JP3331013B2 - Cold rolling oil composition for titanium plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold rolling oil composition for a titanium plate, and more particularly, to an emulsion type cold rolling for a titanium plate used in a cold tandem rolling mill, which is excellent in lubricity and surface quality. It relates to an oil composition.

[0002]

2. Description of the Related Art Conventionally, cold rolling of a titanium plate has been performed using rolling equipment such as a small-diameter multi-stage roll rolling mill for stainless steel. This is because the deformation resistance of titanium is as high as that of stainless steel, and in particular, in forming a titanium plate, the rolling reduction of the rolling mill is made smaller than that of stainless steel, and the rolling speed is performed at a low speed of 200 m or less per minute. I have. The rolling oil used at this time is also usually used in combination with stainless steel rolling oil, for example, mineral oil, natural fats and oils, synthetic esters and mixed oils of these oils with an oiliness improver, neat Rolling oil for stainless steel has been substituted.

However, these rolling oils for metals have poor lubricity on titanium plates, and intense seizure occurs between the titanium plates and the rolling rolls during rolling due to friction. By reducing the rolling reduction and performing multi-pass rolling, a titanium plate of the required thickness is produced.

On the other hand, when a titanium plate is rolled and produced by a cold tandem rolling mill, there is an advantage that productivity is improved and production cost can be reduced. However, when used in neat like conventional oil, a fire is not desirable, and there is no cold rolling oil for emulsion type titanium plate, and the above-mentioned problem is caused by using cold rolling oil for emulsion type steel. There is a problem in that only those having poor sheet surface properties can be obtained.

As a method for solving such problems, for example, a rolling method using a rolling oil described in JP-A-54-145349 and a rolling oil composition described in JP-B-62-14559 have been reported. However, when applied to a cold tandem rolling mill for titanium plates, this was not always enough to solve the above-mentioned problem. Further, even if a method using a surface film as disclosed in JP-A-62-33005 is applied to a cold tandem rolling mill, the film almost completely disappears in the rolling of the first stand, and the conventional stand in the finished final stand does not. The same problem occurs and it is not a fundamental solution.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for producing a fire, severe seizure and crack-like surface defects which cannot be avoided by conventional rolling oil when a titanium plate is rolled by a cold tandem rolling mill. It is an object of the present invention to provide an emulsion-type rolling oil for a cold tandem rolling mill for a titanium plate that solves problems such as safety, has excellent lubricity, and does not cause defects on the titanium plate surface. is there.

[0007]

In view of the above situation, as a result of intensive studies to obtain a cold rolling oil for a titanium plate suitable for a cold tandem rolling mill, an oil-based lubricating oil containing a specific ester compound was added. By making the oil component into an emulsion using a specific polymer compound, it is possible to obtain a cold rolling oil for titanium plates that is safe, has excellent lubricity, and does not cause defects on the plate surface during rolling of titanium plates. That is, the present invention has been completed.

That is, the present invention provides the following components (a) to
(C), (a) 26.4 to 90 parts by weight of fats and oils, (b) esters of polyols and dimer acids or polymer acids of higher aliphatic unsaturated acids having 16 to 20 carbon atoms, and free Has a carboxyl group or a hydroxyl group having 12 carbon atoms
10 to 70 parts by weight of one or more ester compounds having a molecular weight of 750 to 7,500, which are esterified with a monohydric alcohol or monohydric fatty acid having a molecular weight of from 22 to 22;

Embedded image (Wherein R ¹ represents a hydrogen atom or a methyl group; R ² and R ³
Represents an alkyl group having 1 to 3 carbon atoms, and A represents -O- or -NH
-, M represents an integer of 1 to 3), a homopolymer of a monomer represented by the formula (1), a copolymer of two or more of these monomers, or one or more of the monomers and (meth) acrylic acid, or a salt thereof. , A copolymer thereof with one or more alkyl esters or alkyl amides thereof, having an average molecular weight of 10,000 to 1,
A cold rolling oil composition for an emulsion-type titanium plate, comprising 0.05 to 3 parts by weight of one or more of a polymer compound or a salt thereof in the range of 1,000,000. Things.

[0009]

Embedded image

(Wherein R ¹ represents a hydrogen atom or a methyl group;
R ² and R ³ represent an alkyl group having 1 to ³ carbon atoms, and A represents —O
-Or -NH-, m is an integer of 1 to 3), a homopolymer of a monomer represented by the formula (I) or a copolymer of two or more of these monomers, or one or more of these monomers and (meth) acryl A copolymer of at least one of an acid, a salt thereof, an alkyl ester thereof and an alkyl amide thereof, having an average molecular weight of 10,
0.05 to 3 parts by weight of one or more of the high molecular compounds or salts thereof in the range of 000 to 1,000,000,
The present invention provides a cold rolling oil composition for a titanium plate, characterized by containing:

The fats and oils used as the component (a) of the rolling oil of the present invention include, for example, beef tallow, lard, palm oil, coconut oil, fish oil and the like. In the present invention, the use of a mineral oil reduces lubricity, and the use of a synthetic ester such as a monoester or a diester increases the cost and reduces the lubricity.

The mixing amount of the component (a) with the rolling oil is 30 to 9
0% by weight, especially 30-70% by weight is preferred.

The dimer acid or polymer acid as a component of the ester compound of the component (b) of the rolling oil of the present invention is a dimer acid or polymer acid of a higher aliphatic monoenoic acid or dienoic acid having 16 to 20 carbon atoms, For example, a dimer acid or a polymer acid of an acid such as zomaric acid, oleic acid, linoleic acid, and gadolinic acid can be used. Examples of polyols include propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, butanediol, pentanediol, hexanediol, polypropylene glycol, polyethylene glycol, polyoxypropylene-polyoxyethylene-glycol, and trimethylol. Examples include propane, pentaerythritol, glycerin, sorbitol, polyglycerin and the like.

When there is a free carboxyl group in the ester formed from the dimer acid or polymer acid and polyols, this is esterified with a monohydric alcohol having 12 to 22 carbon atoms. As this monohydric alcohol,
Examples include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol and the like. When there is a free hydroxyl group in the ester, it is esterified with a monovalent fatty acid having 12 to 22 carbon atoms. Examples of the monovalent fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, and behenic acid.

The ester compound of the component (b) of the rolling oil of the present invention must have a molecular weight in the range of 750 to 7,500. If the molecular weight is smaller than 750, the lubricating properties are poor, and the molecular weight is lower than 7,500. If it is large, the solubility in the compounding system will be worse, and the viscosity will be high and handling will be difficult,
Not preferred.

The amount of the component (b) in the rolling oil is 10 to 7
0% by weight, particularly preferably 30 to 50% by weight, and if it is less than 10% by weight, the lubricating property of the rolling oil is reduced. In addition, it is not economical because the effect corresponding to the compounding amount cannot be expected.

In the polymer compound of the component (c) of the rolling oil of the present invention, specific examples of the monomer represented by the general formula (1) include, for example, dimethylaminomethyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl methacrylate, Examples thereof include diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylamide, diethylaminomethyl acrylamide, and diethylaminopropyl methacrylamide.

In the (meth) acrylic acids copolymerized with the above-mentioned monomers, the salts thereof include, for example, alkali metals,
Ammonium, alkylamine, polyoxyethylene alkylamine, alkanolamine and the like; examples of the alkyl ester thereof include butyl acrylate, lauryl acrylate, methyl methacrylate, lauryl methacrylate, stearyl methacrylate and the like; Is, for example, acrylamide, dimethylacrylamide, methacrylamide and the like.

The high molecular compound which is the component (c) of the rolling oil of the present invention has an average molecular weight of 10,000 to 1,000,000.
It is necessary to be within the range of 0, and when it is less than 10,000, the stability when emulsified and dispersed as an emulsion is poor, and when it exceeds 1,000,000, the stability of the polymer compound itself is maintained. It is difficult to do this, which is not desirable.

Examples of the acid which forms a salt with the above-mentioned polymer compound include acetic acid, butyric acid, caproic acid, caprylic acid, glycolic acid, succinic acid, tartaric acid, phosphoric acid, butyl acid phosphate, octyl acid phosphate, boric acid and the like. Can be

The component (c) of the rolling oil of the present invention can be used singly or as a mixture of two or more. The compounding amount in the rolling oil is 0.05 to 3.0% by weight, particularly 0.05 to 3.0% by weight. 1.0
% By weight is preferred. If it is less than 0.05% by weight, the emulsion dispersibility of the emulsion decreases, and if it exceeds 3.0% by weight, the lubricating properties of the rolling oil decrease and the seizure resistance also undesirably decreases.

In the rolling oil of the present invention, the above-mentioned essential components (a) to
In addition to (c), if necessary, known additives, for example, an extreme pressure agent for improving seizure resistance, a rust / corrosion inhibitor, an antioxidant, an antiseptic / antifungal agent, and improving initial emulsifiability. An emulsifier or the like can be added for the purpose.

Examples of the phosphorus extreme pressure agent include monooctyl phosphate, monolauryl phosphate, monooleyl phosphate, dibutyl phosphate, dioctyl phosphate, dilauryl phosphate, dioleyl phosphate, tributyl phosphate, trioctyl phosphate, trilauryl phosphate, trioleyl Phosphate, tricresyl phosphate, monooctyl phosphite, monolauryl phosphite, monooleyl phosphite, dibutyl phosphite, dioctyl phosphite, dilauryl phosphite, dioleyl phosphite, tributyl phosphite, trioctyl phosphite, tri Lauryl phosphite, trioil phosphite and the like. Examples of the sulfur-based extreme pressure agent include sulfurized fats and oils such as sulfurized lard and sulfurized tallow, dipentene sulfide, sulfided olefin, dibenzyldisulfide, ditertiarybutene disulfide, zinc-dialkyldithiophosphate, and zinc-dialkyldithiocarbamate. No.

These extreme pressure agents are added in an amount of 0.5 to the total amount of rolling oil.
It is preferable to add the extreme pressure agent in an amount of 0.3 to 5% by weight. If the blending amount in the rolling oil is less than 0.5% by weight, the improvement of seizure resistance is small, and if it exceeds 10% by weight, it becomes expensive and improvement of seizure resistance corresponding to the increase cannot be expected.

As the rust preventive / anticorrosive, for example, alkenyl succinic acid or its derivative, fatty acid such as oleic acid, ester such as sorbitan monooleate, and other amines can be used. Up to 2% by weight.

As the antioxidant, for example, 2,6
Phenolic compounds such as -di-tert-butyl p-cresol, aromatic amines such as phenyl α-naphthylamine and the like can be used, and these can be added up to 5% by weight based on the total amount of rolling oil.

Further, as the emulsifier, for example, an anionic surfactant such as petroleum sulfonate sodium salt, a nonionic surfactant such as polyoxyethylene nonyl phenyl ether and the like can be used. Up to 5% by weight can be added.

The rolling oil of the present invention is used after being diluted with water. The dilution ratio at this time is not particularly limited, but it is preferable that the concentration of the composition is 3 to 20% by weight. If it is less than 3% by weight, a sufficient effect as a rolling oil cannot be obtained, and if it exceeds 20% by weight, the effect corresponding to the increase cannot be expected.

[0029]

The rolling oil of the present invention has an appropriate particle size and its particle size distribution is stable and can maintain a uniform emulsified and dispersed state.
Throughout, the emulsified state is stable, and the appropriate amount of high seizure resistant base oil spreads evenly in the roll bite of the rolling mill, leaks well and has excellent lubricity, so there is little seizure, and In addition, since an increase in the interface temperature between the roll and the titanium plate can be avoided, crack-like surface defects do not occur on the surface of the titanium plate.

[0030]

The cold rolling oil for titanium plate of the present invention has high safety without causing fire and has excellent lubricity as compared with conventional rolling oil.
It has the features of preventing temperature rise during rolling, preventing seizure and crack-like surface defects, and enabling stable production of products with excellent sheet surface quality at low cost.

[0031]

Next, the present invention will be described by way of examples, which should not be construed as limiting the invention thereto. The rolling oils used in the examples are as follows.

[0032]

[Table 1]

The ester, polymer compound and nonionic surfactant of the above composition mean the following.

Ester (A): polymeric acid of oleic acid (dimer acid: polymer acid of trimer acid or higher = 8: 2)
Ester obtained by heat condensation of 100 g and 12 g of diethylene glycol with 38 g of stearyl alcohol (acid value 8, hydroxyl value 6, average molecular weight 1,800) Ester (B): tall oil fatty acid 100 g of polymer acid (dimer acid: polymer acid of trimer acid or higher = 6: 4)
And an ester obtained by heat-condensing an ester obtained by heat-condensing 50 g of pentaerythritol with 304 g of oleic acid (acid value 3, hydroxyl value 6, average molecular weight 2,50)
0) Ester (C): 100 g of a polymer acid of oleic acid (dimer acid: polymer acid of trimer acid or higher = 7: 3) and 49 g of trimethylolpropane are heat-condensed with an ester obtained by heat condensation of 200 g of tallow fatty acid. (Acid value 5, hydroxyl value 5, average molecular weight 1,90)
0)

Polymer compound (A) Copolymer of dimethylaminoethyl acrylate / glycolic acid neutralized product / dodecyl methacrylate / sodium methacrylate = 3/1/1 (molecular weight = 100,000) Polymer compound (B) ... Glycolic acid neutralized homopolymer of dimethylaminopropylacrylamide (molecular weight = 3)
0,000) Polymer compound (C): Copolymer of dimethylaminoethyl methacrylate phosphoric acid neutralized product / sodium acrylate = 6/1 (molecular weight = 600,000) Polymer compound (D): Diethylaminoethyl methacrylate alone Caprylic acid neutralized polymer (Molecular weight = 30,000)

Nonionic surfactant (A): polyoxyethylene nonyl phenyl ether (HLB = 12.4) Nonionic surfactant (B): polyoxyethylene sorbitol tetraoleate (HLB = 11.8)

Example 1 Single Pass Rolling Test Invention Product No. Nos. 1 to 7 and comparative product Nos. A single pass rolling test was performed using rolling oils 1 and 2, and the rolling lubricity of each rolling oil was measured. Table 3 shows the results.

[0038]

[Table 2] (Equipment) Two-high rolling mill: 400 mmφ x 100 mm width, SUJ-2, H
s = 95 (rolling conditions) Rolled material: pure titanium material (CA33, 3.0 mm thickness × 50 mm width × 500 mm length) Roll roughness: Ra = 0.06 to 0.10 μm (adjusted with abrasive paper) Rolling speed: 500 m / Min Rolling reduction: 20%, 30% Rolling number: 2 rolls for each rolling reduction (rolling oil condition) Oil concentration: 4% by volume Liquid temperature: 60 ° C Stirring condition: 8000 rpm with homomixer Spraying amount: 2 liter / min

[0039]

[Table 3]

Results From Table 3, it can be said that each rolling oil shows a uniform rolling load at a low rolling reduction of 20% and good rolling lubricity. However, when the rolling reduction is increased to 30%, Comparative product No. 1 to
The rolling load of the rolling oil of the invention No. 2 was significantly increased, while The rolling loads of the rolling oils 1 to 7 were stable even at a high pressure reduction rate, and showed extremely excellent rolling lubricity.

Example 2 Multi-pass rolling test Invention product No. Nos. 1 to 7 and comparative product Nos. A multi-pass rolling test was performed using the rolling oils Nos. 1 and 2 under the following conditions, and the surface quality of the titanium plate when the titanium plate was subjected to multi-pass rolling under high pressure with each rolling oil was evaluated and measured. Table 5 shows the results.

[0042]

[Table 4] (Apparatus) Two-high rolling mill: 400 mmφ x 100 mm width, SUJ-2, H
s = 95 (rolling conditions) Rolled material: pure titanium material (CA33, 3.0 mm thickness × 50 mm width × 500 mm length) Roll roughness: Ra = 0.09 to 0.10 μm (adjusted with abrasive paper) Rolling speed: 250 Reduction rate: 25% for the first pass, 23% for the second pass, 2 for the third pass
4%, 20% at 4th pass, 6% at 5th pass, 15% at 6th pass (rolling oil condition) Oil concentration: 5% by volume Liquid temperature: 55 ° C Stirring condition: 8000 rpm with homomixer Spraying amount: 2 liter / min

[0043]

[Table 5]

Results As shown in Table 5, in the titanium plate rolling in the multi-pass rolling under high pressure in this test assuming cold tandem rolling, the comparative product No. 1-2
When rolling oil was used, scratches were generated on the surface of the titanium plate. No flaws were observed on the surface of the titanium plate rolled using rolling oils Nos. 1 to 7.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10M 101: 04 C10M 129: 74 129: 74 149: 02 149: 02) C10N 30:06 C10N 30:06 40:24 Z 40: 24 (72) Inventor Yuichi Haraguchi 59 Katsuhara-cho, Katsuhara-ku, Himeji-shi, Hyogo Prefecture Katsuhara Apartment 162 Building 25 (72) Inventor Takehiko Ichimoto 136-16 Enohara, Wakayama-shi, Wakayama Prefecture (72) Inventor Wakayuki Kamada Wakayama Prefecture 2-8-15 Nishihama, Wakayama City (72) Inventor Koichi Kawashita 1450 Nishihama, Wakayama City, Wakayama Prefecture (72) Inventor Kenichi Miyamoto 1450 Nishihama, Wakayama City, Wakayama Prefecture Examiner Masahiro Yamamoto (56) References JP-A 62-33006 JP, A) JP-A-61-213294 (JP, A) JP-A-62-13495 (JP, A) JP-A-59-232187 (JP, A) JP-A-63-46298 (JP, A) 54-145349 (JP, A) JP-A-62-233005 JP, A) (58) investigated the field (Int.Cl. ^7, DB name) C10M 169/04 C10M 101/04 C10M 105/38 C10M 107/42 C10M 129/74 C10M 149/02 C10M 149/06 C10M 159 / 08 C10M 173/00 C10N 30:06 C10N 40:24 B21B 27/10 B21B 45/02

Claims (1)

(57) [Claims] 1. The following components (a) to (c), (a) 26.4 to 90 parts by weight of fats and oils, and (b) dimer acid or polymer of a higher aliphatic unsaturated acid having 16 to 20 carbon atoms. An ester of an acid and a polyol, wherein the free carboxyl group or hydroxyl group has 12 carbon atoms.
10 to 70 parts by weight of one or more of ester compounds having a molecular weight of 750 to 7,500, which are esterified with a monohydric alcohol or monovalent fatty acid having a molecular weight of from 22 to 22; ] (Wherein R ¹ represents a hydrogen atom or a methyl group; R ² and R ³
Represents an alkyl group having 1 to 3 carbon atoms, and A represents -O- or -NH
-, M represents an integer of 1 to 3), a homopolymer of a monomer represented by the formula (1), a copolymer of two or more of these monomers, or one or more of the monomers and (meth) acrylic acid, or a salt thereof. , A copolymer thereof with one or more alkyl esters or alkyl amides thereof, having an average molecular weight of 10,000 to 1,
A cold rolling oil composition for an emulsion type titanium plate, comprising 0.05 to 3 parts by weight of one or more of a polymer compound or a salt thereof in the range of 1,000,000.