CN106133201A

CN106133201A - DC cathode electrolysis constituent, with the metal material of lubricating film and manufacture method thereof

Info

Publication number: CN106133201A
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: 2016-11-16
Anticipated expiration: 2035-02-16
Also published as: KR101815412B1; TW201536963A; KR20160111969A; JP6211678B2; US20170073831A1; WO2015125737A1; CN106133201B; JPWO2015125737A1; MX2016010837A

Abstract

The present invention provides a kind of DC cathode electrolysis constituent that can form the good metal material with lubricating film of the chemical conversion after lubricity and defat.The DC cathode electrolysis constituent of the present invention contains: at least one metal ion selected from the group being made up of typical metal ion (but except by zinc ion) more than divalent and rare earth element ion or its fluor-complex (A)；The organic acid compound (B) of the straight chain alkylene group of carboxyl and carbon number more than 4 is comprised in intramolecular；Water (C).

Description

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

Technical field

The present invention relates to DC cathode electrolysis constituent, particularly to the metal ion containing regulation and organic acid chemical combination The DC cathode electrolysis constituent of thing.

Moreover, it relates to use the metal material with lubricating film that DC cathode electrolysis constituent obtains And manufacture method.

Background technology

Metal material is used in many structures.Such as, iron type materials is from as the plate of base material, line, rod, by squeezing Pressure, drawing, cutting, die-cut etc. pressure are made processing and manufacturing and are gone out the part of structure, by with welding, bonding joint, are assembled into big The shape of body.Then, through antirust treatment, various application (coating process), the goods in view of design are become, according to circumstances Put into electronic component or inner body dispatches from the factory.

Pressure at such material is made needs lubricity in processing, it is proposed that various technology.Such as, in patent documentation 1, As the forming method of lubricating film, disclose a kind of electrolyte used containing zinc ion, phosphate ion and nitrate ion and enter Row catholyte forms chemical conversion epithelium, then makes it with water class or the method for lubricant contact of oils.

Patent documentation 1: Japanese Unexamined Patent Publication 2000-144494 publication.

On the other hand, in recent years, it is desirable to various chemical conversion treatment can be easily implemented with after by metal material processing.More Say, it is desirable to after there is the metal material processing of lubricating film, by lubricating film demoulding, and can be easily implemented with each body Plant chemical conversion treatment (such as, zinc phosphate process, metal oxide treated etc.).That is, for lubricating film, it is desirable to lubricity and demoulding Taking into account under the high level of the chemical conversion after process.Additionally, especially with regard to demoulding process, due to be for coating process prepare , it is desirable to be able to the leading portion being used in chemical conversion treatment generally uses such ungrease treatment to be easily implemented with.

The present inventors formed in the method implemented described in patent documentation 1 lubricating film, to its characteristic (lubricity and Chemical conversion after defat) study after find, after carrying out ungrease treatment formed chemical conversion epithelium in occur irregular, lubricity Insufficient with taking into account of the chemical conversion after defat.Particularly, in the scheme of patent documentation 1, owing to being formed on the metal material Zinc phosphate coat and/or response type soap epithelium can not remove with common ungrease treatment and remain, so implementing thereafter Chemical conversion treatment is carried out the most well.

Summary of the invention

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

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

The present inventors is specialized in about the problems referred to above, it was found that comprised the metal of regulation by use The DC cathode electrolysis constituent of the organic acid compound of ion or its fluor-complex and regulation implements catholyte, can obtain To the lubricating film presenting desired characteristic.

I.e. find, be capable of above-mentioned purpose by following structure.

(1) a kind of DC cathode electrolysis constituent, it is characterised in that contain: from by typical metal ion more than divalent But at least one metal ion selected in the group that (except zinc ion) and rare earth element ion are constituted or its fluor-complex (A)；The organic acid compound (B) of the straight chain alkylene group of carboxyl and carbon number more than 4 is comprised in intramolecular；With water (C).

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

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

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

(5) manufacture method of a kind of metal material with lubricating film, possesses and metal material is impregnated into (1)～(4) In DC cathode electrolysis constituent described in any one, implement to use at the catholyte of direct current with metal material for negative electrode Manage, formed on metal material surface the operation of lubricating film.

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

(7) a kind of metal material with lubricating film, possesses metal material and the profit being arranged on metal material surface Sliding epithelium, lubricating film comprises: from by typical metal elements (but except by zinc element) more than divalent and rare earth element from At least one metallic element selected in the group that son is constituted；Having of the straight chain alkylene group comprising carboxyl and carbon number more than 4 in intramolecular Machine acid compound and/or its salt；Using red-hot Discharge illuminating spectroscopic measurements method, contrary with metal material from lubricating film The surface of side towards metal material side in the analysis of the depth direction of lubricating film, lubricating film and metal material The peak strength (Is) deriving from carbon on the surface of contrary side with away from lubricating film with metal material contrary one The peak value deriving from carbon that the surface of side is equivalent to the middle position of the degree of depth of the 1/2 of the integral thickness of lubricating film is strong The ratio (Im/Is) of degree (Im) is less than 1.0.

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

In accordance with the invention it is possible to provide a kind of can be formed the chemical conversion after lubricity and defat good with lubrication skin The DC cathode electrolysis constituent of the metal material of film.

Additionally, in accordance with the present invention it is further possible to provide a kind of use DC cathode electrolysis constituent with lubricating film Metal material manufacture method and with the metal material of lubricating film.

Accompanying drawing explanation

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

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

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

Detailed description of the invention

Hereinafter, to the DC cathode electrolysis constituent (DC cathode electrolysis treatment fluid) of the present invention, with lubrication skin Metal material and the manufacture method thereof of film describe in detail.It addition, the figure in the present invention is schematic diagram, the relation etc. of the thickness of each layer Might not be consistent with reality.

As one of inventive feature point, can enumerate and use the metal ion containing regulation or its network as described above The DC cathode electrolysis of the organic acid compound of compound and regulation constituent implements catholyte this point.

First, generally have by catholyte make metal precipitate on treated object, be referred to as coating surface process.Right This, in the present invention, dispose, using treated object, the metal ion or its being not easy to separate out as metal even if using as negative electrode Fluor-complex is as the composition in constituent.The metal ion used i.e., in the present invention or its fluor-complex are difficult to make at water apoplexy due to endogenous wind Reduce for metal, easily become the hydroxide containing this metal ion, hydrous oxide and/or oxide.

In the present invention, the film-forming method by DC cathode electrolysis is used.First, if implementing catholyte, then lead to Cross the electrophoresis of each metal ion or its fluor-complex, occur metal ion or its fluor-complex attached to the metal material as treated object Near denseization.Now, as the reduction reaction of the electronics consumed from treated object release, there is hydrionic consumption and hydroxide The increase etc. of thing ion.Such as, if there is the situation that the electricity of water decomposes, then from the metal material surface as treated object Upper generation hydrogen, is promoted so the pH on metal material surface rises.As a result, metal ion or its fluor-complex of denseization is formed Insoluble salt (oxide, hydroxide or hydrate), separates out on metal material surface.Such metal ion or its network The region that compound separates out is processed by the demoulding generally using such ungrease treatment etc. and easily removes, it is possible to be easily implemented with it After chemical conversion treatment.

On the other hand, owing to organic acid compound has carboxyl, if so will from metal material away from, carry out electrophoresis. Therefore, organic acid compound is difficult on metal material surface separate out, and particularly, the highest display of pH near metal material is the strongest Ionic, so this phenomenon becomes more notable.Therefore, at the catholyte initial stage, organic acid compound is difficult at metal material Separate out on surface, along with electricity decomposes progress, organic acid compound gradually form metal ion or its fluor-complex, containing this metal from The oxide of son, hydroxide etc. and salt, it may be considered that on metal material surface, separate out organic acid compound and metal ion Complex salt separate out.That is, organic acid compound is at the exposing surface (table of the side contrary with metal material side of lubricating film Face) side is further concentrated.Therefore, on the surface of lubricating film, there is the organic acid compound that more lubrication property is good, Good lubricity can be played.

As above, the water class constituent of metal ion or its fluor-complex and organic acid compound it is contaminated with by use Carry out DC cathode electrolysis, the increase of the hydroxide ion concentration on generation metal material surface, metal ion and organic acid The sedimentation equilibrium skew of compound, lubricating film separates out.The forming process of such lubricating film and conventional lubricating film Forming process is the most different.

If it addition, use this constituent, then need not when manufacturing lubricating film implement high-temperature process, and with 1 Operation completes to process, so being preferred at payable productive aspect.Even if additionally, because formed lubricating film its Thinner thickness also can obtain desired effect, so being preferred becoming present aspect and productive aspect.

Hereinafter, first to the various compositions constituting DC cathode electrolysis constituent (the most also list is 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 using constituent The manufacture method having the metal material of lubricating film describes in detail.

In constituent, comprise the typical metal ion (but by except zinc ion) more than divalent and rare earth element ion At least one metal ion selected in the group constituted or its fluor-complex (A) (after, as comprising both concept also referred to as " gold Belong to ion (A) ").This metal ion (A) becomes metal-oxide, metal hydroxides or has with described later when catholyte The fluor-complex of machine acid compound (B), for constituting the composition of lubricating film.

As typical metal ion (ion 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 the 2nd race of phase table, the ion of the element of the 12nd race of the periodic chart such as cadmium, hydrargyrum (it addition, except zinc ion), the ion of the element of the belonging to group 13 of periodic table of aluminum, gallium, indium, thallium etc., the periodic chart such as germanium, stannum, lead The ion of the element of the 14th race, the ion of the element of periodic chart the 15th race of antimony, bismuth etc., the element of the 16th race of the periodic charts such as polonium Ion.

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

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

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

It addition, metal ion (A) both can only use a kind, it is also possible to and with 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 comprise chelating agen (chelating agent).It addition, in chelating agen, do not contain organic acid compound described later (B).

As chelating agen, as long as have the function of above-mentioned metal ion-chelant, the effect not damaging the present invention, just Can use.As chelating agen, it is possible to use the organic acid such as gluconic acid, citric acid, succinic acid and salt thereof, organic phosphorus compound, The aminopolycanboxylic acid of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) etc. or its salt etc..Wherein, the present invention effect more The on this point of good, preferably aminopolycanboxylic acid or its salt.Alternatively, it is also possible to use the condensed phosphate conducts such as sodium tripolyphosphate Chelating agen, but due to easily carry out salt formation with metal ion, control more difficult, it is preferred that do not wrap in constituent Contain.

So-called aminopolycanboxylic acid, is the general name of the chelating agen in the molecule with amino and multiple carboxyl.Specifically, may be used To enumerate EDTA(ethylenediaminetetraacetic acid), HEDTA(hydroxyethylethylene diamine tri-acetic acid), NTA(nitrilotriacetic acid), the sub-second of DTPA(bis- Base pentaacetic acid), TTHA(triethylenetetraaminehexaacetic acid) etc..Additionally, the kind of the salt of aminopolycanboxylic acid is not by especially Limit, the ammonium salt of foregoing illustrative compound, sodium salt, potassium salt etc. can be enumerated.

The method supplying above-mentioned metal ion or its fluor-complex in constituent is not specially limited, and can enumerate and will contain Have above-mentioned metal ion salt (such as, carbonate, bicarbonate, acetate, formate, nitrate, sulfate, borate), The inorganic constituentss such as oxide, hydroxide, halogenide (such as fluoride) or the fluor-complex containing above-mentioned metal ion are (organic Fluor-complex) etc. in water add method.It addition, during by the metal material length with lubricating film in the case of keeping, Or in the case of the metal material with lubricating film is taken care of in high temperature and humidity environment, in order to suppress the generation of rust, preferably Be suppression the chloride use to constituent.

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

It addition, in the case of using two or more metal ion (A), the preferably total concentration of metal ion (A) is In above-mentioned scope.

Additionally, in the case of the fluor-complex using metal ion, the metal ion preferably contained in fluor-complex In amount is above-mentioned scope.

Organic acid compound (B) is the compound of the straight chain alkylene group comprising carboxyl and carbon number more than 4 in intramolecular.This organic acid Compound (B) interacts with above-mentioned metal ion (A) via carboxyl and forms fluor-complex, is taken in lubricating film.Have Hydrocarbon skeleton in machine acid compound (B) contributes to the imparting of lubricity.

Comprising carboxyl in organic acid compound (B), the quantity of carboxyl is not particularly limited.It addition, the present invention's The on this point that effect being more preferable, it may be preferred to ground use has the monocarboxylic acid of 1 carboxyl, has the dicarboxylic acids of two carboxyls.

The straight chain alkylene group of carbon number more than 4 is comprised in organic acid compound (B).This straight chain alkylene group, refers to following The base that represents of formula (1).N represents the integer of more than 4.

Formula (1) *-(CH₂)_n-*

N represents the integer of more than 4.Wherein, the effect of the present invention is more preferable on this point, preferably 4～17, more preferably 4～8.It addition, the straight chain in alkylene is the longest, being closer to higher fatty acids, lubricity becomes higher.

It addition, in above-mentioned formula, * represents binding site.

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

［ changing 1 ］

R-COOH formula (1)

HOOC-L-COOH formula (2).

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

It addition, as abovementioned alkyl, as long as the straight chain alkylene group comprising carbon number more than 4 is the most permissible as part structure, example As, as the monocarboxylic preferred configuration of aliphatic represented by formula (1), the change represented by below formula (1-1) can be enumerated Compound.

Formula (1-1) R₁-L-COOH

R₁Represent alkyl.L represents the straight chain alkylene group of carbon number more than 4.By R₁The alkyl represented both can be straight-chain, it is also possible to It it is branch's chain.R₁In the total of carbon number be not particularly limited, but it is preferred that R₁In carbon number and the conjunction of carbon number in L It is calculated as above-mentioned scope (4～18).

The carbon number of the alkylene represented by L preferably more than 4, more preferably 4～17, more preferably 4～8.

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

As aliphatic monocarboxylic acid, can enumerate such as caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, dodecylic acid, 14 Alkanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoid acid etc..

As aliphatic dicarboxylic acid, such as adipic acid (adipic acid), 1,5-pentanedicarboxylic acid. (jambulol), suberic acid (cork can be enumerated Acid), Azelaic Acid (azelaic acid), decanedioic acid (sebacic acid), heneicosanedioic acid, dodecanedioic acid, tridecandioic acid (Brazil base Acid), hexadecandioic acid (hexadecane diacid), octadecane diacid etc..

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

It addition, in the case of using two or more organic acid compound (B), the preferably conjunction of organic acid compound (B) In meter concentration is above-mentioned scope.

In constituent, contain water as solvent.

The amount of the water (C) in constituent is not particularly limited, but effect good in the property disposed, the present invention is more preferable On this point, it is preferably more than 65 mass % relative to constituent all-mass, more than more preferably 75 mass %.The upper limit It is not particularly limited, but is that the situation of below 99 mass % is more.

Mentioned component (metal ion or its fluor-complex (A), organic acid compound (B), water (C)) can also be comprised in constituent Other compositions in addition.

Such as, constituent can also additionally add above-mentioned chelating agen.

The pH of the constituent comprising mentioned component is not particularly limited, but the effect of the present invention is more preferable on this point, Preferably 3.5～12.5, more preferably 4.0～10.0.Additionally, the DC cathode electrolysis of the present invention is not susceptible to metal material The corrosion of material, but in the case of such as implementing the washing of metal material after catholyte, although it is a small amount of, but can form The removal of thing, the pH of constituent is the lowest, is more likely to occur the material corrosion in the corrosion of equipment or washing step.Additionally, such as Fruit remains as mixed component on the metal material, then be also possible to when steel keeping manifest harmful effect.If it is considered that These, then the pH of constituent is particularly preferably 6.0～9.0.

It addition, in the adjustment of the pH of constituent, it is possible to use known acid (hydrochloric acid, nitric acid, formic acid, acetic acid, sulfonic acid, Fluoric acid etc.) and/or alkali (sodium compound, potassium compound, ammonia, amines etc.).

The manufacture method of above-mentioned constituent is not specially limited, and can use known method.For example, it is possible to enumerate by Compound and organic acid compound (B) containing above-mentioned metal ion (A) add in water (C), the method for enforcement stir process Deng.

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

Hereinafter, the manufacture method with the metal material of lubricating film using above-mentioned constituent is described in detail.

Manufacture method with the metal material of lubricating film possesses following operation: metal material is impregnated into above-mentioned direct current In catholyte constituent, with metal material as negative electrode, implement to use the catholyte of direct current to process, at metal material surface Upper formation lubricating film.By implementing this operation, it is possible to obtain the lubricating film that one-tenth described later is grouped on the metal material.

The kind of the metal material used in this operation is not particularly limited, such as, can use cold-rolled steel sheet (SPC Material), hot rolled steel plate (SPH material), ordinary construction rolled steel (SS material), carbon steel (SC material), various steel alloy, rustless steel, Al Or its alloy, Mg or its alloy, Cu or its alloy, Zn or its alloy, Ni base alloy, Co base alloy etc..Additionally, about metal material The shape of material, in addition to tabular, it is also possible to being coiled type, bar-shaped, banding, tubulose, casting forged article, bearing etc., its shape does not has It is specially limited.

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

As long as the method for catholyte uses the metal material as treated object to be that negative electrode is the most permissible, do not limited especially System, can use known method.Generally, employing makes metal material be immersed in constituent, execute between insoluble anode Alive method.As insoluble electrode, it is possible to use platinum electrode, stainless steel electrode, lead electrode etc..

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

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

The temperature of constituent is not particularly limited, but lubricating film efficiently separates out on this point, preferably It is 15～40 DEG C, more preferably 20～35 DEG C.As described above, unlike the prior art, need not group in the present invention Thing is become to maintain high temperature.It addition, the temperature of constituent can also change according to the cycling hot of pump or the ambient atmos in summer.

After catholyte processes, metal material is taken out from constituent, as required, it is also possible to implement to use water to clean Matting.

Additionally, after a washing process, can also implement to impose the drying process of dried as required.

As it is shown in figure 1, the metal material 10 with lubricating film obtained by said method possesses metal material 12 and configuration Lubricating film 14 in its surface.

The kind of metal material 12 is as described above.

Lubricating film is the epithelium separated out by implementing catholyte to process in above-mentioned constituent.At lubricating film In, comprise and select from the group being made up of typical metal elements (except wherein by zinc element) more than divalent and rare earth element At least one metallic element and comprise in intramolecular carboxyl and carbon number more than 4 straight chain alkylene group organic acid compound and/ Or its salt.

The element of the metal ion that the above-mentioned metallic element comprised in lubricating film is derived from constituent.Metallic element Kind can enumerate in above-mentioned metal ion each metallic element of explanation.

It addition, in lubricating film, the existing forms of metallic element is not specially limited, such as, can enumerate metal Oxide, the form such as hydroxide of metal.

The amount of the metallic element in lubricating film is not particularly limited, but in the more preferable this point of effect of the present invention On, preferably 0.05g/m²Above, more preferably 0.1～5g/m², more preferably 0.1～3g/m²。

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

Organic acid compound and the amount of salt thereof in lubricating film are not particularly limited, but in the effect of the present invention The on this point of more preferably, preferably 0.05～3g/m², more preferably 0.1～1g/m²。

It addition, in the case of the salt of organic acid compound, only the part of organic acid compound is by above-mentioned amount Calculating uses.

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

More particularly, as it is shown in figure 1, the peak value deriving from carbon at the surface location 14A of lubricating film 14 is strong The ratio (Im/Is) of the peak strength (Im) deriving from carbon at the centre position 14B of degree (Is) and lubricating film 14 less than 1.0.That is, peak strength (Is) is bigger than peak strength (Im).It addition, the peak value deriving from carbon at surface location 14A is strong Degree (Is), refers to the peak deriving from carbon obtained by red-hot Discharge illuminating spectroscopic measurements method on the surface of lubricating film 14 The size of value.Additionally, the peak strength (Is) deriving from carbon at so-called centre position 14B, refer to from lubricating film 14 The surface (surface location 14A) of the side contrary with metal material 12 side towards metal material 12 side, be equivalent to lubricating film (in other words, the cross-sectional area of the middle position of the thickness direction of lubricating film 14, position of the degree of depth of the 1/2 of the integral thickness of 14 Territory) in the size of the peak value deriving from carbon obtained by red-hot Discharge illuminating spectroscopic measurements method.

Above-mentioned be more than 1.0 than (Im/Is) in the case of, the effect of the present invention is poor.

The above-mentioned peak strength deriving from carbon, can use Ma Kusi type high frequency red-hot Discharge illuminating spectroscopy apparatus (マカス type high frequency グロ give out light spectroscopy apparatus) (common name GDS, hole field makes made JY-5000RF Type) measure.

It addition, as the reason occurring the concentration of carbon as described above to be distributed in lubricating film, as described above, Anticipation is because, and is first derived from the oxide of the metal of metal ion or the epithelium of hydroxide when catholyte at metal Separating out on material, then organic acid compound gradually separates out.

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 the position of the degree of depth, the content ratio of carbon (based on peak strength than) be gradually reduced.

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

As one of preferred configuration of metal material with lubricating film, as in figure 2 it is shown, be preferably capable of enumerating The metal material 100 with lubricating film of oil reservoir 16 containing oil component it is configured with on lubricating film 14.By arranging oil reservoir 16, lubricity improves further.

As this oil reservoir, it is preferred to use the lube layer of the lubricating oil containing Lubrication Composition but it also may be to use The antirust oil reservoir of the antirust oil containing Lubrication Composition.It addition, oil reservoir can also be lubricating oil itself or antirust oil itself.

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

It addition, the measurement of adhesion amount can use surface carbon analytical equipment etc. to measure.

The above-mentioned metal material with lubricating film manifests good lubricity, and prepares for coating process, by The generally leading portion in chemical conversion treatment uses such ungrease treatment easily to be removed by lubricating film, it is possible to de-to being implemented The metal material surface that film processes implements various chemical conversion treatment well.

That is, for the metal material with lubricating film, it is possible to implement deep-draw processing, flatten processing or stretch-draw processing etc. deeply Degree forming, is then carried out ungrease treatment, it is possible to implement the various chemical conversion treatments such as application well.

Embodiment

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

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

In embodiment described later and comparative example, use wire rod and the cold-rolled steel sheet of metal as test film.As wire rod, make With by diameter 3.5, length 300mm SWRM45 from unilateral end to 100mm machining to become 3mm, implement The base material of surface cleaning described later.Additionally, as cold-rolled steel sheet, for width 120mm, length 160mm, thickness 0.8mm Cold-rolled steel sheet, uses the base material implementing surface cleaning described later.

When above-mentioned wire rod and cold-rolled steel sheet are used in embodiment and comparative example, in order to the oil on surface is divided and rubbish Remove, use degreasing agent that wire rod and SPC material have been carried out surface cleaning.

More particularly, by degreasing agent (Nihon Parkerizing Co., Ltd.'s (Japan's パカライジ Application グ strain formula meeting Society) fine cleaner processed (Off ァイ Application Network リ Na) E2001) it is warmed to 43 DEG C, wire rod and cold-rolled steel sheet are impregnated 3 minutes, will The oil on surface divides and adheres to rubbish removing.Then, with flat city tap water, the degreasing agent composition on wire rod and cold-rolled steel sheet is rushed Wash, the moisture on wire rod and cold-rolled steel sheet is removed by air blown.

(measuring method of adhesion amount)

Metallic element in the lubricating film manufactured in embodiment described later and comparative example and the adhesion amount of organic acid compound According to following sequence evaluating.

It addition, in the case of using wire rod as test film, owing to the epithelium amount on wire rod is trace, so using Process equal constituent and DC cathode electrolytic method with the surface of wire rod, make identical lubricating film separate out on SPC material, Measure the adhesion amount of each composition in this lubricating film.It addition, anode uses insoluble anode, (Di Nuola permanent electrode share has Limit company (ペ Le メレッ Network society) oxygen generation DSE processed).

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

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

(the analysis of each composition in lubricating film: the organic intensity from lubricating film surface to metal material surface Check)

Composition from the surface of the lubricating film obtained embodiment described later and comparative example the depth direction to metal material Analyze according to following sequence evaluating.

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

Sputter is carried out with argon in the depth direction from the surface of the lubricating film obtained in embodiment and comparative example, According to the distinctive plasma luminescence of carbon, obtain the intensity of each composition.It addition, when measuring, obtain lubricating film respectively The peak strength (Is) deriving from carbon on surface and the middle position of the thickness direction of lubricating film derive from carbon The peak strength (Im) of element, calculates it than (Im/Is).

(embodiment 1)

Use calcium nitrate, 2 sodium salts of EDTA(ethylenediaminetetraacetic acid) and deionized water, make calcium fluor-complex aqueous solution, then, add Adding isostearic acid, with ammonia and nitric acid, pH is adjusted to 5.0, the concentration obtaining calcium ion is 2000 mass ppm, isostearic acid The DC cathode electrolysis constituent of the embodiment that concentration is 2000 mass ppm 1.

The graduated cylinder of 1L is elected to be treatment trough, fills above-mentioned DC cathode electrolysis constituent, be warmed to 25 DEG C.At treatment trough Inner side, SUS net is elected to be anode and is equipped with.

Using implement surface cleaning process wire rod as cathode dipping at treatment trough center, with commutator (Co., Ltd. STOL makes made ZX-1600LA) carry out electric current density 10A/dm², electricity 20C/dm²Electrolysis procedure.Owing to being relatively low Current value, so being equipped with non-resistance galvanometer in the way of distribution, confirms the electric current being to specify, while carrying out negative electrode electricity Solve.

Then, this test film is taken out from treatment trough, cleans with flat tap water, by air blown, moisture is removed, Wire rod produces lubricating film.

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

On the wire rod of embodiment 1 defining lubricating film, carry out weight measurement and be coated with antirust oil (Parker is emerging Produce (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 2)

Magnesium nitrate is added in deionized water and make magnesium aqueous solution, then add Azelaic Acid, with ammonia and nitric acid, pH is adjusted Be 9.0, obtain the concentration of magnesium ion be 3000 mass ppm, Azelaic Acid be the DC cathode electricity of the embodiment 2 of 2000 mass ppm Solution constituent.

Using implement surface cleaning process wire rod as cathode dipping at treatment trough center, with commutator (Co., Ltd. STOL makes made ZX-1600LA) carry out electric current density 10A/dm², electricity 50C/dm²Electrolysis procedure.Owing to being relatively low Current value, so being equipped with non-resistance galvanometer in the way of distribution, confirms the electric current being to specify, while carrying out negative electrode electricity Solve.

Adhesion amount in lubricating film be magnesium (magnesium elements) be 0.6g/m², Azelaic Acid be 0.2g/m².Additionally, above-mentioned ratio (Im/Is) it is 0.11.

On the wire rod of embodiment 2 defining lubricating film, carry out weight measurement and be coated with antirust oil (Parker is emerging Produce (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 3)

Use aluminum nitrate, 3 sodium salts of NTA(nitrilotriacetic acid) and deionized water making aluminum fluor-complex aqueous solution, then add nonyl two Acid, is adjusted to 6.0 with ammonia and nitric acid by pH, obtain aluminum ions concentration be 3000 mass ppm, the concentration of Azelaic Acid be 5000 matter The DC cathode electrolysis constituent of the embodiment 3 of amount ppm.

The graduated cylinder of 1L is elected to be treatment trough, fills above-mentioned DC cathode electrolysis constituent, be warmed to 30 DEG C.At treatment trough Inner side, SUS net is elected to be anode and is equipped with.

Adhesion amount in lubricating film be aluminum (aluminium element) be 0.4g/m², Azelaic Acid be 0.3g/m².Additionally, above-mentioned ratio (Im/Is) it is 0.13.

On the wire rod of embodiment 3 defining lubricating film, carry out weight measurement and be coated with antirust oil (Parker is emerging Produce (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 4)

Use Yttrium trinitrate and deionized water to make yttrium aqueous solution, then add adipic acid, with ammonia and nitric acid, pH is adjusted to 6.0, Obtain the DC cathode electricity of the embodiment that concentration is 5000 mass ppm 4 that concentration is 3000 mass ppm, adipic acid of ruthenium ion Solution constituent.

Using implement surface cleaning process wire rod as cathode dipping at treatment trough center, with commutator (Co., Ltd. STOL makes made ZX-1600LA) carry out electric current density 20A/dm², electricity 50C/dm²Electrolysis procedure.Owing to being relatively low Current value, so being equipped with non-resistance galvanometer in the way of distribution, confirms the electric current being to specify, while carrying out negative electrode electricity Solve.

Adhesion amount in lubricating film be yttrium (yttrium) be 0.7g/m², Azelaic Acid be 0.3g/m².Additionally, above-mentioned ratio (Im/Is) it is 0.13.

On the wire rod of embodiment 4 defining lubricating film, carry out weight measurement and be coated with antirust oil (Parker is emerging Produce (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 5)

Use calcium nitrate, 2 sodium salts of EDTA(ethylenediaminetetraacetic acid) and deionized water making calcium fluor-complex aqueous solution, then add Isostearic acid, is adjusted to 6.0 with ammonia and nitric acid by pH, and the concentration obtaining calcium ion is 3000 mass ppm, isostearic acid Concentration is the DC cathode electrolysis constituent of the embodiment 5 of 5000 mass ppm.

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

On the wire rod of embodiment 5 defining lubricating film, carry out weight measurement and be coated with antirust oil (Parker is emerging Produce (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 6)

Use magnesium acetate and deionized water to make magnesium aqueous solution, then add Azelaic Acid, with ammonia and acetic acid, pH is adjusted to 9.0, Obtain the DC cathode electricity of the embodiment that concentration is 5000 mass ppm 6 that concentration is 5000 mass ppm, Azelaic Acid of magnesium ion Solution constituent.

The straight of embodiment 6 is filled to the propylene container (inside dimension length 31cm, width 12.6cm, highly 12.5cm) of 5L Stream catholyte constituent, is warmed to 35 DEG C with hot water water proof.Insoluble sun is configured inside the length direction of container Pole (Di Nuola permanent electrode limited company (ペ Le メレッ Network society) oxygen generation DSE processed), centre configuration is implemented in a reservoir The cold-rolled steel sheet that surface cleaning processes is as negative electrode.Anode is 15cm with the distance of negative electrode, shelters, so that area ratio becomes It is 1/3 for annode area.

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

Then, this test film is taken out from treatment trough, cleans with flat tap water, by air blown, moisture is removed, Cold-rolled steel sheet produces lubricating film.

Adhesion amount in lubricating film be magnesium (magnesium elements) be 0.8g/m², Azelaic Acid be 0.2g/m².Additionally, above-mentioned ratio (Im/Is) it is 0.11.

On the cold-rolled steel sheet of embodiment 6 defining lubricating film, with roller coat antirust oil (Parker emerging product (パカ ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 7)

Use aluminum nitrate, 3 sodium salts of NTA(nitrilotriacetic acid) and deionized water making aluminum fluor-complex aqueous solution, then add nonyl two Acid, is adjusted to 9.0 with ammonia and acetic acid by pH, obtain aluminum ions concentration be 2000 mass ppm, Azelaic Acid be 7000 mass ppm The DC cathode electrolysis constituent of embodiment 7.

The straight of embodiment 7 is filled to the propylene container (inside dimension length 31cm, width 12.6cm, highly 12.5cm) of 5L Stream catholyte constituent, is warmed to 35 DEG C with hot water water proof.Insoluble sun is configured inside the length direction of container Pole (Di Nuola permanent electrode limited company (ペ Le メレッ Network society) oxygen generation DSE processed), centre configuration is implemented in a reservoir The cold-rolled steel sheet that surface cleaning processes is as negative electrode.Anode is 15cm with the distance of negative electrode, shelters, so that area ratio becomes It is 1/3 for annode area.

Adhesion amount in lubricating film be aluminum (aluminium element) be 0.2g/m², Azelaic Acid be 0.3g/m².Additionally, above-mentioned ratio (Im/Is) it is 0.13.

On the cold-rolled steel sheet of embodiment 7 defining lubricating film, with roller coat antirust oil (Parker emerging product (パカ ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(embodiment 8)

Use Yttrium trinitrate and deionized water to make yttrium aqueous solution, then add adipic acid, with ammonia and acetic acid, pH is adjusted to 9.0, Obtain the concentration of ruthenium ion be 3000 mass ppm, adipic acid be the DC cathode electrolysis group of the embodiment 8 of 7000 mass ppm Become thing.

The straight of embodiment 8 is filled to the propylene container (inside dimension length 31cm, width 12.6cm, highly 12.5cm) of 5L Stream catholyte constituent, is warmed to 35 DEG C with hot water water proof.Insoluble sun is configured inside the length direction of container Pole (Di Nuola permanent electrode limited company (ペ Le メレッ Network society) oxygen generation DSE processed), centre configuration is implemented in a reservoir The cold-rolled steel sheet that surface cleaning processes is as negative electrode.Anode is 15cm with the distance of negative electrode, shelters, so that area ratio becomes It is 1/3 for annode area.

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

Adhesion amount in lubricating film be yttrium (yttrium) be 0.2g/m², Azelaic Acid be 0.5g/m².Additionally, above-mentioned ratio (Im/Is) it is 0.15.

On the cold-rolled steel sheet of embodiment 8 defining lubricating film, with roller coat antirust oil (Parker emerging product (パカ ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(comparative example 1)

On wire rod, carry out weight measurement and be coated with antirust oil (the emerging product of Parker (パカ) Co., Ltd.'s system NOX-RUST530F), to become 1.0g/m², wire rod produces oil reservoir.

(comparative example 2)

Cold-rolled steel sheet uses roller coat antirust oil (the emerging product of Parker (パカ) Co., Ltd. NOX- RUST530F), to become 1.0g/m², cold-rolled steel sheet produces oil reservoir.

(comparative example 3)

Azelaic acid magnesium is added in deionized water, produces the constituent of comparative example 3.This constituent is nebulousurine, easily sinks The dispersion liquid of fall.

Use it, by constituent dip coating to wire rod and cold-rolled steel sheet, so that azelaic acid magnesium becomes 2g/m², little Heart is dried.After the drying, entirety is white, but can scattered see irregular.Additionally, be easily contemplated to, whenever dispose wire rod and Cold-rolled steel sheet, the powder of white will come off, may be poor with the adhesion of wire rod or cold-rolled steel sheet.In this case, carefully It is coated with antirust oil (the emerging product of Parker (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

It addition, above-mentioned embodiment is equivalently employed without implementing the form of catholyte.

(comparative example 4)

Calcium stearate is added in deionized water, produce the constituent of comparative example 4.This constituent is nebulousurine, easily settles Dispersion liquid.

Use it, by constituent dip coating to wire rod and cold-rolled steel sheet, so that calcium stearate becomes 2g/m², carefully Be dried.After the drying, entirety is white, but can scattered see irregular.Additionally, be easily contemplated to, whenever disposing wire rod and cold Rolled steel plate, the powder of white will come off, may be poor with the adhesion of wire rod or cold-rolled steel sheet.In this case, it is coated with carefully Antirust oil (the emerging product of Parker (パカ) Co., Ltd. NOX-RUST530F), to become 1.0g/m²。

(comparative example 5)

The graduated cylinder of 1L is elected to be treatment trough, fills patent documentation 1(JP 2000-144494) the constituent of embodiment 1, It is heated to 80 DEG C.In the inner side for the treatment of trough, SUS net is elected to be anode and is equipped with.

Modulation at normal temperatures is containing Nihon Parkerizing Co., Ltd. (the Japan パ described in 3 mass % patent documentations 1 カライジ Application グ (strain)) aqueous solution of colloidal titanium processed (U ロイダ Le チタ Application) class surface conditioner (プレパレ Application Z), After the wire rod implementing surface cleaning process is impregnated 1 minute, at treatment trough center with wire rod for negative electrode commutator (strain formula Commercial firm STOL makes made ZX-1600LA) to carry out electric current density be 20A/dm², electricity be 50C/dm²Electrolysis procedure.Due to Being relatively low current value, so configuring non-resistance galvanometer in the way of distribution, confirming entering of the electric current specified Row catholyte.

Then, this test film is taken out from treatment trough, cleans with flat tap water, by air blown, moisture is removed, Wire rod produces zinc phosphate coat.

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

Then, this wire rod is coated with antirust oil (the emerging product of Parker (パカ) Co., Ltd. NOX- RUST530F), to become 1.0g/m²。

(comparative example 6)

By the operation equal with comparative example 5, obtaining having as zinc phosphate is 3.5g/m²The wire rod of zinc phosphate coat.

Then, by this wire rod in response type soap the treatment fluid ((Japan of Nihon Parkerizing Co., Ltd. being heated to 80 DEG C パカライジ Application グ Co., Ltd.) パ Le Block 235,70g/L processed) in dipping 3 minutes.By occur in this operation The reaction that response type soap processes, above-mentioned zinc phosphate dissolves slightly and becomes 3.0g/m².Further, metallic soaps and the band of liquid The total amount of the unreacted soap of output is 3.0g/m²。

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

Following lubricity evaluation (its is implemented use wire rod in above-described embodiment and comparative example as test film in the case of 1), in the case of use cold-rolled steel sheet as test film, implement following lubricity evaluation (its 2), evaluate lubricity.

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

By the wire rod test film that obtains in embodiment and comparative example for 3mmEnd be inserted into supersteel molding jig 3.05mmIn (Fuji's mould (scholar ダイス) system).Then, with accurate universal testing machine (Shimadzu Scisakusho Ltd AG-X) Upper grip portion wire rod is fixed, by fixing for supersteel molding jig on the apparatus.Make upper grip portion with the speed of 1m/min It is moved upward, makes this wire rod pass in mould, carry out drawing processing.Drawing when monitoring in mould with personal computer Load.

On the basis of the value of the drawing load of comparative example 1, the size of the drawing load in each embodiment and comparative example is pressed According to following metewand evaluation.It addition, comparative example 1 be evaluated as "×".

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

"○":, more than half situation of drawing load for comparative example 1 less than the drawing load of comparative example 1

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

Additionally, when drawing, there are not dregs in the preferably entrance at mould.Be there is not slag in the entrance at mould The situation of dregs is evaluated as dregs generation inhibition "○", and the entrance at mould there occurs, the situation of dregs is evaluated as dregs and occurs Inhibition "×".

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

The cold-rolled steel sheet test film obtained in embodiment and comparative example is carried out stamping-out operation to become diameter 110mm, system Make deep-draw processing test film.Then, this steel plate is used, with high speed deep drawing test machine (Co., Ltd.'s Tokyo test system DHV-20/650-8001) deep-draw processing is carried out.Represent the summary of this high speed deep drawing test machine in figure 3.Such as Fig. 3 (A) institute Showing, high speed deep drawing test machine 18 possesses drift 20 and the mould of supporting test film 30 being applied in load on the direction of black arrow 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), act on drift 20 from the direction of black arrow Load, scans the fixing fold extrusion load of test film 30, and inspection test sheet 30 reaches the load of fracture.

On the basis of the value of the fold extrusion load of comparative example 2, evaluate each embodiment and ratio according to following metewand The size of the fold extrusion load in relatively example.It addition, comparative example 2 be evaluated as "×".

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

"○":, situation less than 2 times of fold extrusion load of comparative example 2 bigger than the fold extrusion load of comparative example 2

" ◎ ": the situation of more than 2 times of the fold extrusion load of comparative example 2.

Use the wire rod with lubricating film manufactured respectively about embodiment 1～5, 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 following chemical conversion evaluation (its 1) and chemical conversion property evaluation (its 2).

(chemical conversion property evaluation (its 1): processed, by zinc phosphate, the chemical conversion brought and character confirms)

According to following order, test film is implemented the surface process of the more employing as the base treatment of application.

(1) by degreasing agent (Nihon Parkerizing Co., Ltd. (Japan パカライジ Application グ Co., Ltd.) fine filtering processed Clear device (Off ァイ Application Network リ Na) E2001) it is warmed to 43 DEG C, each test film is impregnated 3 minutes, by the surface of test film Lubricating film and oil reservoir remove.

(2) with flat city tap water, the degreasing agent composition on test film is washed off.

(3) by surface conditioner (Nihon Parkerizing Co., Ltd.'s (the Japan's パカライジ Application グ strain formula for 2g/L Commercial firm) プレパレ Application X processed) adjust with flat tap water, in this surface adjusts liquid, test film is impregnated 30 seconds.

(4) test film is adjusted taking-up liquid from surface, when surface adjustment liquid is attached on test film, will examination Test sheet and be impregnated into zinc phosphate treatment fluid (Nihon Parkerizing Co., Ltd. (the Japan パカライジ Application グ being adjusted to 35 DEG C Co., Ltd.) パ Le ボ Application De SX35 processed, free acidity 0.7pt, promoter concentration (sets this society's accelerator 131 as 3.5pt), Carry out 2 minutes rocking.

(5) after zinc phosphate processes, test film is cleaned with flat tap water, then cleans with deionized water.Then, with sky Gas blowout is blown and is removed by moisture.

The Evaluation for Uniformity of zinc phosphate coat is visually to judge, uniformly and does not has irregular, not have shortcoming situation in form and aspect Lower for " ◎ ", visually under irregular in the case of be "○", have irregular in the case of owing to bringing application irregular, so For "×".

(chemical conversion property evaluation (its 2): the chemical conversion brought by metal oxide treated and character confirm)

As the base treatment of application, the surface of the metal-oxide that test film is implemented extension according to following order processes.

(3) test film is impregnated into be adjusted to 45 DEG C metal-oxide treatment fluid (Japan handkerchief card rapids essence strain formula meeting Society (Japan パカライジ Application グ Co., Ltd.) パ Le シ De 1500, pH4.0 processed) in, carry out 2 minutes rocking.

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

The Evaluation for Uniformity of metal-oxide epithelium is visually to judge, uniformly and does not has irregular, not shortcoming in form and aspect In the case of be " ◎ ", visually under irregular in the case of be "○", have irregular in the case of owing to bringing application irregular, So being "×".

Hereinafter, in Table 1 evaluation result is collected expression.

In Table 1, refer to than (Is/Im) lubricating film the side contrary with metal material surface on derive from carbon The peak strength (Is) of element is to be equivalent to lubricating film with the surface of the side contrary with metal material away from lubricating film The ratio (Im/Is) of the peak strength (Im) deriving from carbon of the middle position of the degree of depth of the 1/2 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 process Ratio (Is/Im) in film, does not accounts for zinc phosphate coat.

Additionally, " metallic element " hurdle of the comparative example 5 and 6 in table 1 refers to the amount of zinc phosphate, " organic acid compound " refers to By the amount of the epithelium that response type metallic soaps process is formed.

Additionally, in " lubricity evaluation " hurdle in Table 1, "-" refers to be not carried out.

As shown in table 1, the lubricating film that the catholyte process of the constituent of the application of the invention obtains manifests well Lubricity and defat after chemical conversion.

On the other hand, only configure oil reservoir comparative example 1 and 2, do not implement catholyte process comparative example 3 and 4, with And in the comparative example 5 and 6 of the embodiment being equivalent to patent documentation 1, do not obtain desired effect.

Description of reference numerals

10,100 with the metal material of lubricating film

12 metal materials

14 lubricating films

16 oil reservoirs

18 high speed deep drawing test machines

20 drifts

22,24,26,28 mould

30 test films.

Claims

1. a DC cathode electrolysis constituent, it is characterised in that contain:

Select at least from the group being made up of typical metal the ion more than divalent in addition to zinc ion and rare earth element ion 1 metal ion species or its fluor-complex (A)；

The organic acid compound (B) of the straight chain alkylene group of carboxyl and carbon number more than 4 is comprised in intramolecular；With

Water (C).

2. DC cathode electrolysis constituent as claimed in claim 1, it is characterised in that

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

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

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

4. the DC cathode electrolysis constituent as according to any one of claims 1 to 3, it is characterised in that

PH is 3.5～12.5.

5. the manufacture method with the metal material of lubricating film, it is characterised in that

Possesses following operation: metal material is impregnated into the DC cathode electrolysis composition according to any one of Claims 1 to 4 In thing, with above-mentioned metal material as negative electrode, implement to use the catholyte of direct current to process, above-mentioned metal material surface is formed Lubricating film.

6. the metal material with lubricating film, it is characterised in that

By the manufacture method manufacture of the metal material with lubricating film described in claim 5.

7., with a metal material for lubricating film, possess metal material and the lubrication being arranged on above-mentioned metal material surface Epithelium, it is characterised in that

Above-mentioned lubricating film comprises:

Select at least from the group being made up of the typical metal elements more than divalent in addition to zinc ion and rare earth element ion 1 kind of metallic element；

Organic acid compound and/or its salt of the straight chain alkylene group of carboxyl and carbon number more than 4 is comprised in intramolecular；

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

The metal material with lubricating film the most as claimed in claims 6 or 7, it is characterised in that

Above-mentioned lubricating film is also equipped with the oil reservoir containing oil component.