TW200404887A - Cold rolling oil composition - Google Patents

Abstract

This invention provides a cold rolling oil composition comprising a base oil loaded with 0.5 to 30 mass% of a diester, in which the diester is obtained from an aliphatic dicarboxylic acid of C12-C28 having a main skeleton constituted of a saturated or unsaturated hydrocarbon chain, and an aliphatic alcohol of C1-C9, and 0.01 to 5.0 mass% of a phosphorus compound. The cold rolling oil composition is excellent in anti-heat-scratching properties (rolling properties) and can suppress gloss irregularity of rolled plate.

Description

200404887 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a cold-rolled oil composition. In more detail, it can improve heat-resistant scratch resistance (rollability), and can particularly suppress rolling of stainless steel. Cold rolling oil composition obtained from unevenness of plate gloss. [Previous technology] In the rolling of metal materials, the rolling delay is normally performed, and a certain coloration phenomenon of a roller coating is generated by the operation of the rolling part of the rolling material. The coating of this roller is that the operating roller often directly contacts the calendered material, so it is greatly related to the calenderability and the surface properties of the rolled product. The operation roller system makes the metal material expand by rolling, and the thermal expansion of friction and processing heat causes uneven rolling pressure in the width direction of the plate, and uneven coating of the roller is prone to cause uneven gloss, especially by high standards. The pressing delay of metallic materials such as stainless steel with the required surface quality causes great problems. However, in the rolling of hard metal materials such as stainless steel, the contact area between the material and the material is reduced, and a small-diameter roller having a high unit load per unit area is used as a roller. However, a small roller diameter reduces the rigidity of the roller itself, so it is necessary to use a large-diameter middle roller and a back-up roller for reinforcement. Known calenders in this form are, for example, multi-roll calenders. In this multi-roll calender, the back-up rolls are divided into five or more rolls in the axial direction, and these are called split back-up rolls. This split back-up roll has a crown adjustment function made of a specially designed cylindrical roller bearing. The squeeze amount of each bearing can be independently operated by an eccentric bushing sequence. Therefore, the roller can be operated -4- (2) (2) 200404887 Make various crown models, and also control the shape of the rolled plate. The calender in the form of a split backing roller is a part of the intermediate back roller that is in contact with the operating roller and the non-contacting portion. Therefore, the foregoing causes of uneven coating of the roller are caused. . However, this roll coating is not the cause of uneven gloss of the surface of the rolled plate which is copied to the rolled plate. In addition, those who perform the rolling oil performance used for the rolling process of this metal material are required to have good rolling properties, that is, those who obtain a high reduction rate under a low pressure rolling load, and who do not generate thermal scratches under strict conditions . [Summary of the Invention] Under the circumstances, the present invention is to provide a method for reducing unevenness of a rolled plate caused by uneven coating of a divided backing roller and reducing unevenness of the coating of the roller in the width direction of the operating roller. Those with uneven gloss on rolled sheets, and cold rolling oil compositions that can improve heat-resistant scratch resistance (calenderability) are targeted. The present inventors carried out a precise investigation on a cold rolling oil composition having such a good function. As a result, they found that the base oil contains branched aliphatic dicarboxylic acids and linear fatty acids in a specific ratio in a predetermined ratio at the same time as the base oil. The purpose of the group alcohol can be achieved by obtaining a composition of a diester, a monoester having a carbon number in a specific range, and a phosphorus-based compound. The present invention has been completed based on this finding. That is, the present invention provides (1) an aliphatic dicarboxylic acid having a carbon number of 6 to 28 and a fatty alcohol having a carbon number of 1 to 9 containing a base oil containing (A) a saturated or unsaturated hydrocarbon chain. 0.5 to 30% by mass of the diester and (c) 0.01 to 5.0% by mass of the phosphorus-based compound are the cold rolling oil compositions characterized by (3) (3) 200404887 (2) the second component of (A) The hydrocarbon chain of the aliphatic dicarboxylic acid in the ester is a branched chain (the cold rolling oil composition contained in the (II) (3) 0.5 to 40% by mass of the monoester containing (B) carbon number of 13 to 48 as It is characterized by the cold rolling oil composition contained in (1) (4) (A) in the diester of the component, the aliphatic dicarboxylic acid is composed of an aliphatic dicarboxylic acid having a carbon number of 12 to 28 and a carbon number of 1 to In the diester obtained from the linear aliphatic alcohol of 6, the cold rolling oil composition (1) contained in the (1) (5) (A) component of the diester, the aliphatic dicarboxylic acid is a saturated aliphatic diresidual acid. In the cold rolling oil composition contained in (1), the phosphorus compound of the component (6) (C) is at least one selected from the group consisting of orthophosphate, its amine salt, and alkyl thiophosphate salt. The cold rolling oil composition contained, and (7) (C) phosphorus The substance is the cold rolling oil composition contained in (1) of the orthophosphate amine salt. [Best Mode for Carrying Out the Invention] As the base oil in the cold rolling oil composition of the present invention, mineral oil and / or Synthetic oil. As the mineral oil, various examples can be listed. For example: those who paraffin-based crude oil, intermediate-based crude oil or naphthalene-based crude oil are distilled at atmospheric pressure, or the residue distilled at atmospheric pressure is distilled under reduced pressure. Distillate oil obtained afterwards, or refined oil obtained by refining according to the usual method, such as: solvent refined oil, hydrogenated refined oil, dewaxed oil, white clay treated oil, etc. Also, as examples of synthetic oil: Poly-α-olefins with 8 to 14 carbons, olefins

Jh4 -6- (4) (4) 200404887 Copolymers (such as ethylene · propylene copolymers, etc.), or branched olefins such as polybutene, polypropylene, etc. This hydrohydride can also be used as a polyol ester (trihydroxyl Fatty acid esters of methyl propane, fatty acid esters of pentaerythritol, etc.), ester compounds, alkanes, etc. As the base oil in the present invention, one kind of the mineral oil or two or more kinds of the combination may be used, and one of the synthetic oils or two or more kinds of the combination may be used. In addition, one or more kinds of the mineral oil and one or more kinds of the synthetic oil may be used. As the base oil, a kinematic viscosity at a temperature of 40 ° C is preferably in the range of 1 to 30 mm2 / S. When the kinematic viscosity is less than 1 mm 2 / s, the ignition point is low, and there is a danger that the fire may increase due to ignition. On the contrary, if it exceeds 30 mm 2 / s, oil dents will be generated on the surface of the rolled plate, and the gloss will be reduced, resulting in Inappropriate conditions such as poor winding. A more ideal kinematic viscosity is 4 to 20 mm 2 / s. In the composition of the present invention, as the component (A), its main skeleton is obtained by using an aliphatic dicarboxylic acid having 6 to 28 carbon atoms and an aliphatic alcohol having 1 to 9 carbon atoms formed from a saturated or unsaturated hydrocarbon chain. Diester. When the aliphatic dicarboxylic acid has a carbon number of less than 6, the heat scratch resistance is deteriorated. On the other hand, when it exceeds 28, the solubility of the diester is deteriorated particularly when a low-viscosity base oil is used. The ideal carbon number is preferably 12 to 28, more preferably 14 to 24, and particularly preferably 16 to 20. The aliphatic dicarboxylic acid is preferably one having a branched shape. The presence of the branched shape improves the solubility of the diester and makes it easy to obtain the advantages of a rolled oil composition having desired properties. In the present invention, as the aliphatic dicarboxylic acid, a saturated or unsaturated one can be arbitrarily used, and among them, a saturated aliphatic dicarboxylic acid is more preferable. As (5) (5) 200404887 The saturated aliphatic dicarboxylic acid is as follows; general formula (I) HOOC- (CH2) m—CH- (CH2) n-COOH (CH2) kCH3 (where k represents 0 Integers of ~ 3, m and n represent integers of 1 to 23, and k, ⑺ and η add up to integers of 8 to 24.) The compounds shown are ideal examples. In the present invention, the aliphatic dicarboxylic acid having 6 to 28 carbon atoms formed by the saturated or unsaturated branched hydrocarbon chain as the main skeleton of the diester used for the component (A) is exemplified by the following chemical formula H? C- (CH2) 5-CH- (CH2) i〇-COOH CH2CH3 (C = 20) HOOC-(CH2) 5-CH— (CH2) 2—CH = CH- (CH2) e-COOH CH = CH2 ( C = 20) HOOC ~ (CH2) 5—CH— (CH2) 6—COOH CH2CH3 (C = 16) HOOC, (CH2) 5H— (CH2) 6_COOH CH = CH2 (C = 16)

HOOC—CH- (CH2) 5-COOH (0H2) 3-CH3 (C = 12)

Examples of compounds such as HOOC-(CH2) S-〒 = CH-(CH2) 2-CH = 〒 (CH 幽 一 CO〇OH CH3 CH3 (C === 22)) (6) (6) 200404887 In addition, as the aliphatic alcohol, those having a carbon number of 1 to 9 can be used. When the number of carbons exceeds 9, the solubility of the diester becomes poor. The ideal number of carbons is 1 to 6; 4. Also, it is preferable that the aliphatic alcohol is linear. When it has a branched chain, the heat-resistant scratch resistance will be deteriorated. Specific examples of the linear alcohol include: methanol, ethanol, Examples of n-propanol, n-butanol, etc. In the present invention, as the component (A), a diester obtained from the aliphatic dicarboxylic acid and an aliphatic alcohol is used, and the diester may be used alone One type may be used in combination of two or more types. The content of the diester in the rolling oil composition is selected in the range of 0.5 to 30% by mass. If the content is less than 0.5% by mass, it will not be sufficient It exerts the effects of reducing the unevenness of gloss of the rolled sheet and improving the heat-resistant scratch resistance, which cannot achieve the purpose of the invention. On the contrary, when it exceeds 30% by mass, the amount ratio cannot be improved, which is unfavorable. Economic aspect. Ideally, the content of the diester is 1-20 mass. / 0, especially 1-15 mass ^. Is more preferred. In the composition of the present invention, the number of carbons contained as the component (B) A monoester of 13 to 48 is preferred. After using the diester of the component (a), the monoester can reduce the unevenness of gloss and improve the resistance to heat scratches than when the diester is used alone. The use of this monoester can reduce the amount of diesters. As examples of monoesters of the (B) component, such as: general formula (j I) RCOOR1 .... (II ) -9- (7) 200404887 (where r is an alkyl group having 11 to 22 carbons, R1 is an alkyl group having 1 to 25 carbons, and the total carbon number of R and R1 is 12 to 47.) Examples of compounds. Ideally, the number of carbons of the monoester represented by the general formula (I1) is 13 to 36. Specific examples of the monoester include methyl stearate, butyl stearate, and stearin. Examples of octanoic acid ester, octyl palmitate, etc., among which the performance of butyl stearate and easy to obtain surface are preferred. In the present invention, as the component (B), one kind of this monoester can be used alone, or it can be used alone. Combine 2 or more types In addition, the content of the monoester in the rolling oil composition is preferably 0.5 to 40% by mass. When the content is less than 0.5% by mass, the effects of reducing the unevenness of the gloss of the rolled plate and improving the heat-resistant scratch resistance cannot be exerted. However, it cannot achieve the purpose of the invention. On the other hand, when it exceeds 40% by mass, the amount ratio cannot be improved, which is disadvantageous to the economic aspect and deteriorates its low-temperature fluidity. Ideally, the content of the monoester is 3 to 30. The mass% is preferable, and especially 5 to 20 mass is more preferable. In the composition of the present invention, a phosphorus-based compound is used as the (C) component. This phosphorus-based compound is not particularly limited, and orthophosphates, amine salts, alkylthiophosphoric salts, and the like can be generally used, and among them, the amine salt of orthophosphate is preferred. As an example of the orthophosphate, the formula (111) 2 〇 < in) R2- 丨 丨 4 ^ / P-0-R4 r3-o ^ -10- (8) (8) 200404887 is shown Examples of compounds. In the orthophosphate ester represented by the general formula (III), 'R2, R3, and R4 are each a hydrogen atom or a hydrocarbon group having 4 to 20 carbon atoms, which may be the same or different from each other', but at least one of them is carbon. A hydrocarbon group of 4 to 20 is preferred. Examples of hydrocarbon groups having 4 to 20 carbon atoms are: linear, branched or cyclic alkyl or aliphatic alkenyl groups having 4 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. Examples include alkylaryl groups of 20 and arylalkyl groups having 7 to 20 carbon atoms. Among them, an alkylaryl group having 7 to 20 carbon atoms is more preferable. Specific examples are: butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, lauryl, myristyl, palmyl, stearyl, oleyl, fluorenyl, phenyl, methyl Examples include methylphenyl, cumyl, monomethyl, hexyl and phenethyl. Among them, methylphenyl and cumyl are particularly preferred. As an example of an orthophosphate amine salt, for example: a compound example represented by the general formula (IV) 0 (R50) aP- (〇H) 3.a * (NHbR63-b) 3-a… (IV) By. In the general formula (IV), R5 is preferably a hydrocarbon group having 4 to 20 carbons, more preferably a hydrocarbon group having 8 to 18 carbons, and more preferably a hydrocarbon group having 12 to 18 carbons. R6 is a linear, branched, or cyclic alkyl or aliphatic alkenyl group having 4 to 20 carbon atoms, preferably 8 to 18 carbon atoms, more preferably a straight chain having 12 to 16 carbon atoms , Branched, cyclic alkyl or aliphatic alkenyl. a and b are 1 to 2 respectively, plural R5 may be the same or different, and plural R6 may be the same or different from each other. The description of the hydrocarbon group of 4 to 20 carbons represented by R5 is the same as the description of the hydrocarbon group of 4 to 20 carbons in R2 to R4 of the aforementioned general formula (III). In addition, as -11-(9) (9) 200404887 R6, such as: butyl, pentyl, hexyl, cyclohexyl, octyl, decyl, lauryl, myristyl, palmyl, stearyl, Examples of oil-based, fluorene-based. In addition, as examples of alkylthiophosphoric salts, for example, various monothiophosphoric salts and dithio groups of which the alkyl group is a linear, branched, cyclic saturated or unsaturated group having 4 to 20 carbon atoms. Examples of phosphorus salts, trithiophosphate salts. Among them, the example of the alkyl group may be the same as the example group described by R6 in the general formula (IV). The (C) component phosphorus-based compound of the present invention may be used singly or in combination of two or more kinds. The content of the phosphorus compound in the rolled oil composition is selected in a range of 0.01 to 5.0% by mass. When the content is less than 0.01% by mass, the effect of controlling gloss unevenness cannot be effectively exerted. On the other hand, when the content is more than 0.5% by mass, the effect of the amount ratio cannot show the improvement of the effect, which is disadvantageous to the economic aspect. The content of the phosphorus-based compound is preferably 0.02 to 4% by mass, and particularly preferably 0.1 to 3% by mass. In the composition of the present invention, various additives, such as an antioxidant, an anticorrosive uranium agent, and an antifoaming agent, may be appropriately contained alone or in combination without impairing the purpose of the present invention. Examples of the antioxidant include amines such as alkylated diphenylamine, phenyl-α-naphthylamine, and alkylated-α-naphthylamine; 2,6-di-tertiary-butyl-p- Phenols such as cresol and sulphur, etc., as rust inhibitors and corrosion inhibitors such as: sorbitan ester, neutral alkali metal or alkaline earth metal sulfate, alkali metal or alkaline earth metal phenate, alkali metal Or alkaline earth metal salicylate, thiadiazole, benzotriazole and other examples. Examples of the defoamer include dimethyl polysiloxane and fluoroether. This is equal to -12- (10) (10) 200404887 if the total content of additives used when necessary is 10% by mass or less, and more preferably 5% by mass or less. In the rolled oil composition of the present invention, the viscosity is not particularly limited. Generally, in order to obtain lubricity and board surface gloss, it is preferably 1 to 20 mm2 / s, and more preferably 2 to 10 mm2 / s. The cold rolling oil composition of the present invention having this composition can exhibit the effects shown below. (1) The calender using the form of split back-up rolls can control the shape of the split back-up rolls to still reduce the uneven coating of the rolls and the uneven gloss of the rolled plate. That is, the shape and surface quality (uneven gloss) of the rolled product can be improved. (2) When the rolling speed is increased, the calorific value per unit time of the rolling delay becomes larger, the roller heat storage becomes larger, and the thermal expansion in the width direction of the plate is uneven. Therefore, uneven coating of the roller is easy to occur, and the gloss of the rolled plate is uneven. If the rolling oil composition according to the present invention is used, even if the rolling speed is increased, uneven gloss phenomenon is unlikely to occur. (3) Improve heat-resistant scratch performance. (4) Through (1) to (3), productivity and product quality can be improved at the same time. There is no particular limitation on the metal materials suitable for the cold rolling oil composition of the present invention, and stainless steel materials are more suitable for general metal materials. [Embodiment] Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples. -13- (11) 200404887 [Examples 1 to 9 and Comparative Example 5] (1) Preparation of cold-rolled oil composition for paraffin-based mineral oil with a dynamic viscosity of 8.0 mm 2 / s at 40 ° C After the total amount is based on the amount shown in Table 1, the components shown in Table 1 are blended, and then the refrigeration rolling oil composition is adjusted.

The ingredients used are as follows. Monoester: Butyl stearate diester 1: H00C- (CH2) 5 one 〒 (— (ch2) 10-cooh CH2CH3 branched aliphatic dicarboxylic acid and methanol mutual diester (use special fair 7-45674 Bulletin Table 1 A) Diester 2: Has

HOOC- (CH2) 6-C = CH- (CH2) 2-CH = C (CH2) e-COOH CH3 ch3 The branched aliphatic dicarboxylic acid and methanol are diesters of each other (use special fair 7-45 I) Table 1 of the 674 Bulletin I) Diester 3: Diisononyl adipate (DINA) TCP: Trisphenol phosphate salt amine salt: Phosphonium dioleate phosphate carbon number 12 to 14 alkylamine salt ( 2) The rolling test is performed under the rolling test conditions shown in Table 2, and the rolling test is performed according to the channel program shown in Table 3. The 3 channel holes are used to evaluate the uneven gloss of the high-speed rolling delay -14- (12) (12) 200404887 degrees. After pressing the roller (outer diameter 135mm, width 10mm) squeezed into the 4-channel hole at 19.6kN, the unevenness of the gloss between the contact part and the non-contact part of the divided roller is evaluated. The hot-scratch limit down-pressing rate was calculated for the 5-channel hole, and the hot-scratch performance was evaluated. (The 51st plastic processing joint lecture (2000.11.3 ~ 5) pre-draft collection, pages 303 ~ 304 "Simulation of uneven surface gloss after split rolls in stainless steel cold rolling") The results are shown in Table 1. Show. In addition, the gloss unevenness was evaluated by visual inspection in the following four stages. 〇: Uniform 1: Slight unevenness 2: Significant unevenness 3: Intensity unevenness -15- (13) 200404887 Table 1-1 Example 1 2 3 4 5 Monoester 15.0 15.0 15.0 15.0 15.0 Diester 1 3.0 3.0 3.0 3.0 3.0 Ingredient diester 2-one-one-composition diester 3-one one one (weight TCP 0.5 1-one 0.5% by weight) amine salt of phosphate one-0.5-0.5 C 8 trithiophosphoric acid salt One to one — 0.8 One 3 channel hole gloss unevenness 0 0 0 0 00 4 channel hole gloss unevenness 1 0 0 0 38.3 Evaluation of 5 channel hole heating scratch down pressure rate (%) 38.5 38.6 38.2 38.1 38.3

-16- (14) 200404887 Table 1-2 Example 6 7 8 9 Monoester 15.0 15.0 5.0 — Diester 1 One by One Ingredient Diester 2 3.0 3.0 One — Composition Diester 3 — One 25.0 30.0 (weight TCP — 0.5 1 — Amount%) Ammonium salt of phosphate ester 0.5 0.5 0.5 0.8 c8 Trithiophosphine salt one by one 3 channel pore gloss unevenness 0 0 0 0 4 channel pore gloss unevenness 0 0 0 0 evaluation 5 Channel hole heating scratch down pressure rate (%) 38.2 38.3 37.6 38.0

-17- (15) 200404887 Table 1-3 Comparative Example 1 2 3 4 5 Ingredient composition (% by weight) Monoester 15.0 18.0 15.0 15.0 Mono-diester 1 — _ 3.0 Mono-diester 2 — Mono-3.0 — diester 3 one one — 30.0 TCP — one one amine salt of phosphate ester one one one — c8 trithiophosphoric salt — one by one evaluation of 3 channel pore gloss unevenness 2 2 1 1 2 4 channel pore gloss Unevenness 2 2 2 2 2 5 Channel hole heating scratch down pressure rate (%) 18.3 19.0 38.2 38.4 38.1

-18- (16) 200404887 Table 2

Calendering test conditions Calender form 1 4-stage reversible calender Size 0 40x200mm Material SUJ-2 Actuating roll hardness H s95 Thickness Ra 0.05 μιη Backing roll size 0 200x200mm Material SUS304 (2B, 0 material) Calender size 1 .5tx50Wmmx ring tension 702N / mm2 oil temperature 4 0 ° C oil supply method 13 L / min single side oil supply on the inlet side-19- (17) (17) 200404887 Table 3 channel program calendar speed tension (kN) plate thickness Down Pressure Rate Channel (m / min) Front Back (mm) (%) 0 _ _ _ 1.500-1 50 9.8 9.8 1.145 23.7 2 250 9.8 9.8 0.925 19.2 3 400 8.8 8.8 0.785 15.1 4 50 7.4 7.4 0.670 14.6 5-1 100 4.4 4.4 0.570 14.9 5-2 100 4.4 4.4 0.540 19.4 5-3 100 4.4 4.4 0.510 23.9 5-4 100 4.4 4.4 0.490 26.9 5-5 100 4.4 4.4 0.460 3 1.3 5-6 100 4.4 4.4 0.440 34.3 5-7 100 4.4 4.4 0.420 37.3 5_8 100 4.4 4.4 0.400 40.3 [Industrial availability] The present invention provides a method for reducing uneven gloss of the rolled plate caused by uneven coating of the rolls of the split back-up rolls, and reducing Roller coating unevenness It can cause uneven gloss of the rolled plate and improve heat-resistant scratch resistance (rolling performance), and can provide a cold rolling oil composition suitable for rolling of stainless steel materials. -20-

Claims (1)

(1) (1) 200404887 Pick up and apply for patent scope 1 · A cold rolling oil composition, characterized in that it contains (A) a fat with 6 to 28 carbons in the main skeleton which is a saturated or unsaturated hydrocarbon chain 0.5 to 30% by mass of the diester and (C) 0.01 to 5.0% by mass of a phosphorus-based compound obtained from a group dicarboxylic acid and an aliphatic alcohol having 1 to 9 carbon atoms. 2. The cold rolling oil composition according to item 丨 of the application, wherein the aliphatic dicarboxylic acid hydrocarbon chain in the diester of the component (A) is branched. 3. The cold rolling oil composition according to item 1 of the scope of patent application, wherein the composition further contains 0.5 to 40 mass% of (B) a monoester having 13 to 48 carbon atoms. 4. The cold rolling oil composition according to item 1 of the scope of the patent application, wherein the aliphatic dicarboxylic acid in the (A) component diester is composed of an aliphatic dicarboxylic acid having 12 to 28 carbon atoms and a carbon number of 1 to 6 Diesters obtained from linear aliphatic alcohols. 5. The cold rolling oil composition according to item 1 of the application, wherein the aliphatic dicarboxylic acid in the (A) component diester is a saturated aliphatic dicarboxylic acid. 6. The cold rolling oil composition according to item 1 of the scope of patent application, wherein the (C) component phosphorus-based compound is at least one selected from the group consisting of orthophosphate, its amine salt, and alkylthiophosphoric acid salt. 7. The cold rolling oil composition according to item 1 of the application, wherein the phosphorus compound of the component (C) is an amine salt of an orthophosphate. 200404887 柒, (a) (two), the designated representative picture in this case is: None, simple description of the representative symbols of the elements in this case: 捌, if there is a chemical formula in this case, please reveal the chemical formula that can best show the characteristics of the invention: