JPS6160886A - Rustproof lubricated steel sheet - Google Patents

Abstract

PURPOSE:To provide a rustproof lubricated steel sheet having superior corrosion resistance and press formability by forming a chromate film on a galvanized steel sheet and a special org. composite silicate film on the chromate film. CONSTITUTION:The chromate film is formed on the galvanized steel sheet by 5-200mg/m<2> (expressed in terms of Cr). A film contg. org. composite silicate which is an acrylic-silica composite body as the principal component and a water-dispersible lubricant such as polyethylene lubricant is formed on the chromate film by coating or other method. The film may further contain one or more kinds of components selected from oxyacids of Mo, W, V, Sn, B, Si, etc. and salts thereof. The treated steel sheet has satisfactory lubricity, superior corrosion resistance and high weldability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a rust-preventing, lubricating, surface-treated steel sheet that has excellent corrosion resistance and press workability.

[Conventional technology and its problems]

Galvanized steel sheets, zinc-based alloy plated steel sheets such as zinc-iron alloy plating, zinc-nickel alloy plating, and zinc-manganese alloy plating are used as excellent corrosion-resistant materials.
For this reason, it is often subjected to various pressing processes. Conventionally, in press working of this type of steel plate, press oil is usually applied in order to obtain good workability, but such oil application has the following problems.

(a) Press oil is often applied using the SpV-method, and the press oil scatters in the form of mist, worsening the working environment.

(b) Press oil cannot effectively prevent mold galling during pressing.

←→ Degreasing is performed after pressing, but there is a problem of poor degreasing due to residual press oil. In order to improve press workability, a method of increasing the viscosity of the press oil is adopted, but the problem is that the higher the viscosity, the more difficult it is to degrease the oil. If such a degreasing defect occurs, a film will not be formed on the defective part in the subsequent chemical conversion treatment step or painting step, resulting in defective chemical conversion treatment and poor paintability (sealability, IIT edibility).

Conventionally, a millbond copper plate, for example, has been known as a steel plate with excellent press workability, and this has the advantage that press work can be performed without applying press oil. However, the Milbond coating on this steel plate has almost no corrosion resistance, and it is necessary to further apply rust preventive oil on the coating to ensure corrosion resistance. On the other hand, as a copper plate with excellent corrosion resistance,
A composite surface-treated steel sheet as shown in No. 8292 is known.

This steel sheet is made of zinc-plated steel sheet and has a two-layer coating of a chromate coating and an organic composite noricate coating formed thereon, and exhibits extremely good corrosion resistance with a 5STO day rust generation time of 400 hours or more. However, this steel sheet has poor press workability because its surface film has no lubricity at all, and therefore requires application of press oil. In addition, there were problems with the processability of the film itself, such as the organic silicate film peeling off or cracking during processing, not to mention the lubricity of this type of steel sheet, and improvements were desired. .

In view of these circumstances, the present invention aims to provide a rust-proof lubricated steel sheet that has sufficient lubrication performance to enable press working without the need for applying press oil, and at the same time has excellent corrosion resistance, especially bare corrosion resistance. [Means for solving all problems] For this reason, as a result of repeated research by the present inventors, the above-mentioned composite surface-treated steel sheet was converted into an organic composite silicate skin, and
It has been found that by adding lubrication properties to this steel sheet, a steel sheet having excellent press workability can be obtained while maintaining the corrosion resistance of this type of steel sheet.

That is, the present invention provides a chromate film with a chromium adhesion amount of 5 to 200 μ/rn2 from the lower layer side and a film thickness of 0 containing all water-dispersible lubricating additives on the plated surface of a steel plate such as a Zn-based plated steel plate.
．． The basic characteristics of the present invention are that the organic composite silicate film of 3 to 3 μm is completely formed on the gold. , zinc-iron alloy plated steel sheet, zinc-nickel alloy plated steel sheet, zinc-manganese alloy plated steel sheet, zinc-aluminum alloy plated steel sheet, zinc-cobalt-
Ni is added to the plating components of zinc-based plated steel sheets such as chromium alloy-plated steel sheets, aluminum-based plated steel sheets, and any of these steel sheets.

Fe + Mn, MO, Co, A1. Elements such as Cr'
Jl: 1 Mi or one with 2 or more added thereto may be used, and a composite plated steel sheet coated with t-2 or more layers of the same or different types of plating as described above may be used.

As a plating method for these galvanized steel sheets, any practicable method among electrolytic method, melting method, vapor phase method, etc. can be adopted.

The amount of plated N for each plated steel plate is 11/m'' per side.
It is preferable to set it as above, and if it is less than this, there is a possibility that corrosion resistance will deteriorate.

The plating components in the various alloy plating films are preferably selected within the following ranges, and outside these ranges there is a risk that corrosion resistance may deteriorate.

Zn-Fe alloy Meggi - Fei 5 to 90 wt% (more preferably 5 to 35 wt% → Zn-Ni alloy Metki Ni 15 to 20 wt% Zn-M
n-alloy plating: Amount: 30 to 85 wt% Zn-AJ alloy Metsky AJ amount: 2 to 60 wt% Even in the case of two or more layers of plating, each Ja plating component can be selected within the above range.

Furthermore, it goes without saying that the present invention can be applied not only to double-sided plated steel plates but also to single-sided plated steel plates.

The present invention forms an organic composite silicate film containing M on the plated surface of such a plated steel sheet, starting from the lower layer as a first layer of chromelt coated gold, and as a second layer of M containing a water-dispersible lubricating additive.

First, the first layer of chromate film has chromium adhesion t(dr
y) from 5 to 200 m9/m' color fx le. If the amount of rubber deposited is less than 51R9/m', the desired corrosion resistance cannot be expected, and if it exceeds 200 m9/m', no further improvement in corrosion resistance can be expected, and on the contrary, the tacomate itself will peel off during pressing. , problems such as deterioration of press workability may occur.

As a method for forming such a romate film, any method such as a coating type, an electrolytic type, and a single reaction type can be used.

As a reactive chromate treatment solution, for example, mineral acid (H2804, HsPO4゜HF) is added to chromic acid as a reaction accelerator.
, containing one or more types of silicofluoric acid, etc.)
(for example, Nippon Parr Ising Co., Ltd. 1!ZM355, etc.), and has a pH of 0.5 to 2.0.
A Cr''/Cr'' ratio in the bath is usually used in the range of 1/1 to 1/1o. By immersing or spraying a plated steel plate in a bath for a predetermined period of time, a reaction sound is generated between the plated surface and the bath, and a talome film is formed. Thereafter, unreacted components are removed by washing with water to obtain a chromate film. The above-mentioned water washing is carried out mainly to completely prevent gelation of the resin if unreacted contaminants, especially Cr'+, are mixed into the next organic composite silicate treatment step, which would lead to gelation of the resin.

The coating-type chromate treatment solution is mainly composed of partially reduced chromic acid solution gold, and if necessary, this is combined with water-dispersible or water-soluble organic resin such as acrylic resin and/or tens to thousands of silica. Those containing particles (silica sol, humid silica) (for example, Nippon Vercalizing Co., Ltd. [BT
3375A, Acomet C manufactured by Kansai Paint Co., Ltd.) are used. In this case, the ratio of Crs+ /Cfh is 1/1~
1/3, pHh 1.5 to 4.0 (more preferably 2 to 3). The ratio of Cr''/C,6+ is adjusted to a predetermined ratio by using general organic reducing agents (e.g. sugars, alcohols, etc.) and inorganic reducing agents.Also, as coating type chromate treatment, roll coater method, In zero-coating chromate treatment, which may be performed using any method such as dipping or spraying, a film is obtained by drying without washing with water after the chromate treatment.Drying without washing with water in this way is usually Since Cr'+ is removed during the water washing, the entire Cr''/Cr'' ratio is maintained stably,
This is to complete the sealing by treatment with an organic composite silicate solution in the next step.

On the other hand, in electrolytic chromate treatment, cathodic electrolysis is performed in a bath containing all of chromic anhydride and one or more of anions such as sulfuric acid, phosphoric acid, fluoride, or nitrogen oxyacid, followed by water washing and Dry to form a film.

Next, the organic composite silicate film, which is the second layer, is made by fully reactively bonding water-dispersible silica and water-soluble or water-dispersible FF1 (24 fat). (additives are included), this point is a major percentage point.

The lubricant used in the present invention is compatible with or dispersible in the above composite resin, has the function of reducing the frictional resistance between the coating film and the mold during the molding process of the pre-coated plate, and has the function of reducing the frictional resistance between the coating film and the mold. This has the effect of preventing wear on the surface and mold.

As such a lubricant, any known lubricant can be used, such as the following.

Hydrocarbon lubricants: For example, natural paraffin, synthetic halaffin, microwax, polyethylene wax, chlorinated hydrocarbon, fluorocarbon, etc.

Fatty acid $ lubricant: For example, lauric a, stearic acid, palmitic acid, oxyfatty acid, etc.

Fatty acid amide lubricants: For example, stearamide, palmitic acid amide, methylene bis stearamide, ethylene bis stearamide, oleic acid amide, ethyl acid amide, alphi-rempis fatty acid amide, etc.

Ester lubricants: For example, lower alcohol esters of fatty acids such as butyl stearate, polyhydric alcohol esters of fatty acids such as hydrogenated castor oil, glycol esters or polyglycol esters of fatty acids such as ethylene glycol monostearate, ester waxes, etc. .

Alcohol-based lubricants: For example, cetyl alcohol, stearyl alcohol, palmityl alcohol, etc.

Metallic soaps: for example, calcium stearate, lead stearate, calcium laurate, calcium norumitate, etc.

Metal sulfides molybdenum disulfide, tungsten disulfide B Others: graphite, graphite fluoride, electrified boron, grease, alkali metal sulfates, etc.

The amount of such lubricating additives added is 0.1 to 0.1 to 100 M solids of the Ij' mechanical composite silicate.
It is preferably selected in the range of 20 parts by weight, preferably 2 to 15 parts by weight. If the amount of the lubricating additive added is less than 0.1 parts by weight, the I4 lubricating effect will not be sufficient, and if it exceeds 20 parts by weight, the corrosion resistance will deteriorate, which is undesirable. Make it thick. If the coating thickness is less than 0.3 μrnf, the corrosion resistance will deteriorate, and if it exceeds 3 μtrL, a commensurate corrosion resistance improvement effect will not be obtained, and weldability, especially spot II bondability, will deteriorate.

Organic composite silicates usually have water-dispersible silica as an essential component, and a water-soluble or water-dispersible organic polymer resin, whole di- or H-alkoxy (or alkoxy alkoxy silane compound) (hereinafter referred to as "silane compound"). It can be obtained by mixing in the presence of (referred to as ) and reacting at a temperature below the boiling point.

It is a particle size of several tens to several thousand λ and is called water teL silica ffj7 lycasol or colloidal silica.

Colloidal silica having a particle size within the above range can be used in the form of an aqueous dispersion, whether acidic or basic. It can be selected as appropriate depending on the stability region.

That is, as the colloidal silica on the acidic side, for example, the product name Snowtex-0 or Snowtex OL is used.
Non-stabilized silica (pH 2 to 4) commercially available from Nichiryo Kagaku Kogyo@ can be used. On the other hand, as colloidal silica on the basic side, silica (QH8, 4-10 ngawashi, product name Snowtex 2o, Snowtex C,
Snowtex N (the above are products of Nissan Chemical Industries, Ltd.)
I can give you money.

As the organic resin, an acrylic copolymer is preferable in order to improve corrosion resistance (particularly bare corrosion resistance), but other organic resins can also be used, such as alkali resin, epoxy resin, polybutadiene resin, base resin, etc. WIL (including fatty acids) or polybasic acid-modified polybutadiene, methylolated phenolic resin, methylolated urea resin, methylolated melamine resin, olefin-methacrylic fluorine resin, polyurethane resin, vinyl chloride resin, vinylidene chloride resin, alkanolamine-modified resin Polyurethane resins, amino resins, polyamine resins, polycarboxylic acid resins, aldehyde resins, unsaturated polyester resins, acrylic resins with unsaturated bonds introduced, alkaline resins and epoxy resins, poly and nylacetals, synthetic drying oils, malein Examples include synthetic oils, synthetic rubbers, mixtures of two or more of these, and addition condensates.

The acrylic copolymer is a water-soluble or water-dispersible acrylic copolymer synthesized by a solution polymerization method, an emulsion polymerization method, or a suspension polymerization method using a common unsaturated ethylenic monomer. The monomers constituting the polymer must each contain at least 2% of a monomer having a hydroxyl group and a monomer having a carboxyl group as essential components at the time of monomer blending. Preferably, a V content of 3 to 50 is selected. These functional monomers are important not only for the purpose of making the acrylic copolymer completely water-soluble or water-dispersible, but also as reactive groups with colloidal silica and the silane compound described below.

Acrylic copolymers synthesized by conventional methods must be water-solubilized or water-dispersed in order to be composited with colloidal silica, and amine compounds are suitable as additives suitable for this purpose. For example, aliphatic amines such as monoethylamine and diethylamine,
Examples include alkanolamines such as jetanolamine/triethanolamine, and cyclic amines such as pyridine and piperidine.

The silane compound functions as a catalyst for the above-mentioned composite of silica and acrylic copolymer, and also plays an important role as a crosslinking agent for both and a crosslinking agent for the total bending substrate and the composite film. In order to exhibit such effects, the silane compound is appropriately selected from those exemplified below depending on whether the aqueous dispersion of colloidal silica is acidic or basic. Such silane compounds include:
For example, divinyldimethoxysilane, divinyldi-β
-methoxyethoxysilane, di(r-glycidoxyglobyl)dimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, r-
Glycidoxyglobiltrimethoxysilane, r-methacryloxyglobiltrimethoxysilane, β-(3,
4-Evoxinchlorohexylene ethyltrimethoxynorane, N-β (aminoethyl) r-propylmethyldimethoxysilane, N-β (aminoethyl) r-aminoprobyltrimethoxysilane, γ-aminoprohyltriethoxysilane, etc. I can get tS.

The blending ratio of the water-dispersible adhesive strength and the water-soluble or water-dispersible organic resin in the above organic composite silicate is preferably in the range of 5:95 to 40:60 in terms of solid content weight percentage. The proportion of the silane compound to be used is determined by the solid content of both water-dispersible silica and water-bathable or water-dispersible organic polymer resin.
It is usually 0.5 to 15 inches, preferably 1 to 10 inches, based on the total amount of JIL, and if it is less than 0.5%, the reaction promotion effect and crosslinking effect by addition will not be clear, and if it exceeds 15%. Even if added, these effects cannot be expected to become even more significant.

In the present invention, in addition to the above organic composite silicate, if necessary, one or two kinds of oxyacids of elements selected from the group consisting of molybdenum, tungsten, vanadium, tin, boron, and silicon, and mineral oxyacids are used. The addition of gold can significantly improve the water resistance, alkali resistance, and anticorrosion properties of the coating, as well as increase the curing speed. Examples of such compounds include the following Nuro Kimono.

- Oxygen acid of molybdenum and its salt molybdenum 7 rR (Hz Mo 04 ・Hz O),
Anhydrous % 17 Butene (MoOs), Lithium Molybdate (L D MO04), Sodium Molybdate (Nat MO04), Potassium Molybdate (I'u
M.

04.5H1O), ammonium heptamolybdate (
(NH4) a Mov Qz+・4HfO), sodium phosphomolybdate (Nas P 04 ・12
MoOs), phosphomolybdic acid (20MoO,・
2I-Is PO4・481-It O),%'J
Zinc (4ZnO・ZnMo 04 ), calcium molybdate (Ca MO 04 ), magnesium molybdate (MgMo 0 4 ), strontium molybdate (SnM, ), barium molybdate A (BaMa 04 ), etc.

・Tungsten oxygen acid and its salt tungsten e
(WOs・HzO), tungstic anhydride (WOs)
, tungsten-brewed lithium (L it WO number), sodium tungstate (Na.

WO4・2Hto), potassium tungstate (K.

WO4), sodium metatungstate (Na=
W4013), sodium halatungstate (N
a. W4041), ammonium heftatungstate ((N)4 Ws O+T・5Hz O), ammonium heftatungstate ((NH4)6
W70□4・6Ht O), sodium phosphotungstate (NasPO4'12WO3' 18Ht
O), barium boronate (Ba@ + CB
(WtOt)a)z) etc.

・ Vanadium oxygen acids and their salts Vanadium trioxide (VI Os ), Nadium pentoxide (VI O5), Lithium orumvanadate (Lis
VO4), iron sodium orthovanadine (Na3 V
O4), mepvanadine@++ fftum (LiVO, -
2HtO), Mel Haf Schiff acid power') ') Mu(
KVOs), sodium metavanadate (N a V
Oa・4HtO), ammonium metavanadate (NH
4VO, or (NH4) 4V4 On), sodium pyrovanadate (Na4v, Ot), etc. 0 Tin oxygen acid and its hydrochloride Tin oxide (Snow or SnO), orthotin W
(Sn(OH)4), metastannic acid (Hz 5nO
s ), sodium metastannate (Nat 5n03 +
3H10), potassium metastannate (K! 5nOs
・3HtO), magnesium stannate, calcium stannate, ammonium stannate, etc.

- Boron oxygen acid and its salts boric acid (HsBOs), lithium metaborate (L
i Box ), sodium metaborate (NaBOt
), potassium metaborate (KBO, ), sodium tetraborate (Nag B40? ・l OHt O), sodium decaborate (Na2 Blo O+a ・1
0)(2Q), metaboric acid power/l/sim(C
a (Bo2h 2Hx O), ammonium metaborate, etc.

Oxygen acids of silicon and their salts silicon rR (S ios ・nHt O), lithium silicate (ns + ot /L120), sodium silicate (n
sioz/NaxO), silicic acid force'J'ymu (nS
iOt /L O), calcium silicate, ammonium silicate, phosphoric acid silica (2SiO, ・Pg Os )
and so on.

When two or more of these oxyacids or oxyacid salts are used in combination, it is necessary to combine them so as not to cause agglomeration and precipitation when mixed. The oxidizing oxyacid or oxyacid salt is usually added to the silica composite as a solution or dispersion in water or alcohol at a concentration of 1 to 20% by weight. 2
If it is added at a high concentration exceeding 0% by weight, care must be taken because agglomerates may partially form and a uniform composition may not be obtained.

These oxygen acids or c1! Theoretically, the appropriate amount of mate salt to be added is the maximum amount that allows metal ions to coordinate with the remaining functional groups and silanol groups in the silica complex, but usually the solid content relative to the silica complex is 5% by weight
Hereinafter, it is preferably determined in the range of 0.3 to 3% by weight for each silica composite and for each oxyacid or oxyacid.

Even if an appropriate amount of oxyacid or oxyacid salt is added in excess, not only will the curing rate not be particularly increased, but the water resistance of the cured film will decrease, or the stability of the composition will deteriorate due to coagulation. There is a risk that sex may be impaired.

As described above, the effects of water resistance, alkali resistance, and corrosion resistance when the oxyacid or oxyacid salt of a specific element is added to the organic composite silicate have not yet been fully clarified.

It is believed that the organic composite silicate used in the present invention has a large amount of hydrophilic 11sk derived from silica and a water-soluble or water-dispersible organic polymer resin, and also has a relatively porous coating mold g'j. Therefore, in order to overcome the drawbacks such as not being able to sufficiently block water, air, anions and cations due to metal corrosion factors, we have developed a composition containing a specific element of oxy-acid or oxy-acid foundation. In the form of a film, when curing with heat, the hydrophilic groups of the organic composite 7 silicate form a high-density bond between the hydrophilic groups within or between the molecules, reducing the total amount of remaining hydrophilic groups, resulting in water resistance, In addition to increasing the alkali resistance of gold, it is thought that the organic composite silicate is completely combined and integrated to form a film with a dense structure, which is expected to block all of the metal corrosion factors mentioned above. For these reasons, in a preferred embodiment of the present invention when emphasis is placed on corrosion resistance, particularly bare corrosion resistance, the organic resin constituting the organic composite silicate is an acrylic copolymer, and the organic composite 7-silicate film contains: An organic composite silicate containing one or more of the above-mentioned oxyacids or analytes of elements selected from the group consisting of molybdenum, tungsten, vanadium, tin, boron, or silicon. The coating method may be any conventionally known method, such as brush coating, spray coating, roll coating,
Methods such as dip coating can be used.

After such coating, a film is formed by drying, and heat treatment can be performed as necessary to accelerate the hardening of the film.

Further, when the free functional groups of the organic composite silicate solution are charged either negative or negative, it is also possible to apply the crown coating method. In addition, if an organic polymer resin with unsaturated double bonds introduced is used, it can be cured using an electron beam or ultraviolet curing method using a conventional ultraviolet beam irradiation device (1°C).
00-300KeV, 30-100fnA) or ultraviolet irradiation equipment a, (30-120W/cm high pressure mercury lamp)
It can also be hardened.

As described above, the steel sheet of the present invention prevents corrosion of the material itself as much as possible by plating as a base material, and also completely improves corrosion resistance by applying a chromate film as a lower layer on top of the metal mold bottom. By sealing with an organic composite silicate film as the upper layer, the elution of Cr, which has a passivating effect in a corrosive environment, can be suppressed to a minimum, and excellent corrosion resistance can be exhibited. By itself, a high corrosion resistance effect can be obtained due to an excellent barrier effect.In addition, due to the action of the lubricating additive in particular, the organic composite silicate in the upper layer has excellent lubrication performance without impairing the above-mentioned corrosion resistance. By obtaining press workability, it is possible to perform press processing without applying all the oil.In addition, the above-mentioned lubrication effect (thanks to the above-mentioned lubrication effect, prevents the die from forming during pressing and the peeling of the surface film. , press working can be performed without causing cracks or the like.

〔Example〕

Example (1)> The influence of yomate skin was investigated.
0 (1/m') galvanized steel sheet is used as the material, and a reactive chromate treatment solution (Japan Parkerizing Co., Ltd. Z) is applied to it.
M355) using ffi, 5Qji/l, Fk5, 5
A chromate film was formed by spraying PT, Cr15pt at a temperature of 40°C, and then an acrylic silica composite (acrylic/silica: 60/30) containing metavanazine [2 wt%] was coated on top of the chromate film. A polyethylene lubricant with a solid content of 11 L parts per 100 parts by weight of solid content was added.A gold-based solution was applied to a film thickness of 1.2 μm using a full roll coater method, and an organic composite silicate was coated with a film thickness of 1.2 μm. The entire bottom of the film was coated. In addition, as comparative materials, a steel plate in which an organic composite silicate was directly formed on the plated surface without forming a chromate film, and a steel plate in which a chromate film was formed with a coating amount of 250 m9/m2 were manufactured.

The obtained test materials were subjected to a salt spray test according to JIS Z2371 for 300 hours to observe the presence or absence of white rust, and to evaluate corrosion resistance. In addition, regarding press workability, the blank diameter is 120 mmφ, and the hole/chip diameter is 50 mmφ.

A cylindrical drawing test was conducted under the conditions of a wrinkle pressing pressure of 1.5 t, and the entire outer diameter before and after the test was measured, and the rate of change in the outer diameter was determined and evaluated. These results are shown in Table 1. (In addition, regarding the press workability in Table 1, Nippon Craft Oil's press oil 1m62
Compare with the outer diameter change rate of 0fi cloth material, if it is inferior, it is defective.
If it was excellent, it was considered good. ) Table 1 *Although the rate of change in outer diameter was good, peeling occurred from the chromate film layer after the cylindrical drawing test. Therefore, the corrosion resistance after processing was significantly deteriorated.

In this example, the influence of the organic post-gold silicate film was investigated. An electrogalvanized steel sheet with a plating of 41209/m' was used as the material, and a coating type chromate treatment bath fi (Kansai Paint A Accomet C) was applied to it. Cr coating amount was 30'''9/n2 by dipping treatment with a solution of 25017/l.
A chromate film of 100 parts by weight is formed on the acrylic composite silicate using a roll coater method, and a solid content of 5f [! A solution containing polyethylene-based Iia lubricant in the proportion of 0.2 am + 0.5 μm, 1i
tm, 1.5 μm, 2.5 μm, and 3.5 μm, and the corrosion resistance and press formability of the obtained test material was evaluated using the same method and conditions as in the above example. , and weldability (
Possibility of welding) tFA solid 0 This welding condition is as follows: Electrode tick: chrome copper RWMA C1ass2 equivalent shape C1 tip diameter 5,4 mm φ Electrode pressure crab 200k) Current application time: 12 cycles Current: 8KA, and whether welding is possible was investigated by a tensile test after welding.

The full results of these tests are shown in Table 2.

Example (3)> The influence of water-dispersible lubricant additives in the organic composite silicate film was investigated, and the amount of plating was 20,! i'/m' electrogalvanized steel sheet metal material was treated with a coating type chromate treatment solution (Acomet C manufactured by Kansai Paint Co., Ltd.) using a roll coater method using gold to achieve a Cr coating amount of 15 m9/TrL.
The chromate film of No. 2 is formed, and a paraffin-based lubricant is further added thereon in an amount of 0 parts by weight per 100 parts by weight of the organic composite silicate.

The alkyd composite silicate gold was coated with 0.5 parts by weight, 15 parts by weight of Ii, and 25 parts by weight to form a film with a thickness of 1 μm. The corrosion resistance and press formability of each of the obtained test materials were examined using the same method and conditions as in the above-mentioned Examples. The results of these tests are shown in Table 3.

Table 3 Sample material (6) i1 Contains a large amount of lubricating additives There is no problem with press workability, but on the contrary, the barrier effect of the M machine composite silicate film against corrosion factors decreases, and the corrosion resistance deteriorates. It is obvious that it has deteriorated.

Example (4)> In this study, the influence of water-dispersible silica in an organic composite silicate film was investigated. An electrogalvanized steel sheet with a plating fi of 20 g/m' was used as a material, and this was treated with a reactive chromate treatment solution ( Coating amount: 20IR9/m'
A chromate and gold film was formed thereon, and the weight ratio of silica and shoulder resin was O/I O0, 2/98.

Acrylic composite silicate (solid content of acrylic composite silicate 10/90.30/70.45155)
Th roll coater (containing calcium gold stearate at a solid content of 5 parts by weight as a lubricant with respect to 0 parts by weight)
to form a film with a thickness of 1 μm. and,
Corrosion resistance and press formability of each of the obtained test materials were examined using the same method and conditions as in the above-mentioned nine examples. The results of these tests are shown in Table 4.

As shown in Table 4 Sample materials (1) and (2), Si′f′ is
/Organic 8J fat: Corrosion resistance is poor in the range of less than 5/95,
Conversely, as shown in sample material (5), in a range exceeding 40/60, press workability deteriorates.

Claims (2)

[Claims] (1) A chromate film with a chromium adhesion amount of 5 to 200 mg/m^2 and a film thickness of 0.3 to 3μ containing a water-dispersible lubricant additive from the bottom layer on the plated surface of a steel plate such as a zinc-based plated steel plate.
A rust-proof lubricating steel sheet formed with an organic composite silicate film of m. (2) The organic resin constituting the organic composite silicate is an acrylic copolymer, and in the organic composite silicate film,
The rust-preventing lubricant according to claim (1), which contains one or more oxyacids or oxyacids of elements selected from the group consisting of molybdenum, tungsten, vanadium, tin, boron, and silicon. steel plate.