CN106133201B

CN106133201B - DC cathode electrolysis constituent, metal material and its manufacturing method with lubricating film

Info

Publication number: CN106133201B
Application number: CN201580009607.9A
Authority: CN
Inventors: 川越亮助; 清水大辅
Original assignee: Nihon Parkerizing Co Ltd
Current assignee: Nihon Parkerizing Co Ltd
Priority date: 2014-02-21
Filing date: 2015-02-16
Publication date: 2018-12-07
Anticipated expiration: 2035-02-16
Also published as: US20170073831A1; KR101815412B1; JPWO2015125737A1; WO2015125737A1; CN106133201A; TW201536963A; JP6211678B2; MX2016010837A; KR20160111969A

Abstract

The present invention provides a kind of DC cathode electrolysis constituent of good metal material with lubricating film of chemical conversion being capable of forming after lubricity and degreasing.DC cathode electrolysis of the invention is contained with constituent: from by it is more than divalent typical metal ion (but will be except zinc ion) and the group that constitutes of rare earth element ion at least one kind of metal ion or its fluor-complex (A) that select；The organic acid compound (B) of straight chain alkylene group in the molecule comprising carboxyl and 4 or more carbon number；Water (C).

Description

DC cathode electrolysis constituent, the metal material with lubricating film and its manufacture Method

Technical field

The present invention relates to DC cathode electrolysis constituents, in particular to contain defined metal ion and organic acid chemical combination Constituent is used in the DC cathode electrolysis of object.

Moreover, it relates to the metal material with lubricating film obtained using DC cathode electrolysis with constituent And its manufacturing method.

Background technique

Metal material is used in many structures.For example, iron type materials are from the plate, line, stick as blank material, by squeezing The pressure of pressure, drawing, cutting, punching etc. makes the part for fabricating out structure, big by being assembled into weld, be bonded engagement The shape of body.Then, by antirust treatment, various coatings (coating process), become the product in view of design, according to circumstances Electronic component or inner body are put into dispatch from the factory.

It is made in processing in the pressure of such material and needs lubricity, propose various technologies.For example, in patent document 1, As the forming method of lubricating film, disclose a kind of electrolyte of the use containing zinc ion, phosphate ion and nitrate ion into Row catholyte forms chemical conversion epithelium and then makes the method for itself and the lubricant contact of water class or oils.

Patent document 1: Japanese Unexamined Patent Publication 2000-144494 bulletin.

On the other hand, in recent years, it is desirable to can easily implement various chemical conversion treatments after by metal material processing.More It says to body, it is desirable to after will have the metal material processing of lubricating film, by lubricating film demoulding, and can easily implement each Kind chemical conversion treatment (for example, trbasic zinc phosphate processing, metal oxide treated etc.).That is, for lubricating film, it is desirable that lubricity and demoulding Taking into account under the high level for chemical conversion property that treated.In addition, especially with regard to demoulding processing, due to being for coating process preparation , it is desirable to be able to the leading portion used in chemical conversion treatment is easily implemented usually using such ungrease treatment.

The present inventors in implementing patent document 1 method recorded and formed lubricating film, to its characteristic (lubricity and Chemical conversion after degreasing) studied after find, irregular, lubricity occurs in the chemical conversion epithelium formed after carrying out ungrease treatment It is insufficient with taking into account for the chemical conversion after degreasing.In particular, in the scheme of patent document 1, due to being formed on the metal material Zinc phosphate coat and/or response type soap epithelium cannot be removed and be remained with common ungrease treatment, so implementing thereafter Chemical conversion treatment does not carry out well.

Summary of the invention

The present invention is in view of the foregoing, it is therefore an objective to it is good to provide a kind of chemical conversion being capable of forming after lubricity and degreasing The DC cathode electrolysis constituent of metal material with lubricating film.

Moreover, it is an object that a kind of gold with lubricating film using DC cathode electrolysis constituent Belong to the manufacturing method of material and the metal material with lubricating film.

The present inventors is specialized in about the above problem, as a result, it has been found that, by using including defined metal The DC cathode electrolysis of ion or its fluor-complex and defined organic acid compound implements catholyte with constituent, can obtain To the lubricating film that desired characteristic is presented.

It finds, above-mentioned purpose can be realized by structure below.

(1) a kind of DC cathode electrolysis constituent, which is characterized in that contain: from by typical metal ion more than divalent At least one kind of metal ion or its fluor-complex selected in the group that (but will be except zinc ion) and rare earth element ion be constituted (A)；The organic acid compound (B) of straight chain alkylene group in the molecule comprising carboxyl and 4 or more carbon number；With water (C).

(2) the DC cathode electrolysis constituent as described in (1), metal ion or its fluor-complex (A) include from by magnesium from At least one kind of metal ion or its fluor-complex selected in the group that son, calcium ion, aluminium ion, ruthenium ion and lanthanum ion are constituted.

(3) the DC cathode electrolysis constituent as described in (1) or (2), organic acid compound (B) includes comprising carbon number 4 The aliphatic dicarboxylic acid of the aliphatic monocarboxylic acid of above straight chain alkylene group or the straight chain alkylene group comprising 4 or more carbon number.

(4) the DC cathode electrolysis constituent as described in any one of (1)~(3), pH is 3.5~12.5.

(5) a kind of manufacturing method of the metal material with lubricating film, has metal material being impregnated into (1)~(4) Described in any item DC cathode electrolysis are implemented at the catholyte using direct current in constituent, by cathode of metal material Reason, the process that lubricating film is formed on metal material surface.

(6) a kind of metal material with lubricating film, the system of the metal material by having lubricating film described in (5) Make method manufacture.

(7) a kind of metal material with lubricating film has the profit of metal material and configuration on metal material surface Sliding epithelium, lubricating film includes: from by it is more than divalent typical metal elements (but will be except Zn-ef ficiency) and rare earth element from At least one kind of metallic element selected in the group that son is constituted；It in the molecule include having for the straight chain alkylene group of carboxyl and 4 or more carbon number Machine acid compound and/or its salt；Using red-hot Discharge illuminating spectroscopic measurements method, from the opposite with metal material of lubricating film Side surface towards metal material side into the analysis of the depth direction of lubricating film, lubricating film and metal material The peak strength (Is) from carbon on the surface of opposite side, with one opposite with metal material away from lubricating film The peak value from carbon that the surface of side is equivalent to the middle position of 1/2 depth of the integral thickness of lubricating film is strong The ratio (Im/Is) of (Im) is spent less than 1.0.

(8) metal material with lubricating film as described in (6) or (7), be also equipped on lubricating film containing oil at The oil reservoir divided.

In accordance with the invention it is possible to which it is good with lubrication skin to provide a kind of chemical conversion being capable of forming after lubricity and degreasing Constituent is used in the DC cathode electrolysis of the metal material of film.

In addition, in accordance with the present invention it is further possible to provide a kind of have lubricating film using DC cathode electrolysis constituent Metal material manufacturing method and metal material with lubricating film.

Detailed description of the invention

Fig. 1 is the schematic sectional view for indicating an embodiment of the metal material with lubricating film of the invention.

Fig. 2 is the schematic sectional view for indicating another embodiment of the metal material with lubricating film of the invention.

Fig. 3 is that the lubricity implemented in embodiment evaluates the schematic diagram of high speed deep drawing test machine used in (its 2).

Specific embodiment

Hereinafter, to DC cathode electrolysis of the invention constituent (DC cathode electrolysis treatment fluid), having lubrication skin The metal material and its manufacturing method of film describe in detail.In addition, the figure in the present invention is schematic diagram, the relationship etc. of the thickness of each layer It might not be consistent with reality.

As one of characteristic point of the invention, it can enumerate to use as described above and contain defined metal ion or its network The DC cathode electrolysis of compound and defined organic acid compound implements catholyte this point with constituent.

Firstly, usually have makes metal precipitate into surface treatment on treated object, being referred to as coating by catholyte.It is right This, in the present invention, use even if using treated object as cathode dispose be not easy as metal be precipitated metal ion or its Fluor-complex is as the ingredient in constituent.That is, the metal ion being used in the present invention or its fluor-complex are not easy to make in water class For metal reduction, the hydroxide containing the metal ion, hydrous oxide and/or oxide are easily become.

In the present invention, using the film-forming method being electrolysed by DC cathode.Firstly, leading to if implementing catholyte Each metal ion or the electrophoresis of its fluor-complex are crossed, metal ion occurs or its fluor-complex is attached to the metal material as treated object Close denseization.At this point, the reduction reaction of the electronics discharged as consumption from treated object, occurs hydrionic consumption and hydroxide The increase etc. of object ion.For example, if it is there is a situation where the electrolysis of water, then from the metal material surface as treated object Upper generation hydrogen, so the pH rising on metal material surface is promoted.As a result, the metal ion of denseization or its fluor-complex are formed Insoluble salt (oxide, hydroxide or hydrate), is precipitated on metal material surface.Such metal ion or its network The region that compound is precipitated easily is removed by the demoulding processing usually using such ungrease treatment etc., can easily implement it Chemical conversion treatment afterwards.

On the other hand, since organic acid compound has carboxyl, so if to carry out electrophoresis far from if from metal material. Therefore, organic acid compound is not easy to be precipitated on metal material surface, in particular, the higher display of the pH near metal material is stronger It is ionic, so the phenomenon becomes more significant.Therefore, at catholyte initial stage, organic acid compound is not easy in metal material Be precipitated on surface, as electrolysis is in progress, organic acid compound gradually form metal ion or its fluor-complex, containing the metal from Oxide, hydroxide of son etc. and salt, it may be considered that organic acid compound and metal ion are precipitated on metal material surface Compound salt out.That is, exposing surface (the table of with metal material side opposite side of the organic acid compound in lubricating film Face) side is further concentrated.Therefore, on the surface of lubricating film, there are the good organic acid compound of more lubrication property, Good lubricity can be played.

As above, by using the water class constituent for being contaminated with metal ion or its fluor-complex and organic acid compound DC cathode electrolysis is carried out, the increase of the hydroxide ion concentration on metal material surface, metal ion and organic acid occurs The sedimentation equilibrium of compound deviates, and lubricating film is precipitated.The forming process of such lubricating film and previous lubricating film Forming process is significantly different.

In addition, if not needing to implement high-temperature process when manufacturing lubricating film, and with 1 using the constituent Process completion processing, so being preferred at payable productive aspect.Even if in addition, because formed lubricating film its Thinner thickness can also obtain desired effect, so in terms of cost and productive aspect is preferred.

Hereinafter, first to the composition DC cathode electrolysis various composition of constituent (later also single to be referred to as " constituent ") (metal ion or its fluor-complex (A), organic acid compound (B), water (C) etc.) describes in detail, then to the band for using constituent There is the manufacturing method of the metal material of lubricating film to describe in detail.

In constituent, include the typical metal ion (but will be except zinc ion) and rare earth element more than divalent At least one kind of metal ion for selecting or its fluor-complex (A) in the group that ion is constituted (after, it is also referred to as the concept comprising the two Make " metal ion (A) ").The metal ion (A) in catholyte become metal oxide, metal hydroxides or with it is rear The fluor-complex for the organic acid compound (B) stated, for the ingredient for constituting lubricating film.

As typical metal ion (ions of typical metal elements), the week of beryllium, magnesium, calcium, strontium, barium, radium etc. can be enumerated The ion (alkaline-earth metal ion) of the element of 2nd race of phase table, the ion of the element of the 12nd race of the periodic tables such as cadmium, mercury (in addition, except zinc ion), the ion of the element of the belonging to group 13 of periodic table of aluminium, gallium, indium, thallium etc., the periodic tables such as germanium, tin, lead The ion of the element of 14th race, the ion of the element of the 15th race of periodic table of antimony, bismuth etc., the element of the 16th race of the periodic tables such as polonium Ion.

So-called rare earth element ion, refers to the ion of rare earth element, refer to including ruthenium ion (ion of yttrium), The concept of scandium ion (ion of scandium element) and lanthanum ion.

So-called lanthanum ion (ion of lanthanum element), refers to that the ion of lanthanum race metallic element is more particularly Refer to the ion of the elements such as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

Wherein, after the lubricity of lubricating film and/or degreasing the more preferable this point of chemical conversion (after, it is also single to be referred to as " this The more preferable this point of The effect of invention ") on, preferably magnesium ion, calcium ion, aluminium ion, ruthenium ion or lanthanum ion are more excellent Choosing is magnesium ion, calcium ion, aluminium ion.

In addition, metal ion (A) can both be used only a kind, also can be used together two or more.

The fluor-complex of so-called above-mentioned metal ion refers to the fluor-complex (organic fluor-complex) comprising above-mentioned metal ion.? In fluor-complex, preferably include chelating agent (complexing agent).In addition, not containing aftermentioned organic acid compound in chelating agent (B).

As chelating agent, as long as have the effect of by the function of above-mentioned metal ion-chelant, do not damage it is of the invention, just It is able to use.As chelating agent, can be used the organic acids such as gluconic acid, citric acid, succinic acid and its salt, organic phosphorus compound, The aminopolycanboxylic acid of ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA) etc. or its salt etc..Wherein, effect of the invention more On this point good, preferably aminopolycanboxylic acid or its salt.Alternatively, it is also possible to use the condensed phosphates such as sodium tripolyphosphate as Chelating agent, but it is more difficult with the formation of the salt of metal ion, control due to being easy to carry out, it is preferred that not wrapped in constituent Contain.

So-called aminopolycanboxylic acid is the general name of the chelating agent in the molecule with amino and multiple carboxyls.Specifically, can To enumerate EDTA(ethylenediamine tetra-acetic acid), HEDTA(hydroxyethylethylene diamine tri-acetic acid), NTA(nitrilotriacetic acid), the sub- second of DTPA(bis- Base pentaacetic acid), TTHA(triethylenetetraaminehexaacetic acid) etc..In addition, the type of the salt of aminopolycanboxylic acid is not special It limits, ammonium salt, sodium salt, sylvite of foregoing illustrative compound etc. can be enumerated.

The method that above-mentioned metal ion or its fluor-complex are supplied into constituent is not specially limited, and can enumerate will contain Have above-mentioned metal ion salt (for example, carbonate, bicarbonate, acetate, formate, nitrate, sulfate, borate), The inorganic constituents such as oxide, hydroxide, halide (such as fluoride) or fluor-complex containing above-mentioned metal ion are (organic Fluor-complex) etc. the method added into water.In addition, in the case where being taken care of during the metal material that will have lubricating film is long, Or in the case where taking care of the metal material with lubricating film in high temperature and humidity environment, in order to inhibit the generation of rust, preferably Be inhibit use of the chloride to constituent.

The concentration of metal ion or its fluor-complex in constituent is not particularly limited, but more preferable in effect of the invention On this point, preferably 50~50000 mass ppm, more preferably 500~10000 mass ppm.

In addition, total concentration of preferably metal ion (A) is using two or more metal ion (A) In above range.

In addition, using the fluor-complex of metal ion, the metal ion that preferably contains in fluor-complex Amount is in above range.

Organic acid compound (B) is the compound of the straight chain alkylene group in the molecule comprising carboxyl and 4 or more carbon number.This has Machine acid compound (B) interacts via carboxyl and above-mentioned metal ion (A) and forms fluor-complex, is taken into lubricating film Enter.Hydrocarbon skeleton in organic acid compound (B) facilitates the imparting of lubricity.

It include carboxyl in organic acid compound (B), the quantity of carboxyl is not particularly limited.In addition, of the invention On this point effect is more preferable, monocarboxylic acid, tool with 1 carboxyl can be preferably used, and there are two the dicarboxylic acids of carboxyl.

Include the straight chain alkylene group of 4 or more carbon number in organic acid compound (B).The straight chain alkylene group refers to following Formula (1) indicate base.N indicates 4 or more integer.

Formula (1) *-(CH₂)_n- *

N indicates 4 or more integer.Wherein, on this point effect of the invention is more preferable, preferably 4~17, more preferably Be 4~8.In addition, the straight chain in alkylene is longer, closer to higher fatty acids, lubricity becomes higher.

In addition, * indicates binding site in above-mentioned formula.

As the preferred configuration of organic acid compound (B), the fat of the straight chain alkylene group comprising 4 or more carbon number can be enumerated The aliphatic dicarboxylic acid of race's monocarboxylic acid or the straight chain alkylene group comprising 4 or more carbon number.As above-mentioned aliphatic monocarboxylic acid and The preferred configuration of above-mentioned aliphatic dicarboxylic acid can enumerate the aliphatic monocarboxylic acid indicated with formula (1) and with formula (2) table respectively The aliphatic dicarboxylic acid shown.

[ changing 1 ]

R-COOH formula (1)

HOOC-L-COOH formula (2).

In formula (1), R indicates alkyl of the straight chain alkylene group comprising 4 or more carbon number as part construction.Carbon in alkyl As long as 4 or more number, but on this point effect of the invention is more preferable, preferably 4~18, more preferably 4~ 16, more preferably 5~12.

In addition, as abovementioned alkyl, as long as the straight chain alkylene group comprising 4 or more carbon number is constructed as part, example Such as, as the monocarboxylic preferred configuration of aliphatic indicated by formula (1), the change indicated with formula below (1-1) can be enumerated Close object.

Formula (1-1) R₁- L-COOH

R₁Indicate alkyl.The straight chain alkylene group of L 4 or more carbon number of expression.By R₁The alkyl of expression either straight-chain, It can be branch's chain state.R₁In the total of carbon number be not particularly limited, but it is preferred that R₁In carbon number and L in carbon number Add up to above range (4~18).

4 or more, more preferably 4~17, more preferably 4~8 are preferably by the carbon number of the L alkylene indicated.

In formula (2), L indicates the straight chain alkylene group of 4 or more carbon number.As long as 4 or more carbon number in alkylene, But on this point effect of the invention is more preferable, preferably 5 or more, more preferably 7 or more.The upper limit is not limited especially System, but disposition property on this point, preferably 16 or less.

As aliphatic monocarboxylic acid, it can be cited for example that caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, dodecanoic acid, 14 Alkanoic acid, hexadecanoic acid, Heptadecanoic acide, octadecanoid acid etc..

As aliphatic dicarboxylic acid, it can be cited for example that adipic acid (adipic acid), pimelic acid (jambulol), suberic acid (cork Acid), azelaic acid (azalaic acid), decanedioic acid (sebacic acid), heneicosanedioic acid, dodecanedioic acid, tridecandioic acid (Brazilian base Acid), hexadecandioic acid (hexadecane diacid), octadecane diacid etc..

The concentration of organic acid compound (B) in constituent is not particularly limited, but effect of the invention it is more preferable this On a bit, preferably 50~50000 mass ppm, more preferably 500~10000 mass ppm.

In addition, using two or more organic acid compound (B), the preferably conjunction of organic acid compound (B) Counting concentration is in above range.

In constituent, water is contained as solvent.

The amount of water (C) in constituent is not particularly limited, but more preferable in disposition property effect good, of the invention On this point, preferably relative to constituent all-mass be 65 mass % or more, more preferably 75 mass % or more.The upper limit It is not particularly limited, but more for the situation of 99 mass % or less.

It also may include mentioned component (metal ion or its fluor-complex (A), organic acid compound (B), water in constituent (C)) other compositions other than.

For example, can also in addition add above-mentioned chelating agent in constituent.

The pH of constituent comprising mentioned component is not particularly limited, but on this point effect of the invention is more preferable, Preferably 3.5~12.5, more preferably 4.0~10.0.In addition, DC cathode electrolysis of the invention is not susceptible to metal material The corrosion of material, such as in the case where implementing the washing of metal material after catholyte, although it is a small amount of, but can form The pH of the removal of object, constituent is lower, the material corrosion being more likely to occur in the corrosion or washing step of equipment.In addition, such as Fruit is used as mixed component to remain on the metal material, then is also possible to show adverse effect when steel are taken care of.If it is considered that These, then the pH of constituent is particularly preferably 6.0~9.0.

In addition, in the adjustment of the pH of constituent, can be used known acid (hydrochloric acid, nitric acid, formic acid, acetic acid, sulfonic acid, Fluoric acid etc.) and/or alkali (sodium compound, potassium compound, ammonia, amine compounds etc.).

The manufacturing method of above-mentioned constituent is not specially limited, and can use known method.For example, can enumerate by The method that compound containing above-mentioned metal ion (A) and organic acid compound (B) added into water (C), implemented stir process Deng.

As described later, above-mentioned constituent is used for DC cathode electrolysis use.That is, being to implement for as processed The metal material of object, handled using the catholyte of direct current and the constituent that uses.

Hereinafter, being described in detail to the manufacturing method for the metal material with lubricating film for using above-mentioned constituent.

The manufacturing method of metal material with lubricating film has following process: metal material is impregnated into above-mentioned direct current In catholyte constituent, using metal material as cathode, implement to handle using the catholyte of direct current, in metal material surface Upper formation lubricating film.By implementing this process, can obtain on the metal material aftermentioned at the lubricating film being grouped as.

The type of the metal material used in this process is not particularly limited, and cold-rolled steel sheet (SPC can be used for example Material), hot rolled steel plate (SPH material), general construction rolled steel (SS material), carbon steel (SC material), various steel alloys, stainless steel, Al Or its alloy, Mg or its alloy, Cu or its alloy, Zn or its alloy, Ni based alloy, Co based alloy etc..In addition, about metal material The shape of material is also possible to coiled type, rodlike, band-like, tubulose, casting forged article, bearing etc., shape does not have other than plate It is specially limited.

In addition, on the surface of metal material, as needed can ungrease treatment in advance and clean.

As long as the method for catholyte is cathode used as the metal material of treated object, do not limited especially System, can use known method.In general, using making metal material be immersed in constituent, apply between insoluble anode Alive method.As insoluble electrode, platinum electrode, stainless steel electrode, lead electrode etc. can be used.

Current density is not particularly limited, but on this point effect of the invention is more preferable, preferably 0.01~ 100A/dm², more preferably 0.05~50A/dm²。

Turn on angle is not particularly limited, but on this point effect of the invention is more preferable, preferably 5~300C/ dm², more preferably 15~180C/dm²。

The temperature of constituent is not particularly limited, but on this point lubricating film is efficiently precipitated, preferably It is 15~40 DEG C, more preferably 20~35 DEG C.As described above, unlike the prior art, it does not need group in the present invention High temperature is maintained at object.In addition, the temperature of constituent can also be changed according to the cycling hot of pump or the ambient atmos of summer.

After catholyte processing, metal material is taken out from constituent, as needed, also can be implemented makes to wash with water Cleaning process.

In addition, after a washing process, the drying process for imposing drying process also can be implemented as needed.

As shown in Figure 1, having 12 He of metal material by the metal material 10 obtained by the above method with lubricating film The lubricating film 14 of configuration on the surface thereof.

The type of metal material 12 is as described above.

Lubricating film is the epithelium being precipitated in above-mentioned constituent by implementing catholyte processing.In lubricating film In, comprising from by it is more than divalent typical metal elements (wherein will be except Zn-ef ficiency) and the group that constitutes of rare earth element in select At least one kind of metallic element and in the molecule the organic acid compound of the straight chain alkylene group comprising carboxyl and 4 or more carbon number and/ Or its salt.

The above-mentioned metallic element for including in lubricating film is derived from the element of the metal ion in constituent.Metallic element Type can enumerate each metallic element illustrated in above-mentioned metal ion.

In addition, the existing forms of metallic element are not specially limited in lubricating film, for example, metal The forms such as hydroxide of oxide, metal.

The amount of metallic element in lubricating film is not particularly limited, but in the more preferable this point of effect of the invention On, preferably 0.05g/m²More than, more preferably 0.1~5g/m², more preferably 0.1~3g/m²。

In addition, the organic acid compound for including in lubricating film is the organic acid compound in above-mentioned constituent.Constituent In organic acid compound precipitate into lubricating film together with above-mentioned metallic element in catholyte.In addition, so-called organic The salt of acid compound can enumerate the salt of above-mentioned organic acid compound and above-mentioned metal ion.

The amount of organic acid compound and its salt in lubricating film is not particularly limited, but in effect of the invention On this point more preferable, preferably 0.05~3g/m², more preferably 0.1~1g/m²。

In addition, only the part of organic acid compound is by above-mentioned amount in the case where the salt of organic acid compound It is used in calculating.

Using red-hot Discharge illuminating spectroscopic measurements method, table to the side opposite with metal material from lubricating film Facing towards in the analysis of the depth direction of the lubricating film of metal material side, the side opposite with metal material of lubricating film The surface of the peak strength (Is) from carbon on surface and the side opposite with metal material away from lubricating film is It is equivalent to the peak strength (Im) from carbon of the middle position of 1/2 depth of the integral thickness of lubricating film Than (Im/Is) less than 1.0.Wherein, on this point effect of the invention is more preferable, 0.5 is preferably hereinafter, more than (Im/Is) Preferably 0.2 or less.Lower limit is not particularly limited, but on manufacturing sequence, is that 0.05 or more situation is more.

More particularly, as shown in Figure 1, the peak value from carbon at the surface location 14A of lubricating film 14 is strong Spend the ratio (Im/Is) of the peak strength (Im) from carbon at the middle position 14B of (Is) and lubricating film 14 less than 1.0.That is, peak strength (Is) is bigger than peak strength (Im).In addition, the peak value from carbon at surface location 14A is strong It spends (Is), refers to the peak from carbon found out by red-hot Discharge illuminating spectroscopic measurements method on the surface of lubricating film 14 The size of value.In addition, the peak strength (Is) from carbon at so-called middle position 14B, refers to from lubricating film 14 The side opposite with 12 side of metal material surface (surface location 14A) towards 12 side of metal material, be equivalent to lubricating film Position (in other words, the cross-sectional area of the middle position of the thickness direction of lubricating film 14 of 1/2 depth of 14 integral thickness Domain) in the peak value from carbon found out by red-hot Discharge illuminating spectroscopic measurements method size.

It is above-mentioned than (Im/Is) be 1.0 or more in the case where, effect of the invention is poor.

The above-mentioned peak strength from carbon can use the red-hot Discharge illuminating spectroscopy apparatus of Ma Kusi type high frequency (マーカス type high frequency グロー Fang electricity development light spectroscopy apparatus) (common name GDS, hole field make made JY-5000RF Type) measurement.

In addition, the reasons why as the concentration distribution that carbon as described above occurs in lubricating film, as described above, Anticipation is because being first derived from the oxide of the metal of metal ion or the epithelium of hydroxide in catholyte in metal It is precipitated on material, then organic acid compound is gradually precipitated.

One of preferred configuration as lubricating film, it is preferred that from the surface of lubricating film to being equivalent to lubricating film Integral thickness 1/2 depth position, the content ratio (be based on peak strength ratio) of carbon is gradually reduced.

The thickness of lubricating film is not particularly limited, but on this point effect of the invention is more preferable, and preferably 0.5 ~10 μm, more preferably 0.5~5 μm.

As one of the preferred configuration of metal material for having lubricating film, as shown in Fig. 2, being preferably capable of enumerating The metal material 100 with lubricating film of the oil reservoir 16 containing oil component is configured on lubricating film 14.By the way that oil reservoir is arranged 16, lubricity further increases.

As the oil reservoir, it is preferred to use the lube layer of the lubricating oil containing Lubrication Composition is but it is also possible to be using The antirust oil reservoir of antirust oil containing Lubrication Composition.In addition, oil reservoir is also possible to lubricating oil itself or antirust oil itself.

The adhesion amount of oil reservoir is not particularly limited, but on this point of lubricity and more preferable removability, and preferably 0.1 ~3.0g/m², more preferably 0.3~2.0g/m², more preferably 0.5~1.5g/m²。

In addition, the measurement such as surface carbon analytical equipment can be used in the measurement of adhesion amount.

The above-mentioned metal material with lubricating film shows good lubricity, and is prepared for coating process, by Usually lubricating film is easily removed using such ungrease treatment in the leading portion of chemical conversion treatment, it can be de- to being implemented The metal material surface of film process implements various chemical conversion treatments well.

That is, it is deep that deep-draw processing, pressing processing or tensioning processing etc. can be implemented for the metal material for having lubricating film Degree forming, then implements ungrease treatment, can implement the various chemical conversion treatments such as coating well.

Embodiment

Hereinafter, specifically describing the present invention for embodiment, but the present invention is not limited to these.

(clean method of wire rod and cold-rolled steel sheet (also referred to as SPC material later))

In aftermentioned Examples and Comparative Examples, the wire rod and cold-rolled steel sheet of metal are used as test film.As line Material, using by diameter 3.5, length 300mm SWRM45 from unilateral end to 100mm machining to become 3mm , implement the blank material of aftermentioned surface cleaning.In addition, being for width 120mm, length 160mm, thickness as cold-rolled steel sheet The cold-rolled steel sheet of 0.8mm uses the blank material for implementing aftermentioned surface cleaning.

When by above-mentioned wire rod and cold-rolled steel sheet in Examples and Comparative Examples in use, in order to by the oil and rubbish on surface Removal, has carried out surface cleaning to wire rod and SPC material using degreasing agent.

More particularly, by degreasing agent (Nihon Parkerizing Co., Ltd.'s (Japanese パーカライグ plants of formula meetings of ジ Application Society) fine cleaner (Off ァイ Application クリーナー) E2001 processed) 43 DEG C are warmed to, wire rod and cold-rolled steel sheet are impregnated 3 minutes, it will The oil and attachment rubbish on surface remove.Then, the degreasing agent ingredient on wire rod and cold-rolled steel sheet is rushed with the city Ping Zhong tap water It washes, the moisture on wire rod and cold-rolled steel sheet is removed by air blown.

(measuring method of adhesion amount)

The metallic element in lubricating film that is manufactured in aftermentioned Examples and Comparative Examples and organic acid compound it is attached Amount according to sequence evaluating below.

In addition, in the case where using wire rod as test film, since the epithelium amount on wire rod is micro, so with Same constituent and DC cathode electrolytic method, are precipitated identical lubricating film on SPC material with the surface treatment of wire rod, Measure the adhesion amount of each ingredient in the lubricating film.In addition, anode is using insoluble anode, (Di Nuola permanent electrode share has Limit company (ペ Le メレッ Network society) oxygen processed occurs to use DSE).

Metallic element measures metallic element with fluorescent X-ray (company's (Co., Ltd.'s リガ Network) of science ZSX Primus2 processed) Intensity, calculate adhesion amount (g/m according to by intensity and the calibration curve that constitutes of amount²).

For organic acid compound, using carbon analytical equipment (Leco Corporation (LECO society) RC412 processed) with 500 DEG C, 180 seconds Heating, making the organic acid compound being attached on surface of steel plate burning is carbon dioxide, finds out the carbon amounts of attachment.Then, according to Ratio (carbon containing ratio) of the obtained carbon in carbon amounts and organic acid compound relative to full molecular weight, calculates organic Adhesion amount (the g/m of acid compound²).In addition, test film is being not coated with oily by Examples and Comparative Examples when implementing above-mentioned measurement 2cm × 5cm × 0.8mm(thickness is cut under state) shape.In addition, using the SPC material of the surface cleaning of same size as blank Disposition measures the surface carbon amounts of blank in advance, and confirmation is zero.

(the analysis of each ingredient in lubricating film: the intensity of the organic matter from lubricating film surface to metal material surface It checks)

Depth direction from the surface of the lubricating film obtained in aftermentioned Examples and Comparative Examples to metal material Constituent analysis is according to sequence evaluating below.

As analysis method, using the red-hot electric discharge spectroscopy apparatus of Ma Kusi type high frequency, (common name GDS, hole field make institute JY-5000RF type processed), analyze the distribution of the carbon of (wire rod or cold-rolled steel sheet) from lubricating film surface to blank material.

Sputter is carried out with argon gas in the depth direction from the surface of the lubricating film obtained in Examples and Comparative Examples, According to the distinctive plasma luminescence of carbon, the intensity of each ingredient is found out.In addition, finding out lubricating film respectively in measurement The middle position of the thickness direction of the peak strength (Is) and lubricating film from carbon on surface derives from carbon The peak strength (Im) of element, calculates it than (Im/Is).

(embodiment 1)

Use calcium nitrate, 2 sodium salts of EDTA(ethylenediamine tetra-acetic acid) and deionized water, calcium fluor-complex aqueous solution is made, is connect , isostearic acid is added, pH is adjusted to 5.0 with ammonia and nitric acid, the concentration for obtaining calcium ion is 2000 mass ppm, different ten The concentration of eight alkanoic acids is that constituent is used in the DC cathode electrolysis of the embodiment 1 of 2000 mass ppm.

The graduated cylinder of 1L is elected to be treatment trough, above-mentioned DC cathode electrolysis constituent is filled, is warmed to 25 DEG C.In treatment trough Inside, SUS net is elected to be anode to be equipped with.

Groove center is being handled using the wire rod for implementing surface cleaning processing as cathode dipping, with rectifier (Co., Ltd. Takasago makes made ZX-1600LA) carry out current density 10A/dm², electricity 20C/dm²Electrolysis procedure.Due to being lower Current value, so being equipped with non-resistance galvanometer in the way of wiring, confirmation is defined electric current on one side, carries out cathode electricity on one side Solution.

Then, which is taken out from treatment trough, is cleaned with flat tomb tap water, removes moisture by air blown, Lubricating film is produced on wire rod.

Adhesion amount in lubricating film is that calcium (calcium constituent) is 0.3g/m², isostearic acid 0.2g/m².In addition, above-mentioned It is 0.11 than (Im/Is).

On the wire rod for the embodiment 1 for foring lubricating film, applies antirust oil while carrying out weight measurement (Parker is emerging Produce the emerging production of (パーカー) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 2)

Magnesium nitrate is added in deionized water to make magnesium aqueous solution, then adds azelaic acid, with ammonia and nitric acid by pH 9.0 are adjusted to, the concentration for obtaining magnesium ion is 3000 mass ppm, the direct current for the embodiment 2 that azelaic acid is 2000 mass ppm is negative Constituent is used in pole electrolysis.

Groove center is being handled using the wire rod for implementing surface cleaning processing as cathode dipping, with rectifier (Co., Ltd. Takasago makes made ZX-1600LA) carry out current density 10A/dm², electricity 50C/dm²Electrolysis procedure.Due to being lower Current value, so being equipped with non-resistance galvanometer in the way of wiring, confirmation is defined electric current on one side, carries out cathode electricity on one side Solution.

Adhesion amount in lubricating film is that magnesium (magnesium elements) are 0.6g/m², azelaic acid 0.2g/m².In addition, above-mentioned ratio It (Im/Is) is 0.11.

On the wire rod for the embodiment 2 for foring lubricating film, applies antirust oil while carrying out weight measurement (Parker is emerging Produce the emerging production of (パーカー) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 3)

Use aluminum nitrate, 3 sodium salts of NTA(nitrilotriacetic acid) and deionized water production aluminium fluor-complex aqueous solution, then add PH is adjusted to 6.0 with ammonia and nitric acid by azelaic acid, obtains that aluminum ions concentration is 3000 mass ppm, the concentration of azelaic acid is Constituent is used in the DC cathode electrolysis of the embodiment 3 of 5000 mass ppm.

The graduated cylinder of 1L is elected to be treatment trough, above-mentioned DC cathode electrolysis constituent is filled, is warmed to 30 DEG C.In treatment trough Inside, SUS net is elected to be anode to be equipped with.

Adhesion amount in lubricating film is that aluminium (aluminium element) is 0.4g/m², azelaic acid 0.3g/m².In addition, above-mentioned ratio It (Im/Is) is 0.13.

On the wire rod for the embodiment 3 for foring lubricating film, applies antirust oil while carrying out weight measurement (Parker is emerging Produce the emerging production of (パーカー) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 4)

Yttrium aqueous solution is made using yttrium nitrate and deionized water, adipic acid is then added, is adjusted to pH with ammonia and nitric acid 6.0, the concentration for obtaining ruthenium ion is 3000 mass ppm, the direct current for the embodiment 4 that the concentration of adipic acid is 5000 mass ppm is negative Constituent is used in pole electrolysis.

Groove center is being handled using the wire rod for implementing surface cleaning processing as cathode dipping, with rectifier (Co., Ltd. Takasago makes made ZX-1600LA) carry out current density 20A/dm², electricity 50C/dm²Electrolysis procedure.Due to being lower Current value, so being equipped with non-resistance galvanometer in the way of wiring, confirmation is defined electric current on one side, carries out cathode electricity on one side Solution.

Adhesion amount in lubricating film is that yttrium (yttrium) is 0.7g/m², azelaic acid 0.3g/m².In addition, above-mentioned ratio It (Im/Is) is 0.13.

On the wire rod for the embodiment 4 for foring lubricating film, applies antirust oil while carrying out weight measurement (Parker is emerging Produce the emerging production of (パーカー) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 5)

Use calcium nitrate, 2 sodium salts of EDTA(ethylenediamine tetra-acetic acid) and deionized water production calcium fluor-complex aqueous solution, then Isostearic acid is added, pH is adjusted to 6.0 with ammonia and nitric acid, the concentration for obtaining calcium ion is 3000 mass ppm, isooctadecane The concentration of acid is that constituent is used in the DC cathode electrolysis of the embodiment 5 of 5000 mass ppm.

Adhesion amount in lubricating film is that calcium (calcium constituent) is 0.2g/m², isostearic acid 0.3g/m².In addition, above-mentioned It is 0.13 than (Im/Is).

On the wire rod for the embodiment 5 for foring lubricating film, applies antirust oil while carrying out weight measurement (Parker is emerging Produce the emerging production of (パーカー) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 6)

Magnesium aqueous solution is made using magnesium acetate and deionized water, azelaic acid is then added, is adjusted to pH with ammonia and acetic acid 8.0, the concentration for obtaining magnesium ion is 5000 mass ppm, the direct current for the embodiment 6 that the concentration of azelaic acid is 5000 mass ppm is negative Constituent is used in pole electrolysis.

To the straight of the propylene container (inside dimension length 31cm, width 12.6cm, height 12.5cm) of 5L filling embodiment 6 Catholyte constituent is flowed, is warmed to 35 DEG C with hot water water proof.Insoluble sun is configured on the inside of the length direction of container Pole (Di Nuola permanent electrode limited liability company (ペ Le メレッ Network society) oxygen processed occurs to use DSE), centre configuration in a reservoir is implemented The cold-rolled steel sheet of surface cleaning processing is as cathode.Anode at a distance from cathode be 15cm, sheltered so that area ratio at It is 1/3 for annode area.

Carrying out current density with rectifier (Co., Ltd.'s takasago makes made ZX-1600LA) is 5A/dm², electricity be 100C/dm²Electrolysis procedure.

Then, which is taken out from treatment trough, is cleaned with flat tomb tap water, removes moisture by air blown, Lubricating film is produced on cold-rolled steel sheet.

Adhesion amount in lubricating film is that magnesium (magnesium elements) are 0.8g/m², azelaic acid 0.2g/m².In addition, above-mentioned ratio It (Im/Is) is 0.11.

On the cold-rolled steel sheet for the embodiment 6 for foring lubricating film, with roller coating antirust oil (the emerging production (パーカー of Parker Emerging production) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 7)

Use aluminum nitrate, 3 sodium salts of NTA(nitrilotriacetic acid) and deionized water production aluminium fluor-complex aqueous solution, then add PH is adjusted to 9.0 with ammonia and acetic acid by azelaic acid, obtains that aluminum ions concentration is 2000 mass ppm, azelaic acid is 7000 mass Constituent is used in the DC cathode electrolysis of the embodiment 7 of ppm.

To the straight of the propylene container (inside dimension length 31cm, width 12.6cm, height 12.5cm) of 5L filling embodiment 7 Catholyte constituent is flowed, is warmed to 35 DEG C with hot water water proof.Insoluble sun is configured on the inside of the length direction of container Pole (Di Nuola permanent electrode limited liability company (ペ Le メレッ Network society) oxygen processed occurs to use DSE), centre configuration in a reservoir is implemented The cold-rolled steel sheet of surface cleaning processing is as cathode.Anode at a distance from cathode be 15cm, sheltered so that area ratio at It is 1/3 for annode area.

Adhesion amount in lubricating film is that aluminium (aluminium element) is 0.2g/m², azelaic acid 0.3g/m².In addition, above-mentioned ratio It (Im/Is) is 0.13.

On the cold-rolled steel sheet for the embodiment 7 for foring lubricating film, with roller coating antirust oil (the emerging production (パーカー of Parker Emerging production) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(embodiment 8)

Yttrium aqueous solution is made using yttrium nitrate and deionized water, adipic acid is then added, is adjusted to pH with ammonia and acetic acid 9.0, the concentration for obtaining ruthenium ion is 3000 mass ppm, the DC cathode for the embodiment 8 that adipic acid is 7000 mass ppm is electrolysed Use constituent.

To the straight of the propylene container (inside dimension length 31cm, width 12.6cm, height 12.5cm) of 5L filling embodiment 8 Catholyte constituent is flowed, is warmed to 35 DEG C with hot water water proof.Insoluble sun is configured on the inside of the length direction of container Pole (Di Nuola permanent electrode limited liability company (ペ Le メレッ Network society) oxygen processed occurs to use DSE), centre configuration in a reservoir is implemented The cold-rolled steel sheet of surface cleaning processing is as cathode.Anode at a distance from cathode be 15cm, sheltered so that area ratio at It is 1/3 for annode area.

Carrying out current density with rectifier (Co., Ltd.'s takasago makes made ZX-1600LA) is 5A/dm², electricity be 20C/dm²Electrolysis procedure.

Adhesion amount in lubricating film is that yttrium (yttrium) is 0.2g/m², azelaic acid 0.5g/m².In addition, above-mentioned ratio It (Im/Is) is 0.15.

On the cold-rolled steel sheet for the embodiment 8 for foring lubricating film, with roller coating antirust oil (the emerging production (パーカー of Parker Emerging production) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(comparative example 1)

On wire rod, antirust oil (emerging production (the emerging production of パーカー) Co., Ltd. of Parker is applied while carrying out weight measurement NOX-RUST530F processed), to become 1.0g/m², oil-yielding stratum is manufactured on wire rod.

(comparative example 2)

Roller coating antirust oil (the emerging emerging production of production (パーカー of Parker) Co. Ltd. system NOX- is used on cold-rolled steel sheet RUST530F), to become 1.0g/m², oil-yielding stratum is manufactured on cold-rolled steel sheet.

(comparative example 3)

Azalaic acid magnesium is added in deionized water, the constituent of comparative example 3 is produced.The constituent is gonorrhoea, holds Easily settled dispersion liquid.

Using it, by constituent dip coating to wire rod and cold-rolled steel sheet, so that azalaic acid magnesium becomes 2g/m², small Heart is dry.After the drying, it is integrally white, but scattered can sees irregular.In addition, be easy to be contemplated to, whenever disposition wire rod and Cold-rolled steel sheet, white powder will fall off, may be poor with the adhesion of wire rod or cold-rolled steel sheet.In this case, carefully Apply antirust oil (the emerging emerging production of production (パーカー of Parker) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

In addition, above embodiment is equivalently employed without the form for implementing catholyte.

(comparative example 4)

Calcium stearate is added in deionized water, the constituent of comparative example 4 is produced.The constituent is gonorrhoea, is easy The dispersion liquid of sedimentation.

Using it, by constituent dip coating to wire rod and cold-rolled steel sheet, so that calcium stearate becomes 2g/m², carefully Ground is dry.After the drying, it is integrally white, but scattered can sees irregular.In addition, be easy to be contemplated to, whenever disposition wire rod and cold Rolled steel plate, white powder will fall off, may be poor with the adhesion of wire rod or cold-rolled steel sheet.In this case, it carefully applies Antirust oil (the emerging emerging production of production (パーカー of Parker) Co. Ltd. system NOX-RUST530F), to become 1.0g/m²。

(comparative example 5)

The graduated cylinder of 1L is elected to be treatment trough, fills patent document 1(special open 2000-144494) embodiment 1 composition Object is heated to 80 DEG C.In the inside for the treatment of trough, SUS net is elected to be anode to be equipped with.

Modulation contains Nihon Parkerizing Co., Ltd. (Japanese パー documented by 3 mass % patent documents 1 at normal temperature カライジ Application グ (strain)) colloidal titanium (U ロイダ Le チタ Application) class surface conditioner (プレパレ Application Z) processed aqueous solution, After the wire rod that will implement surface cleaning processing impregnates 1 minute, in processing groove center using wire rod as cathode rectifier (strain formula Commercial firm's takasago makes made ZX-1600LA) progresss current density is 20A/dm², electricity 50C/dm²Electrolysis procedure.Due to It is lower current value, so configuring non-resistance galvanometer in the way of wiring, enters while confirming is defined electric current Row catholyte.

Then, which is taken out from treatment trough, is cleaned with flat tomb tap water, removes moisture by air blown, Zinc phosphate coat is produced on wire rod.

The adhesion amount of zinc phosphate coat is to be dissolved zinc phosphate coat with the chromic acid aqueous solution for being heated to 75 DEG C to remove, according to Weight difference before and after it calculates adhesion amount.The adhesion amount is 3.5g/m as trbasic zinc phosphate²。

Then, antirust oil (the emerging emerging production of production (パーカー of Parker) Co. Ltd. system NOX- is applied on the wire rod RUST530F), to become 1.0g/m²。

(comparative example 6)

By the operation same with comparative example 5, obtaining having as trbasic zinc phosphate is 3.5g/m²Zinc phosphate coat line Material.

Then, which is being heated to 80 DEG C of response type soap treatment fluid ((Japan of Nihon Parkerizing Co., Ltd. パーカライジ Application グ Co., Ltd.) パルー Block 235,70g/L processed) middle dipping 3 minutes.Pass through what is occurred in this operation The reaction of response type soap processing, above-mentioned trbasic zinc phosphate dissolve slightly and become 3.0g/m².Also, the band of metallic soaps and liquid The total amount of the unreacted soap of output is 3.0g/m²。

Using the wire rod obtained in above-described embodiment and comparative example and cold-rolled steel sheet, implement evaluation test below.

In above-described embodiment and comparative example as test film and using wire rod in the case where implements lubricity below and comments Valence (its 1) implements lubricity evaluation (its 2) below, evaluation lubrication as test film and using cold-rolled steel sheet Property.

(lubricity evaluates (its 1): the drawing evaluation of wire rod)

It is 3mm by the wire rod test film obtained in Examples and Comparative ExamplesEnd be inserted into supersteel molding jig 3.05mmIn (Fuji's mold (Tomita scholar ダイス) system).Then, with accurate universal testing machine (Shimadzu Scisakusho Ltd's system AG-X wire rod is fixed in upper grip portion), and supersteel molding jig is fixed on the apparatus.Make upper grip portion with 1m/min Speed be moved upward, make the wire rod pass through mold in, carry out drawing processing.When with personal computer monitoring in mold Drawing load.

On the basis of the value of the drawing load of comparative example 1, the size of the drawing load in each Examples and Comparative Examples is pressed It is evaluated according to evaluation criteria below.In addition, comparative example 1 is evaluated as "×".

"×": its big situation of or drawing load ratio identical as the drawing load of comparative example 1

"○": drawing load smaller than the drawing load of comparative example 1, for comparative example 1 more than half the case where

" ◎ ": the situation smaller than the half of the drawing load of comparative example 1.

In addition, dregs preferably do not occur in the entrance of mold in drawing.By in the entrance of mold, there is no slags The case where dregs, is evaluated as dregs and inhibition "○" occurs, and dregs will be evaluated as the case where dregs have occurred in the entrance of mold Inhibition "×".

(lubricity evaluates (its 2): the drawing process evaluation of SPC material)

Punching operation will be carried out to become diameter 110mm in cold-rolled steel sheet test film obtained in Examples and Comparative Examples, Produce deep-draw processing test film.Then, using the steel plate, (mechanism is tested in Co., Ltd. Tokyo with high speed deep drawing test machine DHV-20/650-8001 deep-draw processing) is carried out.The summary of the high speed deep drawing test machine is indicated in Fig. 3.Such as Fig. 3 (A) institute Show, high speed deep drawing test machine 18 has the formed punch 20 for being applied load on the direction of black arrow and supports the mould of test film 30 Son 22~28.Mould 24 and mould 28 are fixed, by from the direction of white arrow on mould 22 and mould 26 used load (pleat Wrinkle extrusion load), the both ends of test film 30 be fixed between mould 22 and mould 24 and mould 26 and mould 28 it Between.After test film 30 is installed in testing machine 18, as shown in Fig. 3 (B), acted on formed punch 20 from the direction of black arrow Load, the scanning fold extrusion load that test film 30 is fixed, inspection test sheet 30 reach the load of fracture.

On the basis of the value of the fold extrusion load of comparative example 2, each embodiment and ratio are evaluated according to evaluation criteria below Compared with the size of the fold extrusion load in example.In addition, comparative example 2 is evaluated as "×".

"×": or situation that fold extrusion load smaller identical as the fold extrusion load of comparative example 2

"○": it is bigger than the fold extrusion load of comparative example 2, less than 2 times of the fold extrusion load of comparative example 2 the case where

" ◎ ": the case where the 2 times or more of the fold extrusion load of comparative example 2.

Use the wire rod with lubricating film that manufactures respectively about Examples 1 to 5, comparative example 5 and 6 as test film, Use the cold-rolled steel sheet with lubricating film manufactured respectively about embodiment 6~8 as test film, implements chemical conversion below Evaluate (its 1) and chemical conversion property evaluation (its 2).

(chemical conversion property evaluation (its 1): being confirmed by trbasic zinc phosphate processing bring chemical conversion property and character)

According to sequence below, the surface treatment that test film implementation is relatively mostly used as the base treatment of coating.

(1) by degreasing agent (Nihon Parkerizing Co., Ltd. (Japanese パーカライジ Application グ Co., Ltd.) fine filtering processed Clear device (Off ァイ Application クリーナー) E2001) 43 DEG C are warmed to, each test film is impregnated 3 minutes, by the surface of test film Lubricating film and oil reservoir remove.

(2) the degreasing agent ingredient on test film is washed off with the city Ping Zhong tap water.

It (3) will be for the surface conditioner of 2g/L (Nihon Parkerizing Co., Ltd.'s (Japanese パーカライグ plants of formulas of ジ Application Commercial firm) プレパレ Application X processed) it is adjusted with flat tomb tap water, test film is impregnated 30 seconds in surface adjustment liquid.

(4) test film is taken out from surface adjustment liquid, in the state that adjustment liquid is attached on test film on surface, will be tried It tests piece and is impregnated into and be adjusted to 35 DEG C of trbasic zinc phosphate treatment fluid (Nihon Parkerizing Co., Ltd. (Japanese パーカライジ Application グ Co., Ltd.) パ Le ボ Application De SX35 processed, free acidity 0.7pt, promoter concentration (set society's promotor 131 as 3.5pt), Shake within 2 minutes.

(5) after trbasic zinc phosphate processing, test film is cleaned with flat tomb tap water, then is cleaned with deionized water.Then, with sky Gas blowout, which is blown, removes moisture.

The Evaluation for Uniformity of zinc phosphate coat be visually judgement, form and aspect uniformly and without it is irregular, be not short of the case where Lower is " ◎ ", without visually it is lower it is irregular in the case where for "○", in the case where having irregular due to bringing coating irregular, so For "×".

(chemical conversion property evaluation (its 2): being confirmed by metal oxide treated bring chemical conversion property and character)

As the base treatment of coating, at the surface for implementing the metal oxide of extension to test film according to sequence below Reason.

(3) test film is impregnated into and is adjusted to treatment fluid (the rapids smart strain formula meeting of Japanese pa card of 45 DEG C of metal oxide Society (Japanese パーカライジ Application グ Co., Ltd.) パルシー De 1500, pH4.0 processed) in, shake within 2 minutes.

(4) after treatment, test film is cleaned with flat tomb tap water, then is cleaned with deionized water.Then, air blown is used Moisture is removed.

The Evaluation for Uniformity of metal oxide epithelium is visually judgement, form and aspect uniformly and without it is irregular, be not short of In the case of be " ◎ ", without visually it is lower it is irregular in the case where for "○", in the case where having irregular due to bringing coating irregular, So being "×".

Hereinafter, evaluation result is summarized expression in table 1.

In table 1, than deriving from carbon on the surface for the side opposite with metal material that (Is/Im) refers to lubricating film The peak strength (Is) of element with the surface of the side opposite with metal material away from lubricating film is to be equivalent to lubricating film The ratio (Im/Is) of the peak strength (Im) from carbon of the middle position of 1/2 depth of integral thickness.

The ratio (Is/Im) of the lubricating film in comparative example 6 in table 1 refers to the skin formed by response type metallic soaps processing Ratio (Is/Im) in film, does not account for zinc phosphate coat.

In addition, " metallic element " column of the comparative example 5 and 6 in table 1 refers to the amount of trbasic zinc phosphate, " organic acid compound " refers to Pass through the amount for the epithelium that response type metallic soaps processing is formed.

In addition, "-", which refers to, to be not carried out in " lubricity evaluation " column in table 1.

As shown in table 1, shown well by using the lubricating film that the catholyte of constituent of the invention is handled Lubricity and degreasing after chemical conversion.

On the other hand, only configure oil reservoir comparative example 1 and 2, without implement catholyte handle comparative example 3 and 4, with And be equivalent in the comparative example 5 and 6 of embodiment of patent document 1, do not obtain desired effect.

Description of symbols

10,100 metal material with lubricating film

12 metal materials

14 lubricating films

16 oil reservoirs

18 high speed deep drawing test machines

20 formed punches

22,24,26,28 mould

30 test films.

Claims

1. a kind of DC cathode electrolysis constituent, which is characterized in that contain:

From by it is more than the divalent in addition to zinc ion typical metal ion and the group that constitutes of rare earth element ion in select at least 1 metal ion species or its fluor-complex (A)；

The organic acid compound (B) of straight chain alkylene group in the molecule comprising carboxyl and 4 or more carbon number；With

Water (C)；

Above-mentioned metal ion or its fluor-complex (A) include from by magnesium ion, calcium ion, aluminium ion, ruthenium ion and lanthanum ion At least one kind of metal ion or its fluor-complex selected in the group of composition.

2. DC cathode electrolysis constituent as described in claim 1, which is characterized in that

Above-mentioned organic acid compound (B) include comprising 4 or more carbon number straight chain alkylene group aliphatic monocarboxylic acid or comprising carbon The aliphatic dicarboxylic acid of the straight chain alkylene group of 4 or more number.

3. DC cathode electrolysis constituent as claimed in claim 1 or 2, which is characterized in that

PH is 3.5~12.5.

4. a kind of manufacturing method of the metal material with lubricating film, which is characterized in that

Have following process: metal material is impregnated into DC cathode electrolysis composition according to any one of claims 1 to 3 In object, using above-mentioned metal material as cathode, implements to handle using the catholyte of direct current, be formed on above-mentioned metal material surface Lubricating film.

5. a kind of metal material with lubricating film, which is characterized in that

It is manufactured by the manufacturing method of the metal material as claimed in claim 4 with lubricating film.

6. a kind of metal material with lubricating film has the lubrication of metal material and configuration on above-mentioned metal material surface Epithelium, which is characterized in that

Above-mentioned lubricating film includes:

From by it is more than the divalent in addition to zinc ion typical metal elements and the group that constitutes of rare earth element ion in select at least 1 kind of metallic element；

The organic acid compound and/or its salt of straight chain alkylene group in the molecule comprising carboxyl and 4 or more carbon number；

Typical metal elements more than aforementioned divalent include beryllium, magnesium, calcium, strontium, barium, radium, cadmium, mercury, aluminium, gallium, indium, thallium, germanium, tin, Lead, antimony, bismuth, polonium；

Using red-hot Discharge illuminating spectroscopic measurements method, the side opposite with above-mentioned metal material from above-mentioned lubricating film Surface towards in the analysis of the depth direction to above-mentioned lubricating film of above-mentioned metal material side, above-mentioned lubricating film with it is above-mentioned The peak strength (Is) from carbon on the surface of the opposite side of metal material, with away from above-mentioned lubricating film with it is above-mentioned The surface of the opposite side of metal material is equivalent to the middle position of 1/2 depth of the integral thickness of above-mentioned lubricating film From carbon peak strength (Im) ratio (Im/Is) less than 1.0.

7. having the metal material of lubricating film as claimed in claim 6, which is characterized in that

The oil reservoir containing oil component is also equipped on above-mentioned lubricating film.