasic zinc phosphate coating layer 103, in phosphoric acid Local heating is carried out in zinc processing bath 20, if by making the surface of matrix steel plate 101 increase treatment temperature and contacting steam, It will not then make trbasic zinc phosphate coating processing bath 20 is whole to become apparent high temperature, and can be in the short processing for not damaging productivity Time content, which is changed places, forms trbasic zinc phosphate coating layer 103 with island.Steam temperature is higher, more promotes the shape of trbasic zinc phosphate coating layer 103 At.Therefore, preferably 100 DEG C or more, more preferable 120 DEG C of steam temperature or more.When the temperature of steam is got higher, cost of energy rises, And its effect is saturated, therefore, steam temperature is preferably set to 200 DEG C or less.
In this way, when so that the surface of matrix steel plate 101 is contacted steam in trbasic zinc phosphate processing bath 20, with island shape on steel band At every single side 1.5g/m2~15.0g/m2Trbasic zinc phosphate overlay film the reasons why it is unclear.However, on the surface of matrix steel plate 101, The growth for starting from the trbasic zinc phosphate crystal of some growth point of trbasic zinc phosphate crystal is interfered, and forms trbasic zinc phosphate overlay film with island, another Aspect rises to 100 DEG C or more due to steam with the trbasic zinc phosphate crystal that island is formed and is activated, in trbasic zinc phosphate processing bath 20 It is contacted with trbasic zinc phosphate treatment fluid, so that its growth is further promoted, presumption can may form every single side 1.5g/ with island m2~15.0g/m2Trbasic zinc phosphate overlay film.
It should be noted that for forming every single side 1.5g/m with island2~15.0g/m2Trbasic zinc phosphate coating layer 103 Device is not particularly limited.It can be the type for contacting matrix steel plate 101 directly with steam, or with trbasic zinc phosphate processing The type for contacting matrix steel plate 101 directly with steam after liquid mixing.Furthermore, it is also possible to for trbasic zinc phosphate processing bath will be set to certainly The steam that the heater 21 of 20 wall surface generates is stirred in blender 22, makes matrix steel plate 101 and trbasic zinc phosphate treatment fluid And the type that steam contacts simultaneously.
It should be noted that device shown in A, B by using Fig. 3, can make 103 island of trbasic zinc phosphate coating layer, The maximum value for blowing the adhesion amount of trbasic zinc phosphate coating layer 103 caused by steam is 15.0g/m2Left and right.By covering trbasic zinc phosphate The adhesion amount of film layer 103 is every single side 1.5g/m2~15.0g/m2, lubricating film coated layer 105 can be made more reliably closely sealed in matrix On steel plate 101, even if trbasic zinc phosphate coating layer 103 does not also disappear under the processing and forming under high surface pressure, can more reliably it keep Final process of the lubricating film coated layer 105 up to processing and forming.
More than, while referring to Fig.1~Fig. 3 while the surface-treated steel strips 10 of present embodiment are illustrated in detail.
Measuring method > of the < about various physics values
Then, the measuring method for the various physics values surface-treated steel strips of present embodiment 10 realized, simply It is illustrated.
Firstly, constituting contained in the average grain diameter of the trbasic zinc phosphate crystal of trbasic zinc phosphate coating layer 103, lubricating film coated layer 105 The average grain diameter of macromolecule wax can be by utilizing field emission scanning electron microscope (Field Emission Scanning Electron Microscope:FE-SEM), the well known measuring method of surface of steel plate or the like is observed under low accelerating voltage And it measures.
In addition, the adhesion amount of every single side of trbasic zinc phosphate coating layer 103 and lubricating film coated layer 105 can be such by gravimetric method Well known measuring method and measure.
It should be noted that for the thickness of trbasic zinc phosphate coating layer 103 and lubricating film coated layer 105, with electron microscopics such as SEM The section of sem observation surface-treated steel strips and can measure, but for the thickness of lubricating film coated layer 105, side below can also be used Method measurement.Firstly, from surface along depth direction, utilizing glow discharge optical emission spectrometry device to the section of surface-treated steel strips 10 (Glow Discharge Spectroscopy:GDS) measures the ingredient (such as Si) and trbasic zinc phosphate crystal of lubricating film coated layer 105 The luminous spectrum intensity of ingredient (such as Zn).By said determination, available 2 corresponding with each ingredient in luminescent spectrum Peak.It herein, can be by each 50% value of the peak intensity of 2 ingredients (surface layer that 50% value that Si is matrix steel plate side, Zn are steel band 50% value of side) between thickness of the corresponding thickness as lubricating film coated layer 105.
In addition, utilizing the electronic displays such as SEM for the area ratio that trbasic zinc phosphate crystal exposes on the surface of lubricating film coated layer 105 Micro mirror observes the surface of surface-treated steel strips 10, with the area of the trbasic zinc phosphate crystal detected in well known method specific field of view, So as to obtain.Herein, when particular area rate, many places on the surface of preferred view surface-treated steel strips 10 are calculated specific The area ratio is averaged.
In addition, the confficient of static friction of lubricating film coated layer 105 can pass through round flanging muscle pull-out test etc. described below Various test methods and measure.
More than, the measuring method for the various physics values that the surface-treated steel strips 10 of present embodiment are realized simply is carried out Explanation.It should be noted that said determination method only an example, it can also be specific by measuring method well known to other Each physics value.
(manufacturing method about surface-treated steel strips)
Then, the manufacturing method of the surface-treated steel strips of present embodiment 10 is illustrated while referring to Fig. 4.Fig. 4 is The flow chart of an example of the process of the manufacturing method of the surface-treated steel strips 10 of present embodiment is shown.
In the manufacturing method of the surface-treated steel strips 10 of present embodiment, batched firstly, for defined matrix steel plate 101 Made of steel band, implement ungrease treatment, the pre-treatments (pre-treatment step S101) such as cleaning treatment as needed.
Later, quenched (quenched step is carried out using the surface conditioner comprising colloidal titanium to the surface of matrix steel plate 101 S103).The colloidal titanium with coarse partial size is attached to the surface of matrix steel plate 101 as a result,.
Then, by above explained method, make matrix steel plate 101 of the acicular crystal of trbasic zinc phosphate after surface tempering (trbasic zinc phosphate coating layer forming step S105) is precipitated in surface.The acicular crystal of trbasic zinc phosphate is with island in matrix steel plate 101 as a result, Surface is precipitated, and forms trbasic zinc phosphate coating layer 103.It should be noted that being carried out as above-mentioned by device shown in A, B with Fig. 3 The precipitation of trbasic zinc phosphate compatibly can form trbasic zinc phosphate coating layer 103 with island.
Then, lubricated agent is coated on matrix steel plate 101 and trbasic zinc phosphate coating layer 103, in drying condition appropriate Under be dried, to form lubricating film coated layer 105 (lubricating film coated layer forming step S107).Thus, it is possible to manufacture the A of Fig. 2 Surface-treated steel strips 10 shown in B with Fig. 2.
Later, as needed, for the surface-treated steel strips 10 manufactured, well known post-processing (rear place also can be implemented Manage step S109).
More than, to an example letter of the process of the manufacturing method of the surface-treated steel strips 10 of present embodiment while referring to Fig. 4 Singly it is illustrated.
Embodiment
In below, while embodiment and comparative example are shown, while to surface-treated steel strips and surface-treated steel strips of the invention Manufacturing method is specifically illustrated.It should be noted that embodiment described below only surface treated steel of the invention An example of the manufacturing method of band and surface-treated steel strips, the manufacturing method of surface-treated steel strips of the invention and surface-treated steel strips Be not limited to it is following shown in example.
It should be noted that in embodiment below, the record of " % " just refers to " quality % " as long as no specifying. In addition, adhesion amount each means the adhesion amount of every single side in embodiment below.
(1) the trbasic zinc phosphate processing of steel plate
For the cutting plate (300mm of the SPH590 steel plate (hot rolled steel plate of tensile strength 590MPa or more) of plate thickness 3.2mm × 300mm) two sides, carry out trbasic zinc phosphate processing with impregnation.At this point, for the present embodiment, to steel plate in impregnation Two sides stirs the steam generated by the heater for the wall surface for being set to device with blender, thus 100 DEG C~120 DEG C of contact Steam 5 seconds.Change dip time between 5 seconds~120 seconds, adjusts the adhesion amount of trbasic zinc phosphate crystal, obtain shown in table 1 Trbasic zinc phosphate handles steel plate.The mass change of steel plate of the adhesion amount of trbasic zinc phosphate crystal by trbasic zinc phosphate before and after the processing is found out.
(2) formation of lubricating film coated
In the pure water (deionized water) addition it is following shown in Binder Composition, Lubrication Composition and EP agent, sufficiently Stirring makes its dispersion, is diluted with pure water, so that solid content becomes 20%, chemical solution used in preparation coating. The chemical solution is coated on to the surface of above-mentioned trbasic zinc phosphate processing steel plate using one, the face of bar coater one face, makes it with 60 DEG C It is dry, lubricating film coated is formed on surface, makes lubricated steel plate.The adhesion amount of lubricating film coated forms front and back by lubricating film coated The mass change of steel plate calculates.
Chemical solution (2-1)
A) Binder Composition
Sodium metasilicate (SiO2/Na2The molar ratio of O: 4)
Acrylic resin (monomer composition: acrylic acid 8%, methacrylic acid 52%, butyl acrylate 40%)
B) Lubrication Composition
Organic high molecular compound: polyethylene wax (3 μm of molecular weight 20000, average grain diameter)
Solid lubricant: molybdenum disulfide (2 μm of average grain diameter)
Soap: odium stearate
C) EP agent
Phosphite ester
D) solid component content
The solid content of the sodium metasilicate of all solids component amount relative to lubricating film coated layer: 88%
The solid content of the polyethylene wax of all solids component amount relative to lubricating film coated layer: 5%
Chemical solution (2-2)
A) Binder Composition
Sodium metasilicate (SiO2/Na2The molar ratio of O: 5)
Acrylic resin (monomer composition: acrylic acid 8%, methacrylic acid 52%, butyl acrylate 40%)
B) Lubrication Composition
Organic high molecular compound: polyethylene wax (0.5 μm of molecular weight 2000, average grain diameter)
Solid lubricant: molybdenum disulfide (2 μm of average grain diameter)
Soap: odium stearate
C) EP agent
Phosphite ester
D) solid component content
The solid content of the sodium metasilicate of all solids component amount relative to lubricating film coated layer: 80%
The solid content of the polyethylene wax of all solids component amount relative to lubricating film coated layer: 5%
Chemical solution (2-3)
A) Binder Composition
Sodium metasilicate (SiO2/Na2The molar ratio of O: 2)
Acrylic resin (monomer composition: acrylic acid 8%, methacrylic acid 52%, butyl acrylate 40%)
B) Lubrication Composition
Organic high molecular compound: polyethylene wax (1.0 μm of molecular weight 10000, average grain diameter)
Solid lubricant: molybdenum disulfide (2 μm of average grain diameter)
Soap: odium stearate
C) EP agent
Phosphite ester
D) solid component content
The solid content of the sodium metasilicate of all solids component amount relative to lubricating film coated layer: 60%
The solid content of the polyethylene wax of all solids component amount relative to lubricating film coated layer: 30%
(3) crystalline size
Trbasic zinc phosphate treated surface of steel plate is observed by SEM under acceleration voltage 5kV, 500 times of multiplying power.Trbasic zinc phosphate is brilliant Body is as follows in the area ratio that surface is exposed: image being carried out 2 values, is calculated with the area of crystal block section.In addition, arbitrarily selection 4 A above crystal exposed on surface, measures the length of long axis and short axle, calculates average crystalline size, the crystalline substance as trbasic zinc phosphate Body size.
(4) evaluation method
A-1) resistent mucous membrane
In order to simulate the multistep plastic processing under high surface pressure, as Fig. 5 shows summary, set using the extrusion forming of L font It is standby, for the side of the L bending machining sample of lubricated steel plate, multistep is carried out with following step, processing is thinned, evaluate its profit Slip energy.At this point, molding number is 2 times or less and in the case where surface of steel plate is engaged, multistep molding can not be carried out, because This, the steel plate that 3 times or more are not engaged is as qualification.It should be noted that the case where having occurred below occlusion for 2 times note Make ×, there is a situation where be engaged to be denoted as zero by 3 times or more.
A-2) step
General antirust oil is become 1.5g/m with adhesion amount by step (1)2Mode be coated on the two sides of sample.
The gap of formed punch and mold is arranged in step (2), so that become plate thickness -0.25 (plate thickness reduces width=0.15mm), Implement initial thinned processing (L-type molding) to sample.
Step (3) is for having carried out the L font sample of thinned processing in step (2), side is further with the diminution of -0.25 spacing Gap generates sticking to mould in surface of steel plate while being repeated up to, finds out and produce the thinned number of sticking to mould.
B-1) skid-resistant roller
In order to simulate the resistance to roller transporting under high surface pressure, as Fig. 6 shows summary, with round flanging muscle clamping steel plate Surface and the back side, load when by drawing steel plate calculate confficient of static friction.Confirmed respectively: confficient of static friction is 0.09 or less When, the power for sending out steel plate can not be applied, it is difficult to which the logical plate and confficient of static friction carried out on actual production line is more than 0.20 When, in order to which power needed for sending out steel plate becomes excessive, it is difficult to carry out the logical plate on actual production line.Therefore, by confficient of static friction It is 0.10 or more and 0.20 steel plate below as qualified.It should be noted that being the feelings except the range by confficient of static friction Condition is denoted as ×, within that range the case where be denoted as zero.
B-2) step
General antirust oil is become 1.5g/m with adhesion amount by step (1)2Mode be coated on the two sides of sample.
With round flanging muscle (R5) by the two sides of laminated steel and with load 1 [kN] clamping, drawing steel plate calculates step (2) Confficient of static friction when drawing.
[table 1]
(5) evaluation result
Above-mentioned table 1, which is shown, to be formed with lubrication on the different various trbasic zinc phosphates processing steel plate of the adhesion amount in trbasic zinc phosphate crystal and covers The evaluation result of the case where film.
Shown by table 1 for preferred trbasic zinc phosphate coating layer and lubricating film coated layer and the dew for meeting trbasic zinc phosphate crystal The sufficient property for taking into account resistent mucous membrane Yu skid-resistant roller is embodied in No.2~4 of the area ratio, 6~10,12~15,17~18,20 out Energy.
It on the other hand, is 0 or the NO.1 less than 0,19 for the adhesion amount of trbasic zinc phosphate coating layer, confficient of static friction is lower, Result as resistent mucous membrane and skid-resistant roller difference.Even if the lubricating film coated of adhesion amount and upper layer for trbasic zinc phosphate coating layer is full The preferred condition of foot, trbasic zinc phosphate crystal long axis direction average grain diameter or short-axis direction average grain diameter in the scope of the present invention Except NO.11,24,29,30,31, confficient of static friction is lower, and becomes the result of skid-resistant roller difference.For trbasic zinc phosphate crystal compared with The No.5 mostly exposed, lubricating film coated itself is few, therefore, becomes the result of resistent mucous membrane difference.For NO.16, trbasic zinc phosphate crystal Exposing the area ratio it is few, confficient of static friction does not become 0.10 or more.
The enlarged photograph of the surface-treated steel strips of comparative example and example of the present invention is shown in Fig. 7~10.For ratio shown in Fig. 7 Compared with example (No.30), the adhesion amount of island trbasic zinc phosphate coating layer is 1.9g/m2, major diameter be 100 μm, minor axis is 20 μm, lubricating film coated The adhesion amount of layer (chemical solution 2-1) is 3.3g/m2, trbasic zinc phosphate expose the area ratio be 10%, for comparative example shown in Fig. 8 (No.31), the adhesion amount of island trbasic zinc phosphate coating layer is 4.5g/m2, major diameter be 200 μm, minor axis is 50 μm, lubricating film coated layer The adhesion amount of (chemical solution 2-1) is 3.3g/m2, trbasic zinc phosphate expose the area ratio be 24%.For example of the present invention shown in Fig. 9 (No.14), the adhesion amount of island trbasic zinc phosphate coating layer is 8.0g/m2, major diameter be 64 μm, minor axis is 7 μm, lubricating film coated layer (change Learn solution 2-1) adhesion amount be 3.7g/m2, trbasic zinc phosphate expose the area ratio be 80%, for example of the present invention shown in Fig. 10, island The adhesion amount of shape trbasic zinc phosphate coating layer is 8.0g/m2, major diameter be 31 μm, minor axis is 4 μm, lubricating film coated layer (chemical solution 2-1) Adhesion amount be 3.7g/m2, trbasic zinc phosphate expose the area ratio be 60%.
In example of the present invention, by the way that the temperature of trbasic zinc phosphate processing bath is locally increased temperature with steam, increasing trbasic zinc phosphate On the basis of the adhesion amount of crystal, making trbasic zinc phosphate crystal further is needle-shaped (sharp keen shape), so that trbasic zinc phosphate crystal is fluffy Looseness improves, and the head of trbasic zinc phosphate crystal more exposes from lubricating film coated layer.Trbasic zinc phosphate crystal itself does not have bottom surface pressure Sliding property, therefore, confficient of static friction become larger.On the other hand, under high surface pressure, trbasic zinc phosphate crystal is crushed, with lubricating film coated layer Be conducive to sliding property together, therefore, in the past equally maintain high surface pressure mouldability=resistent mucous membrane (with L font pressurization at Pattern is quasi-).In this way, can be embodied as carrying on the back the skid-resistant roller and resistent mucous membrane of reflexive energy together.
More than, suitable embodiment of the invention is illustrated in detail while referring to attached drawing, but the present invention is unlimited Due to above-mentioned example.Show if it is the people with the usual knowledge in technical field belonging to the present invention, in claim In the range of the technical concept that secretary carries, it is contemplated that various modifications or fixed case understand certainly and also belong to this for these The protection scope of invention.
Description of symbols
1 pinch roller
2 molds
10 surface-treated steel strips
The processing bath of 20 trbasic zinc phosphates
21 heaters
22 blenders
101 matrix steel plates
103 trbasic zinc phosphate coating layers
105 lubricating film coated layers

Claims (8)

1. a kind of surface-treated steel strips, have:
Matrix steel plate；
Trbasic zinc phosphate coating layer is formed in the surface of described matrix steel plate with island and by acicular trbasic zinc phosphate Crystallization； With,
Lubricating film coated layer covers the surface of described matrix steel plate and a part of the trbasic zinc phosphate coating layer and includes at least Lubrication Composition,
The trbasic zinc phosphate crystal is 25%~90% in the area ratio that the surface of the lubricating film coated layer is exposed.
2. surface-treated steel strips according to claim 1, wherein the average grain diameter of the long axis direction of the trbasic zinc phosphate crystal Average grain diameter for 25 μm~70 μm, short-axis direction is 3 μm~10 μm.
3. surface-treated steel strips according to any one of claim 1 or 2, wherein the attachment of the trbasic zinc phosphate coating layer Amount is every single side 1.5g/m2~15.0g/m2。
4. surface-treated steel strips described in any one of claim 1 to 3, wherein the adhesion amount of the lubricating film coated layer For every single side 1.0g/m2~12.0g/m2。
5. surface-treated steel strips according to any one of claims 1 to 4, the lubricating film coated layer includes: SiO2/M2O institute The silicic acid alkali metal salt that the molar ratio shown is 2~5, wherein M is alkali metal；Be 0.1 μm~3.0 μm poly- by average grain diameter The macromolecule wax that at least either in ethylene waxes or polypropylene wax is formed,
Relative to all solids composition quality of the lubricating film coated layer, the solid component content of the silicic acid alkali metal salt is 60 The mass of quality %~90 %, the solid component content of the macromolecule wax are 5 mass of mass %~40 %.
6. a kind of manufacturing method of surface-treated steel strips comprising following steps:
Quenched step carries out the quenched of the surface of matrix steel plate using the surface conditioner comprising colloidal titanium；
Trbasic zinc phosphate coating layer forming step makes the needle-shaped crystalline substance of trbasic zinc phosphate on the surface for the described matrix steel plate for implementing surface tempering Body is grown to island, forms trbasic zinc phosphate coating layer on the surface of the matrix steel plate；With,
Lubricating film coated layer forming step, by the lubricated agent for including at least Lubrication Composition with adhesion amount for every single side 1.0g/m2~ 12.0g/m2Mode be coated on the surface of described matrix steel plate and the trbasic zinc phosphate coating layer, form lubricating film coated layer, make institute It is 25%~90% that trbasic zinc phosphate crystal, which is stated, in the area ratio that the surface of the lubricating film coated layer is exposed.
7. the manufacturing method of surface-treated steel strips according to claim 6, wherein formed and walked in the trbasic zinc phosphate coating layer In rapid, described matrix steel plate is heated.
8. the manufacturing method of surface-treated steel strips according to claim 7, wherein contact described matrix steel plate with steam It is heated.
CN201780023567.2A 2016-04-13 2017-04-13 Surface-treated steel strip and method for producing surface-treated steel strip Expired - Fee Related CN109072447B (en)

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