JPH10152690A - Rust preventive press oil for galvanized steel plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multifunctional press oil for galvanized steel plate which can endow excellent pressing property, rust prevention, and degreasing with a once application of the oil. SOLUTION: This press oil comprises 30-90 pts. mass of at least one of mineral oil, fat and oil, and liquid synthetic oil as base oil, 1-20 pts. mass at least one of not less than 16C alkyl sulfonate, not less than 12C carboxylic acid, and its salt as a rust preventive additive, 1-20 pts. mass of trialkyl trirthiophosphate compd. as a lubricating additive, 1-20 mass % of at least one of fatty acid ester compd. contg. 5-15 mass % of S, sulfur bonded fat and oil, and a compd. which is made by bonding fat and oil with a 8-18C olefin by sulfur as a sulfur type extreme pressure additive, and 5-40 mass % of polyhydric alcohol full ester of lanolin fatty acid as an oiliness agent. And the ratio of the trialkyl trithiophosphite compd. and the sulfur type extreme pressure additive is 1:15-2:1, active sulfur content is not more than 0.5 mass %, saponification value is not more than 80mgKOH/g, and kinematic viscosity is 2-30mm<2> /s at 40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust-preventing press working oil (hereinafter simply referred to as a press working oil) for a steel sheet, and more particularly, to a cold-rolled steel sheet, an electrogalvanized steel sheet, a hot-dip galvanized steel sheet, a galvannealed steel sheet. The present invention relates to a rust-preventive oil for a steel sheet, which is applied to a steel sheet such as a plated steel sheet and has rust prevention, discoloration prevention, degreasing and press workability. If a low-viscosity base oil is used, it can be applied to a steel plate cleaning rust preventive oil (hereinafter simply referred to as a cleaning oil) used immediately before a pressing process of an automobile company.

[0002]

2. Description of the Related Art In the recent automobile industry, due to the long-term market demand for rust prevention of vehicle bodies, in order to make conventional rust-resistant steel sheets even more rust-proof, the weight per unit area of galvanizing increases and difficult workability becomes a problem. ing. Also, with the diversification of designs, the number of automobile parts having more complex shapes has increased, and the demand for press workability of steel sheets has been increasing.

[0003] The applicant of the present invention has developed a multifunctional press working oil for galvanized steel sheet, which is excellent in workability, discoloration resistance, rust prevention and degreasing property in pre-coating treatment with a single application of oil. To provide press working oil, Japanese Patent Publication No. 7-4247
No. 1 proposed a press working oil for galvanized steel sheet having the following configuration.

[0004] That is, the contents are mineral oil,
Fats, and with one or 65 to 95 parts by weight of two or more oils selected from liquid synthetic oils, as rust-preventive agent, C ₁₆ or higher alkyl sulfonates, the C ₁₂ or higher carboxylic acids and salts thereof 1 to 20 parts by mass of the selected compound, 1 to 20 parts by mass of a trialkyltrithiophosphite compound as a lubricating aid, and a fatty acid containing 5 to 15% by mass of sulfur as an inert type sulfur-based extreme pressure additive ester compounds, pressing oil which also serves as a rust preventive consisting of 1 to 20 parts by weight of one or more compounds and olefinic sulfur bond fats and oils and C ₈ -C ₁₈ selected from the compounds sulfur bond It is.

The press working oil has a content ratio of the trialkyltrithiophosphite compound to the inert type sulfur-based extreme pressure additive of 1:15 to 2: 1 by mass and an active sulfur content of 0.5% by mass. % Or less, and a viscosity of 5 to 30 mm ² / s at 40 ° C. for a galvanized steel sheet.

[0006] However, the above-mentioned invention has the rust-preventive properties and degreasing properties required of a press-working oil for galvanized steel sheets and, in the usual case, also has satisfactory press-workability.
Press workability for some difficult-to-process materials is insufficient,
In order to satisfy the recent demand for steel sheets, there has been a demand for further improving the press workability.

[0007] In addition, automobile manufacturers generally use cleaning oil immediately before the pressing process to prevent the occurrence of stars (scratching of steel sheets caused by dust, chips, etc.) generated when pressing the outer panel of an automobile. At this time, the press workability is reduced because the press working oil is replaced by the cleaning oil.
In order to improve the press workability of cleaning oil, simply replacing the base oil of conventional press processing oil with low viscosity is not sufficient in press workability, and it is necessary to improve press workability in cleaning oil as well. It was.

[0008] The combination of the press working oil and the cleaning oil has the same composition, but preferably differs only in the base oil. This is because it is necessary to consider the compatibility between additives when the press working oil and the cleaning oil are replaced.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems by using a single application of a multi-function press working oil for galvanized steel sheets, which provides press workability, rust prevention, An object of the present invention is to provide a press working oil for steel sheets having excellent degreasing properties. This press working oil has a small viscosity dependency, and is characterized in that the viscosity of the working oil can be easily adjusted by substituting the base oil according to the intended use.

[0010]

The present inventors have studied the press working oil for galvanized steel sheets which can solve the above-mentioned problems, and have obtained the following new knowledge. (A) A compound selected from an alkyl sulfonate, a carboxylic acid and a salt thereof is added to a press working oil as a rust preventive additive for imparting white rust resistance and red rust resistance. In addition, it is necessary to limit the amount of the rust preventive additive to prevent the degreasing property from being impaired.

(B) As a lubricating aid for keeping the press working performance at an appropriate level, the type of the trialkyltrithiophosphite compound to be blended with the base oil, the number of carbon atoms in the molecular structure thereof, the blending amount in the press working oil, etc. Need to be limited. (C) In order to maintain the press working performance to an appropriate level, it is necessary to limit the type of sulfur-bonded compound, the number of carbon atoms in its molecular structure, the content of active sulfur, and the amount of the sulfur-bonded compound in the press working oil. There is.

(D) In order to suppress the discoloration of the surface of the steel plate to be oiled, an inert type of sulfur-based extreme pressure agent is appropriate, and the content of active sulfur in press working oil is set to 0.5%. (% By mass, the same applies hereinafter). (E) In order to further enhance the press working performance of galvanized steel sheets and to enhance the press workability of cold-rolled steel sheets, the type of fatty acid ester to be blended with the base oil as an oil agent, the number of carbon atoms in its molecular structure and the press working It is necessary to limit the amount to be mixed with oil.

(F) White rust and red rust on the surface of the steel plate to be oiled are suppressed, and the degreasing property of the oiled oil film is not impaired.
The saponification value of the press working oil must be limited to 80 mgKOH / g or less. (G) In order to impart degreasing properties to the oil film of the pressing oil,
Limiting the viscosity of the processing oil to ² to 30 mm2 / s at 40C.

As a result of further study on the basis of the above-mentioned findings, a target press working oil meeting the above-mentioned demand has been completed. That is, the press working oil of the present invention has both rust prevention and lubricity, and its composition is as follows: (a) base oil, rust prevention additive, lubrication auxiliary agent, extreme pressure additive, and oil agent (B) As a limited range of each substance: 1) Base oil: 30 to 90 parts (parts by mass, hereinafter the same) of one or more selected from mineral oil, fat and liquid synthetic oil )

[0015] 2) anti-rust additives: C ₁₆ or higher alkyl sulfonates, are contained 20 parts of one or more compounds selected from C ₁₂ or higher carboxylic acids and salts thereof. 3) Lubricating aid: 1 to 20 parts of a trialkyltrithiophosphite compound is contained.

4) Extreme pressure additive: an inert type sulfur type extreme pressure additive, which is a fatty acid ester compound containing 5 to 15% of sulfur, a sulfur-bound fat or oil, a fat or oil and a C _{8 to} C ₁₈ olefin. From 1 to 20 parts of one or more compounds selected from sulfur-bonded compounds.

Further, in these formulations, the mass ratio of the trialkyltrithiophosphite to the inert sulfur extreme pressure additive is 1:15 to 2: 1, and the active sulfur content in the press working oil is Is set to 0.5% or less.

[0018] 5) Oily agent: be contained 5 to 40 parts of a full ester comprising a trivalent or higher alcohol lanolin fatty acids separated and purified from lanolin and C ₃ -C _8. further,
The requirement is that the saponification value of the press working oil formed by these blends be 80 mg KOH / g or less, and the viscosity of the working oil be ² to 30 mm ² / s at 40 ° C. Conventional press working oil for steel plate (Japanese Patent Publication No. 7-4)
2471) is a feature of the present invention in that an oil agent is newly added.

The base oil applied to the press working oil for steel sheets of the present invention may be any one or more selected from mineral oils, fats and oils, and liquid synthetic oils. Although the viscosity of the oil is not specified, the kinematic viscosity at 40 ° C. of the press working oil is set to 2 in order to keep the oil film removability after applying and working the press working oil.
It should be kept ~30mm ² / s, in order that the type of each component in the press processing oil, it is necessary to select a viscosity of the base oil in view of the such amount.

The kinematic viscosity of the pressing oil is 2 mm ² at 40 ° C.
If it is lower than 30 mm ² / s, the lubricating performance at the time of press working cannot be satisfactorily exerted. Conversely, if it is higher than 30 mm ² / s, the cleaning efficiency decreases and the oil film amount becomes more than necessary, which is uneconomical. It is not preferable because of the fact that the oil film after press working is deteriorated in cleaning and removability. In particular, the oil removal property at the joint part of the spot welding is deteriorated, and the oil easily oozes out from the joint part even after the cleaning, which adversely affects the surface treatment performed thereafter.

Next, the alkyl sulfonate added as a rust preventive additive is preferably C ₁₆ or more, and the carboxylic acid or carboxylate is preferably C ₁₂ or more. If the carbon number is less than this, the rust-preventing effect is insufficient, and specific examples include the following compounds.

Examples of the alkyl sulfonate include dinonyl naphthalene sulfonate metal salts (Ba, Ca,
Zn, Mg, Na, etc.) and amine salts, metal salts of didodecylbenzenesulfonic acid (Ba, Ca, Zn, Mg, Na)
And amine salts, metal salts of petroleum sulfonic acid and amine salts.

[0023] C ₁₂ or higher carboxylic acid or a salt thereof, for example Isoorein acid, oleic acid, dimer acid, alkenyl succinic acid, petroleum oxidized wax or a metal salt (Ba,
Ca, Zn, Mg, Na, etc.) and amine salts. C ₁₂
Examples of the nitrogen-containing compounds of the above carboxylic acids, for example benzotriazole, and a C ₁₂ or higher carboxylic acid compound of the imidazoline.

Of the above-listed compounds, particularly preferred are
Barium dinonylnaphthalenesulfonate, barium didodecylbenzenesulfonate, barium salt of petroleum oxidized wax and the like. The compounding amount of these rust-preventive components in the base oil is 1 to 20 parts, and if less than 1 part, the rust-preventive effect becomes insufficient. In addition, since it becomes difficult to wash and remove the oil film, the upper limit is 20 parts.

Next, a trialkyltrithiophosphite compound is suitable as a lubricating aid. Although these compounds are not specified, those represented by the following general formula are more preferred.

(1) Trialkyltrithiophosphite (RS) ₃ P (1) In the formula, R is a hydrocarbon group having 8 to 22 carbon atoms. Examples include octyl, lauryl, cetyl, palmityl, oleyl, stearyl, and synthetic oil-based groups such as isodecyl, tridecyl, and isostearyl.

(2) Trialkylcarboxytrithiophosphite (RCOOS) ₃ P (11) In the formula, R is a hydrocarbon group having 8 to 22 carbon atoms, and specific examples thereof include fatty acid octyl, lauryl, and cetyl. , Palmityl, oleyl, stearyl, synthetic oil-based isodecyl, tridecyl, isostearyl and the like.

The compounding amount of the compound is preferably 1 to 20 parts, and if it is less than 1 part, the press workability becomes insufficient, and the upper limit is 20 parts in order to prevent discoloration of the steel sheet after the pressing. Is preferred.

Next, the extreme pressure additive is an inert sulfur type extreme pressure additive, which is a sulfur-binding compound containing 5 to 15% of sulfur. That is, fats and oils, compounds that are sulfur bonds and olefinic sulfur-binding compound and fats and C ₈ -C _18, such as a fatty acid ester used. Particularly preferred examples of the selection of fats and oils, fatty acid esters, and olefins are shown below.

(1) Fats and oils are glyceride-based lard oil, rapeseed oil, chicken oil and the like represented by the following general formula. R ₁ COO is a group containing a C ₁₂ or higher unsaturated fatty acid as a main component.

(2) Fatty acid esters include orange rough oil, oleyl oleate, methyl oleate and the like. The general formula R ₁ COOR ₂ R ₁ is a fatty acid group as described above, and R ₂ is a C ₁ or higher aliphatic alcohol group.

[0032] (3) a sulfur binding level of the olefinic the compounds of C ₈ -C ₁₈ in order to impart pressure properties suitable electrode, it is necessary 5-15%, extreme pressure is insufficient at less than 5% On the contrary, if it exceeds 15%, the active sulfur content in the press working oil exceeds 0.5%, which is not preferable.

Next, the active sulfur content in the pressing oil is 0.5
% Or less and preferably more than 0.5%, the reactivity with the steel sheet surface is too strong, and the discoloration of the surface tends to become strong after press working. It is preferably at most 0.3%. In addition, the lower limit of the number of carbon atoms is all press workability,
In particular, it is determined in consideration of prevention of a decrease in press workability when the press working temperature of the steel sheet increases (70 to 100 ° C.).

The fatty acid ester is added as an oily agent for the most characteristic of the present invention is then made of tri- or higher alcohols lanolin fatty acids separated and purified from lanolin and C ₃ -C ₈ are preferred. If lanolin fatty acid is not used for the fatty acid, the press workability becomes insufficient, and if lanolin fatty acid having a large number of high melting points is insufficiently separated,
Viscosity is too high or storage stability is poor, causing precipitation. Specifically, it is preferable to set the melting point of lanolin fatty acid to 35 to 45 ° C.

The alcohol having three or more carbon atoms has a carbon number of C _8.
If the amount is too large, the viscosity becomes too high when blended in a press working oil. The trivalent or higher alcohol is, for example, glycerin or trimethylolpropane. It is pentaerythritol, and its ester is preferably a full ester. In the case of a part ester, the press workability is good, but it has a bad influence on the degreasing property in the coating pretreatment step.

Of the above-listed compounds, particularly preferred are
Trimethylolpropane full ester and pentaerythritol full ester. The compounding amount of the compound is 5
40 is preferable, and if it is less than 5 parts, press workability will be insufficient, and if it exceeds 40 parts, improvement in press workability cannot be expected. Also, the saponification value of the press working oil is 80mgKOH
/ G has an adverse effect on rust prevention and degreasing properties. In this case, the amount of the lanolin fatty acid ester is reduced to 5%.
It must be reduced within the range of 40 parts.

Next, a highly stable compound is formed by mixing the trialkyltrithiophosphite {(a)} with the inert type sulfur-based extreme pressure additive {(b)}. When the mixing ratio {(a) :( b)} is more than 1:15, the effect of improving the press workability is not obtained even if (b) is added in excess, and when the mixture ratio is less than 2: 1, the press workability is not improved. Good, but unfavorable because the rust-prevention property is reduced. Thus the range is 1:15 to 2: 1 and
More preferred is 1: 4 to 2: 3.

Further, in the press working oil of the present invention, less than a few% of an oil-soluble surfactant is added to enhance the oil film removability of the working oil, and if necessary, a pour point depressant,
It does not refuse to add an antioxidant, a viscosity index improver and the like.

[0039]

EXAMPLES Next, the effects of the present invention will be specifically described with reference to examples and comparative examples. Using test oils Nos. 1 to 5 of Examples of the present invention shown in Table 1, the test pieces were applied by a roll coater method, and the following deep drawing test, rust prevention test, and degreasing test were performed. Test oil Nos. 6 to 13 in Table 2 are comparative examples. The amount of oil applied was adjusted to be 2.0 ± 0.1 g / m ² .

[0040]

[Table 1]

[0041]

[Table 2]

The test methods and criteria are shown below. (1) Press workability test (deep drawing test) a. Test piece Material: Alloyed hot-dip galvanized steel sheet 60/60 (g / m
² ) Dimensions: 105mm (diameter) x 0.7mm (thickness) b. Tool Die diameter: 52.0 mm (diameter) Punch diameter: 50.0 mm (diameter) Punch shoulder radius: 5.0 mm c. Test conditions Drawing speed: 30 m / min Wrinkle holding load: variable d. Judgment Non-break limit wrinkle holding load The above non-break limit wrinkle holding load is measured, and determined according to the following table. The higher the non-rupture limit wrinkle holding load, the better the lubricity.

[0043]

[Table 3] Judgment table

(2) Rust prevention test (2) -1 Wetting test a. Test piece Material: Alloyed hot-dip galvanized steel sheet 60 × 60 (g / m
² ) Dimensions: 60mm x 80mm x 0.7mm b. Test conditions Wet test method (based on JIS K-2246 5.34) Temperature: 49 ± 1 ° C Relative humidity: 95% or more Time: 10 days c. Judgment: The degree of discoloration and rust generation of the test piece is judged according to the following table.

[0045]

[Table 4] Judgment table

(2) -2 Stack test a. Test piece Material: Alloyed hot-dip galvanized steel sheet 60/60 (g / m
² ) Dimensions: 70mm x 150mm x 0.7mm b. Test conditions Using a constant temperature and humidity tester Temperature: 49 ± 1 ° C Relative humidity: 95% or more Stacking force: 700N Period: 10 days c. Judgment: The degree of discoloration and rust generation of the test piece is judged in the same manner as in the wet test.

(3) Degreasing test a. Test piece Material: Galvannealed steel sheet 60 × 60 (g / m
² ) Dimensions: 70mm x 150mm x 0.7mm b. Adjustment of test pieces After applying each test piece, a stack of 700N was applied, and the temperature was adjusted to 50N.
The specimen was allowed to stand for 7 days in a thermo-hygrostat at 95 ° C. and a relative humidity of 95% to obtain a test material.

C. Test conditions Dip degreased in complete static bath. Degreasing agent: trade name Fine Cleaner L4480 [manufactured by Nippon Parkerizing Co., Ltd.], concentration 1.8%, temperature 40 ° C, time 5 minutes d. Judgment: After degreased test pieces were washed in running water for 30 seconds, they were judged by the water wetted area (%) after standing still in the room for 30 seconds. The judgment is as shown in the table below.

[0049]

[Table 5] Judgment table

(4) Detergency test a. Test piece Material: Alloyed hot-dip galvanized steel sheet 60/60 Dimensions: 70 mm x 150 mm x 0.7 mm b. Adjustment of test After applying 2 g / mm ^{2 of} rust preventive oil for steel plate to a test piece, put it horizontally and sprinkle 2 g / m ^{2 of} JIS No. 8 standard dust on the upper surface using a 200 mesh sieve. c. Test conditions The test oil is washed for 10 seconds as shown below.

D. Judgment This test piece was ultrasonically washed with petroleum ether, and 0.8 μm
And the residual dust is recovered. Cleaning rate [%] = {(W ₁ −W ₂ ) / W ₁ } × 100 W ₁ : initial dust adhesion amount, W ₂ : residual dust recovery amount.

[0052]

[Table 6] Judgment table

(5) Active sulfur content Implemented according to ASTM D1622. (6) Saponification value Implemented according to JIS K 2503 (7) Viscosity Implemented according to JIS K 2283 Tables 1 and 2 show the test results.

[0054]

As can be seen from Tables 1 and 2, the compositions of Examples of the present invention are superior to those of Comparative Examples in all of the press workability, rust prevention and degreasing properties.

As described above, the press working oil for steel sheets of the present invention can be used in the press working of cold rolled steel sheets and galvanized steel sheets.
With a single application of oil, excellent press workability over press oil provides discoloration resistance and rust prevention comparable to those of rust-preventive oil, and good degreasing in pre-coating treatment. .

Moreover, this press working oil has little viscosity dependency, and is characterized in that the viscosity of the working oil can be adjusted by substituting the base oil according to the intended use.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10M 135: 02 159: 06) C10N 20:00 20:02 30:12 30:20 40:24

Claims (3)

[Claims] As claimed in claim 1] base oil, mineral oil, fat, and a 30 to 90 parts by weight of one or more oils selected from liquid synthetic oils, as rust-preventive agent, an alkyl sulfonate or more C ₁₆ , a 1 to 20 parts by weight of one or more compounds selected from C ₁₂ or higher carboxylic acids and salts thereof, as a lubricant aid, and 1 to 20 parts by weight of the trialkyl trithiophosphite compounds, inert as the type sulfur-based extreme pressure additive, a fatty acid ester compound containing a sulfur 5-15 wt%, of one or more of the olefinic sulfur bond fats and oils and C ₈ -C ₁₈ selected from the compounds sulfur bond A rust-preventing press working oil comprising 1 to 20 parts by mass of a compound of formula (I) and 5 to 40 parts by mass of a polyhydric alcohol full ester of lanolin fatty acid as an oily agent, wherein the working oil is a trialkyltrithiol Content ratio of Sufaito compound and inert type sulfur-based extreme pressure additive in a weight ratio of 1: 15 to 2: 1
A zinc plating characterized by having an active sulfur content of 0.5% by mass or less, a saponification value of 80 mg KOH / g or less, and a kinematic viscosity of ² to 30 mm ² / s at 40 ° C. Rust-prevention and press-working oil for galvanized steel sheets that has both rust-preventive properties, washing-removal properties, and anti-discoloration properties applied to steel sheets. 2. The trialkyltrithiophosphite, which is represented by the following general formula, has a rust-preventing property, a washing-removing property and a discoloration-preventing property which are applied to the galvanized steel sheet according to claim 1. Rust prevention and press working oil for galvanized steel sheets. General formula (RS) ₃ P trialkyltrithiophosphite (RCOOS) ₃ P trialkylcarboxytrithiophosphite wherein R is a hydrocarbon group having 8 to 22 carbon atoms. 3. The lanolin fatty acid polyhydric alcohol full ester is obtained by mixing lanolin fatty acid separated and produced from lanolin with C ₃
Rust resistance suitable for galvanized steel sheet Claims claim 1 wherein a full ester of a trihydric or more alcohol -C _8, galvanized steel sheet rust which also serves as a washing removability and discoloration preventing property Pressing oil.