JP2005200610A - Cold-rolling oil composition and method for cold-rolling - Google Patents
Cold-rolling oil composition and method for cold-rolling Download PDFInfo
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Abstract
Description
本発明は、鋼などの鉄系金属、ステンレス鋼などの鉄合金、アルミニウム等の非鉄金属を圧延する時に用いる冷間圧延油組成物に関し、特に鉄鋼の直接給油式冷間圧延時に用いるのに好適な冷間圧延油組成物及びこれを用いた冷間圧延方法に関する。 The present invention relates to a cold rolling oil composition used when rolling a ferrous metal such as steel, a ferrous alloy such as stainless steel, and a non-ferrous metal such as aluminum, and particularly suitable for use in direct oil-type cold rolling of steel. The present invention relates to a cold rolling oil composition and a cold rolling method using the same.
鉄鋼のブリキ板等の薄板を圧延する際に使用される圧延油の給油には、直接給油式（ダイレクト給油）と循環給油式（リサーキュレーション給油）が用いられている。特に直接給油式の圧延油は、牛脂やパーム油等の天然油脂を、水に強制的に分散して材料やロールに給油されている（例えば、特許文献１参照）。この圧延油には、油脂単体、または脂肪酸のような油性剤の他、カチオン性高分子添加剤を添加し、給油された後、材料に付着し易い（油水分離し易い）状態にするなどの工夫がなされ、圧延操業されている場合がある（例えば、特許文献２及び特許文献３参照）。しかし、圧延ロールバイト内の鋼板材料温度は、圧延速度が速くなるにつれて高くなり、１５０℃以上の高温に達する場合が多い。このように、圧延操業条件が高温化、高速化、高圧下等の厳しい条件になると、材料とロール間で焼き付きが発生し、ヒートスクラッチなどと呼ばれる疵が材料に入る。そのため、従来は速度等を規制して操業する必要があった。 Direct oil supply (direct oil supply) and circulating oil supply (recirculation oil supply) are used to supply rolling oil used when rolling thin plates such as steel tin plates. In particular, the direct oil supply type rolling oil is forcibly dispersed in water with natural oils and fats such as beef tallow and palm oil and supplied to materials and rolls (for example, see Patent Document 1). In addition to oil alone or an oily agent such as a fatty acid, a cationic polymer additive is added to this rolling oil, and after being supplied with oil, it is easy to adhere to the material (easily separate from oil and water). There is a case where a device is devised and a rolling operation is performed (for example, see Patent Document 2 and Patent Document 3). However, the steel sheet material temperature in the rolling roll bite increases as the rolling speed increases and often reaches a high temperature of 150 ° C. or higher. Thus, when the rolling operation conditions are severe such as high temperature, high speed, high pressure, etc., seizure occurs between the material and the roll, and soot called heat scratch enters the material. For this reason, conventionally, it has been necessary to control the speed and the like.
本発明の目的は、冷間圧延油組成物を提供することであり、特に耐焼き付き性及び油水分離性に優れ、高速化、高圧下圧延等の厳しい操業条件下でも、材料とロール間で焼き付きの発生や、ヒートスクラッチなどと呼ばれる疵が材料に入ることがなく、そのため、速度等を規制して操業する必要のない冷間圧延油組成物、特に直接給油式冷間圧延油組成物を提供することである。
本発明の他の目的は、上記冷間圧延油組成物を使用した冷間圧延方法、特に直接給油式冷間圧延方法を提供することである。
An object of the present invention is to provide a cold-rolled oil composition, which is particularly excellent in seizure resistance and oil-water separation properties, and seizes between materials and rolls even under severe operating conditions such as high speed and high-pressure rolling. Of cold rolling oil composition, especially direct oil supply type cold rolling oil composition, which does not need to be operated by regulating the speed etc. It is to be.
Another object of the present invention is to provide a cold rolling method using the cold rolling oil composition, particularly a direct oil supply type cold rolling method.
本発明は以下に示す冷間圧延油組成物及び冷間圧延方法を提供するものである。
１．下記の成分１〜３を含む冷間圧延油組成物。
成分１：鉱油、合成エステル油及び動植物油からなる群から選ばれる少なくとも１種の基油、
成分２：下記Ａ群から選ばれる少なくとも１種のカチオン性モノマーのホモポリマー又はコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、又は
Ａ群から選ばれる少なくとも１種のカチオン性モノマーと、下記Ｂ群から選ばれる少なくとも１種のモノマーとのコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、及び
成分３：硫黄系化合物及びリン−硫黄系化合物からなる群から選ばれる少なくとも１種の極圧剤。
Ａ群：下記式（１）、（２）又は（３）で表される化合物。
Ｂ群：側鎖にアルキル基又はアルケニル基を有するアクリル酸又はメタクリル酸のエステル又はアミド、ビニルアルコール誘導体、フマル酸エステル及びマレイン酸エステル。
式（１）
The present invention provides the following cold rolling oil composition and cold rolling method.
1. A cold rolling oil composition comprising the following components 1 to 3.
Component 1: at least one base oil selected from the group consisting of mineral oil, synthetic ester oil and animal and vegetable oils,
Component 2: A homopolymer or copolymer of at least one cationic monomer selected from the following group A, a cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, or at least one cation selected from group A A cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, and Component 3: a sulfur compound and a phosphorus-sulfur compound. At least one extreme pressure agent selected from the group consisting of:
Group A: A compound represented by the following formula (1), (2) or (3).
Group B: Acrylic or methacrylic acid ester or amide, vinyl alcohol derivative, fumaric acid ester and maleic acid ester having an alkyl group or alkenyl group in the side chain.
Formula (1)
（式中、Ｒ1及びＲ2は、独立して水素原子又はメチル基を示す。）
式（２） ＣＨ2＝ＣＲ3−ＣＯ−ＮＨ−（ＣＨ2）mＮＲ4Ｒ5
（式中、Ｒ3は、水素原子又はメチル基を示し、Ｒ4及びＲ5は独立して炭素原子数１〜４のアルキル基を示し、ｍは１〜５の整数を示す。）
式（３） ＣＨ2＝ＣＲ6−ＣＯ−Ｏ−（ＣＨ2）nＮＲ7Ｒ8
（式中、Ｒ6は、水素原子又はメチル基を示し、Ｒ7及びＲ8は独立して炭素原子数１〜４のアルキル基を示し、ｎは１〜５の整数を示す。）
(In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
Equation (2) CH 2 = CR 3 -CO-NH- (CH 2) m NR 4 R 5
(In the formula, R 3 represents a hydrogen atom or a methyl group, R 4 and R 5 independently represent an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 5).
Equation (3) CH 2 = CR 6 -CO-O- (CH 2) n NR 7 R 8
(In the formula, R 6 represents a hydrogen atom or a methyl group, R 7 and R 8 independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 5).
２．下記の成分１〜３を含む冷間圧延油組成物。
成分１：鉱油、合成エステル油及び動植物油からなる群から選ばれる少なくとも１種の基油、
成分２：下記Ａ群から選ばれる少なくとも１種のカチオン性モノマーのホモポリマー又はコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、又は
Ａ群から選ばれる少なくとも１種のカチオン性モノマーと、下記Ｂ群から選ばれる少なくとも１種のモノマーとのコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、及び
成分３：硫黄系化合物、リン−硫黄系化合物及びリン系化合物からなる群から選ばれる少なくとも１種の極圧剤。
Ａ群：下記式（１）、（２）又は（３）で表される化合物。
Ｂ群：側鎖にアルキル基又はアルケニル基を有するアクリル酸又はメタクリル酸のエステル又はアミド、ビニルアルコール誘導体、フマル酸エステル及びマレイン酸エステル。
式（１）
2. A cold rolling oil composition comprising the following components 1 to 3.
Component 1: at least one base oil selected from the group consisting of mineral oil, synthetic ester oil and animal and vegetable oils,
Component 2: A homopolymer or copolymer of at least one cationic monomer selected from the following group A, a cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, or at least one cation selected from group A A cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, and component 3: a sulfur compound, a phosphorus-sulfur compound, and a copolymer of a functional monomer and at least one monomer selected from the following group B: At least one extreme pressure agent selected from the group consisting of phosphorus compounds;
Group A: A compound represented by the following formula (1), (2) or (3).
Group B: Acrylic or methacrylic acid ester or amide, vinyl alcohol derivative, fumaric acid ester and maleic acid ester having an alkyl group or alkenyl group in the side chain.
Formula (1)
（式中、Ｒ1及びＲ2は、独立して水素原子又はメチル基を示す。）
式（２） ＣＨ2＝ＣＲ3−ＣＯ−ＮＨ−（ＣＨ2）mＮＲ4Ｒ5
（式中、Ｒ3は、水素原子又はメチル基を示し、Ｒ4及びＲ5は独立して炭素原子数１〜４のアルキル基を示し、ｍは２〜５の整数を示す。）
式（３） ＣＨ2＝ＣＲ6−ＣＯ−Ｏ−（ＣＨ2）nＮＲ7Ｒ8
（式中、Ｒ6は、水素原子又はメチル基を示し、Ｒ7及びＲ8は独立して炭素原子数１〜４のアルキル基を示し、ｎは３〜５の整数を示す。）
(In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
Equation (2) CH 2 = CR 3 -CO-NH- (CH 2) m NR 4 R 5
(In the formula, R 3 represents a hydrogen atom or a methyl group, R 4 and R 5 independently represent an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 2 to 5).
Equation (3) CH 2 = CR 6 -CO-O- (CH 2) n NR 7 R 8
(In the formula, R 6 represents a hydrogen atom or a methyl group, R 7 and R 8 independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 3 to 5)
３．成分２のカチオン性高分子化合物が、Ａ群の化合物のホモポリマーであり、圧延油組成物中に１０〜５０００ｐｐｍ含まれていることを特徴とする、上記１又は２記載の冷間圧延油組成物。
４．成分２のカチオン性高分子化合物が、Ａ群の化合物とＢ群の化合物の質量比率が１：１０〜１０：１のコポリマーであり、圧延油組成物中に１０〜５０００ｐｐｍ含まれていることを特徴とする、上記１又は２記載の冷間圧延油組成物。
５．成分３の極圧剤が、それぞれ圧延油組成物中に０．１〜１０．０質量％含まれていることを特徴とする、上記１〜４のいずれか１項記載の冷間圧延油組成物。
６．成分３の極圧剤が、硫化油脂、ポリサルファイド又はホスホロチオエートである上記１〜５のいずれか１項記載の冷間圧延油組成物。
７．直接給油式用冷間圧延油組成物である上記１〜６のいずれか１項記載の冷間圧延油組成物。
８．上記１〜７のいずれか１項記載の冷間圧延油組成物を用いて冷間圧延を行う事を特徴とする冷間圧延方法。
3. The cold rolling oil composition according to 1 or 2 above, wherein the cationic polymer compound of component 2 is a homopolymer of a compound of group A and is contained in the rolling oil composition in an amount of 10 to 5000 ppm. Stuff.
4). The cationic polymer compound of component 2 is a copolymer having a mass ratio of the group A compound to the group B compound of 1:10 to 10: 1, and is contained in the rolling oil composition at 10 to 5000 ppm. 3. The cold-rolled oil composition as described in 1 or 2 above.
5). The cold rolling oil composition according to any one of the above items 1 to 4, wherein the extreme pressure agent of component 3 is contained in the rolling oil composition in an amount of 0.1 to 10.0% by mass. Stuff.
6). The cold-rolled oil composition according to any one of 1 to 5 above, wherein the extreme pressure agent of Component 3 is sulfurized fat, polysulfide, or phosphorothioate.
7). The cold rolling oil composition according to any one of the above 1 to 6, which is a cold rolling oil composition for direct oil supply.
8). A cold rolling method, wherein cold rolling is performed using the cold rolling oil composition according to any one of 1 to 7 above.
本発明の冷間圧延油組成物は、特定の基油、特定のカチオン性高分子化合物及び特定の極圧剤を含んでいるため、耐焼き付き性及び油水分離性に優れ、高速化、高圧下圧延等の厳しい操業条件下でも、材料とロール間で焼き付きの発生や、ヒートスクラッチなどと呼ばれる疵が材料に入ることがなく、そのため、速度等を規制して操業する必要がない。
本発明の冷間圧延油組成物は、圧延加工のみならず、金属材料の切削加工、研削加工、引抜き加工、プレス加工、鍛造加工等の塑性加工にも使用できる。
Since the cold rolling oil composition of the present invention contains a specific base oil, a specific cationic polymer compound and a specific extreme pressure agent, it is excellent in seizure resistance and oil-water separation, and is increased in speed and pressure. Even under severe operating conditions such as rolling, seizure does not occur between the material and the rolls, and soot called heat scratches do not enter the material, so there is no need to operate with regulated speed.
The cold rolling oil composition of the present invention can be used not only for rolling processing but also for plastic processing such as cutting, grinding, drawing, pressing, forging, etc. of metal materials.
本発明の組成物に使用する成分１の基油は、鉱油、合成エステル油及び動植物油からなる群から選ばれる少なくとも１種である。さらに具体的には、鉱油としては、スピンドル油、マシン油、シリンダー油等が、合成エステル油としては、脂肪酸オクチルエステル、トリメチロールプロパン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル等が、動植物油としては、パーム油、なたね油、牛脂、豚脂、重合油脂（大豆重合油、なたね重合油、ヒマシ重合油等）等の１種あるいは２種類以上の混合物が挙げられる。また、融点の低いウインタリング処理をした物でも良い。 The base oil of component 1 used in the composition of the present invention is at least one selected from the group consisting of mineral oil, synthetic ester oil and animal and vegetable oil. More specifically, as mineral oil, spindle oil, machine oil, cylinder oil, etc., as synthetic ester oil, fatty acid octyl ester, trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester, etc., as animal and vegetable oil, palm oil Examples thereof include one or a mixture of two or more of oil, rapeseed oil, beef tallow, lard, polymerized fat (soybean polymerized oil, rapeseed polymerized oil, castor polymerized oil, etc.). Moreover, the thing of the wintering process with low melting | fusing point may be used.
本発明に使用する成分２は、（１）Ａ群から選ばれる少なくとも１種のカチオン性モノマーのホモポリマー又はコポリマーであって、数平均分子量が3,000〜1,000,000、好ましくは5,000〜100,000のカチオン性高分子化合物、又は（２）Ａ群から選ばれる少なくとも１種のカチオン性モノマーと、Ｂ群から選ばれる少なくとも１種のモノマーとのコポリマーであって、数平均分子量が3,000〜1,000,000、好ましくは5,000〜100,000のカチオン性高分子化合物である。カチオン性高分子化合物の数平均分子量が大きすぎると高粘度になり、又、組み合わせによっては樹脂状となって適切でない。分子量が小さ過ぎると、溶剤や油剤に混入した水を効率良く分離できなくなる。
本発明に使用する成分２のカチオン性高分子化合物の数平均分子量は、より好ましくは、5,000〜100,000であり、最も好ましくは7,000から50,000である。
本発明に使用する成分２としてＡ群の化合物とＢ群の化合物のコポリマーを使用する場合、Ａ群の化合物：Ｂ群の化合物の質量比率は、好ましくは１：１０〜１０：１、さらに好ましくは１：５〜５：１である。Ａ群の化合物の比率が多いと、溶剤や基油に対する溶解性が低下し効果が低くなる。またＢ群の化合物の比率が多いと、カチオン性が低下する。Ａ群の化合物：Ｂ群の化合物の質量比率はより好ましくは１：３から３：１であり、更に好ましくは１：２から２：１である。
Component 2 used in the present invention is (1) a homopolymer or copolymer of at least one cationic monomer selected from Group A, having a number average molecular weight of 3,000 to 1,000,000, preferably 5,000 to 100,000. A molecular compound or (2) a copolymer of at least one cationic monomer selected from Group A and at least one monomer selected from Group B, having a number average molecular weight of 3,000 to 1,000,000, preferably 5,000 to 100,000 cationic polymer compounds. If the number average molecular weight of the cationic polymer compound is too large, the viscosity becomes high, and depending on the combination, it is not suitable because it is resinous. If the molecular weight is too small, water mixed in the solvent or oil cannot be efficiently separated.
The number average molecular weight of the cationic polymer compound of component 2 used in the present invention is more preferably 5,000 to 100,000, and most preferably 7,000 to 50,000.
When a copolymer of a group A compound and a group B compound is used as component 2 used in the present invention, the mass ratio of the group A compound to the group B compound is preferably 1:10 to 10: 1, more preferably Is 1: 5-5: 1. When there are many ratios of the compound of A group, the solubility with respect to a solvent or base oil will fall and an effect will become low. Moreover, when there are many ratios of the compound of B group, cationic property will fall. The mass ratio of the compound of Group A: the compound of Group B is more preferably 1: 3 to 3: 1, and further preferably 1: 2 to 2: 1.
本発明の成分２のカチオン性高分子化合物の製造に使用するＡ群の化合物の好ましい例としては、式１において、Ｒ1がメチル基、Ｒ2が水素原子である化合物、式２において、Ｒ3、Ｒ4及びＲ5がメチル基、ｍが２又は３の化合物、式３において、Ｒ6、Ｒ7及びＲ8がメチル基、ｎが３の化合物等が挙げられる。
本発明の成分２のカチオン性高分子化合物の製造に使用するＢ群の化合物の好ましい例としては、アクリル酸メチルエステル、メタアクリル酸ラウリルエステル、メタアクリル酸２−エチルヘキシルエステル、メタアクリル酸ステアリルエステル、メタアクリル酸アリルエステル、ビニルパルミチルエーテル、オレイン酸ビニルエステル、フマル酸ジオレイルエステル、マレイン酸モノオレイルエステル、マレイン酸モノ２−エチルヘキシルエステルなどの側鎖にアルキル基又はアルケニル基を有する化合物が挙げられる。
Preferred examples of the group A compounds used for the production of the cationic polymer compound of component 2 of the present invention include compounds in which R 1 is a methyl group and R 2 is a hydrogen atom in formula 1, 3 , R 4 and R 5 are methyl groups, m is a compound having 2 or 3, and in formula 3, R 6 , R 7 and R 8 are methyl groups, and n is 3 or the like.
Preferred examples of the group B compounds used for the production of the cationic polymer compound of component 2 of the present invention include acrylic acid methyl ester, methacrylic acid lauryl ester, methacrylic acid 2-ethylhexyl ester, and methacrylic acid stearyl ester. A compound having an alkyl group or an alkenyl group in the side chain, such as allyl methacrylate, vinyl palmityl ether, vinyl oleate, dioleyl fumarate, monooleyl maleate, mono-2-ethylhexyl maleate, etc. Can be mentioned.
本発明のカチオン性高分子化合物は、一般的な方法により合成できる。例えば、トルエンなどの溶剤にＡ群の化合物を溶解し、必要によりこれにＢ群の化合物を加え、重合開始剤として、アゾ系又は過酸化物系の化合物を用いて、７０℃〜１２０℃の温度で５〜１０時間程度反応させることにより容易に合成できる。 The cationic polymer compound of the present invention can be synthesized by a general method. For example, a group A compound is dissolved in a solvent such as toluene, and if necessary, a group B compound is added thereto, and an azo- or peroxide-based compound is used as a polymerization initiator. It can be easily synthesized by reacting at a temperature for about 5 to 10 hours.
本発明の圧延油組成物中の成分２のカチオン性高分子化合物の含有量は、圧延油組成物の使用時の濃度で１０〜５０００ｐｐｍの範囲が好ましい。１０ｐｐｍより少ないと効果が発現しにくくなり、５０００ｐｐｍより多いと、分散剤として作用するため、油水分離性が低下する。圧延油組成物中の成分２のカチオン性高分子化合物の含有量は、より好ましくは、５０〜２０００ｐｐｍであり、更に好ましくは、１００〜１０００ｐｐｍである。 The content of the cationic polymer compound of component 2 in the rolling oil composition of the present invention is preferably in the range of 10 to 5000 ppm as a concentration when the rolling oil composition is used. If it is less than 10 ppm, the effect is difficult to be exhibited, and if it exceeds 5000 ppm, it acts as a dispersant, so that the oil-water separation property is lowered. The content of the cationic polymer compound of component 2 in the rolling oil composition is more preferably 50 to 2000 ppm, and still more preferably 100 to 1000 ppm.
本発明に使用する成分３の極圧剤は、硫黄系化合物、リン−硫黄系化合物及びリン系化合物からなる群から選ばれる少なくとも１種である。硫黄系極圧剤としては、硫化油脂、ポリサルファイド（例えば、ジドデシルポリサルファイド）等が、リン−硫黄系極圧剤としては、ホスホロチオエート等が、また、リン系極圧剤としては、リン酸エステル（例えば、リン酸トリクレシル）、亜リン酸エステル、酸性リン酸エステル等が挙げられる。
これらの極圧剤の使用量は、本発明の冷間圧延油組成物中、圧延油組成物の使用時の濃度で好ましくは0.1〜10.0質量%であり、さらに好ましくは0.1〜5.0質量%である。
The extreme pressure agent of component 3 used in the present invention is at least one selected from the group consisting of sulfur compounds, phosphorus-sulfur compounds and phosphorus compounds. Sulfur-based extreme pressure agents include sulfurized fats and oils, polysulfide (eg, didodecyl polysulfide), phosphorus-sulfur extreme pressure agents include phosphorothioates, and phosphorus-based extreme pressure agents include phosphate esters ( Examples thereof include tricresyl phosphate), phosphites, and acidic phosphates.
The amount of these extreme pressure agents used is preferably 0.1 to 10.0% by mass, more preferably 0.1 to 5.0% by mass in the cold rolling oil composition of the present invention at the concentration when the rolling oil composition is used. is there.
本発明の冷間圧延油組成物には、油性向上剤（例えば、ステアリン酸、オレイン酸等の脂肪酸）、酸化防止剤（例えば、ナフチルアミン等のアミン系酸化防止剤）、乳化剤（例えば、ポリオキシエチレンノニルフェニルエーテル等のノニオン系界面活性剤）等を含有させてもよい。
本発明の圧延油組成物（原液）は、一般に、3.0〜20.0質量％程度に水で希釈し、被圧延材料表面、圧延ロール表面に適量、例えば、スタンド当り0.1〜15.0Ｌ/min程度供給する。本発明の圧延油組成物は、直接給油式の冷間圧延油として特に優れている。
The cold rolling oil composition of the present invention includes an oil improver (for example, fatty acids such as stearic acid and oleic acid), an antioxidant (for example, an amine-based antioxidant such as naphthylamine), an emulsifier (for example, polyoxy). Nonionic surfactants such as ethylene nonylphenyl ether) may be included.
The rolling oil composition (stock solution) of the present invention is generally diluted with water to about 3.0 to 20.0% by mass and supplied to the surface of the material to be rolled and the surface of the rolling roll, for example, about 0.1 to 15.0 L / min per stand. . The rolling oil composition of the present invention is particularly excellent as a direct oil supply type cold rolling oil.
実施例で用いた成分２のカチオン性高分子化合物１〜４を以下のように合成した。
（カチオン性高分子化合物１）
なたね油２３３０ｇに式２の化合物（Ｒ3、Ｒ4、Ｒ5＝ＣＨ3 、ｍ＝３）４００ｇとステアリルメタクリレート６００ｇを溶解し、ターシャリーブチルパーオキシイソプロピルカーボネート１５．０ｇを加え、窒素雰囲気下で、１１０℃、８時間反応させた。この反応物は、カチオン性高分子化合物１を３０質量％含有する添加剤であり、カチオン性高分子化合物１の数平均分子量は、約１５０００であった。
（カチオン性高分子化合物２）
トルエン２０００ｇに式１の化合物（Ｒ1 ＝ＣＨ3 、Ｒ2 ＝Ｈ）４００ｇとステアリルメタクリレート６００ｇを溶解し、２，２’−アゾビス（２，４−ジメチルバレロニトリル）８１.２ｇを加え、窒素雰囲気下で、７０℃、７時間反応させた。これになたね油２０００ｇを加えて減圧下でトルエンを除去した。この反応物は、カチオン性高分子化合物２を３３質量％含有する添加剤であり、カチオン性高分子化合物２の数平均分子量は、約２００００であった。
The cationic polymer compounds 1 to 4 of component 2 used in the examples were synthesized as follows.
(Cationic polymer compound 1)
In 2330 g of rapeseed oil, 400 g of the compound of formula 2 (R 3 , R 4 , R 5 = CH 3 , m = 3) and 600 g of stearyl methacrylate are dissolved, and 15.0 g of tertiary butyl peroxyisopropyl carbonate is added under a nitrogen atmosphere. , 110 ° C. for 8 hours. This reaction product was an additive containing 30% by mass of the cationic polymer compound 1, and the number average molecular weight of the cationic polymer compound 1 was about 15,000.
(Cationic polymer compound 2)
In 2000 g of toluene, 400 g of the compound of formula 1 (R 1 = CH 3 , R 2 = H) and 600 g of stearyl methacrylate are dissolved, 81.2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is added, and nitrogen is added. The reaction was carried out at 70 ° C. for 7 hours under an atmosphere. To this, 2000 g of rapeseed oil was added and toluene was removed under reduced pressure. This reaction product was an additive containing 33% by mass of the cationic polymer compound 2, and the number average molecular weight of the cationic polymer compound 2 was about 20,000.
（カチオン性高分子化合物３）
なたね油２３３０ｇに式２の化合物（Ｒ3、Ｒ4、Ｒ5＝ＣＨ3 、ｍ＝１）６００ｇとステアリルメタクリレート２００ｇを溶解し、ターシャリーブチルパーオキシイソプロピルカーボネート１５．０ｇを加え、窒素雰囲気下で、１１０℃、８時間反応させた。この反応物は、カチオン性高分子化合物３を２５質量％含有する添加剤であり、カチオン性高分子化合物３の数平均分子量は、約１０００００であった。
（カチオン性高分子化合物４）
トルエン２０００ｇに式３の化合物（Ｒ6、Ｒ7、Ｒ8＝ＣＨ3 、ｎ＝３）５００ｇを溶解し、２，２’−アゾビス（２，４−ジメチルバレロニトリル）６７．７ｇを加え、窒素雰囲気下で、７０℃、８時間反応させた。これになたね油２０００ｇを加えて減圧下でトルエンを除去した。この反応物は、カチオン性高分子化合物４を２０質量％含有する添加剤であり、カチオン性高分子化合物４の数平均分子量は、約７００００であった。
(Cationic polymer compound 3)
In 2330 g of rapeseed oil, 600 g of the compound of formula 2 (R 3 , R 4 , R 5 = CH 3 , m = 1) and 200 g of stearyl methacrylate are dissolved, and 15.0 g of tertiary butyl peroxyisopropyl carbonate is added under a nitrogen atmosphere. , 110 ° C. for 8 hours. This reaction product was an additive containing 25% by mass of the cationic polymer compound 3, and the number average molecular weight of the cationic polymer compound 3 was about 100,000.
(Cationic polymer compound 4)
In 2000 g of toluene, 500 g of the compound of the formula 3 (R 6 , R 7 , R 8 = CH 3 , n = 3) is dissolved, and 67.7 g of 2,2′-azobis (2,4-dimethylvaleronitrile) is added, The reaction was performed at 70 ° C. for 8 hours under a nitrogen atmosphere. To this, 2000 g of rapeseed oil was added and toluene was removed under reduced pressure. This reaction product was an additive containing 20% by mass of the cationic polymer compound 4, and the number average molecular weight of the cationic polymer compound 4 was about 70000.
実施例１〜１５及び比較例１〜６
表１〜４に示す成分を所定の割合で混合して実施例１〜１５、比較例１〜６の冷間圧延油組成物を調製し、各組成物の耐焼き付き性及び油水分離性を評価した。結果を表１〜４に示す。
耐焼き付き性の評価
ＪＩＳ Ｋ−２５４１に準じて、非焼き付き荷重を測定し評価した。曾田四球試験機を用い、非焼き付き荷重が８．５Ｋｇｆ以上を合格（○）とし、８．５Ｋｇｆ未満を不合格（×）とした。
油水分離性の評価
８０℃の水３８８ｍｌに試料油剤１２ｇを入れ、ホモジナイザー（日本精器（株）製）を用いて８０００ｒｐｍで１分間攪拌して分液ロートに移し、３０秒静置した後、下層１００ｍｌを採取し油分量を測定した。下層油分量が１．０ｍｌ未満を合格（○）とし、１．０ｍｌ以上を不合格（×）とした。
Examples 1-15 and Comparative Examples 1-6
The components shown in Tables 1 to 4 were mixed at a predetermined ratio to prepare the cold-rolled oil compositions of Examples 1 to 15 and Comparative Examples 1 to 6, and the seizure resistance and oil / water separation property of each composition were evaluated. did. The results are shown in Tables 1-4.
Evaluation of seizure resistance Non-seizure load was measured and evaluated according to JIS K-2541. Using an Iwata four-ball tester, a non-seizure load of 8.5 kgf or more was evaluated as acceptable (◯), and less than 8.5 kgf was rejected (x).
Evaluation of oil-water separation property 12 g of sample oil was placed in 388 ml of water at 80 ° C., stirred for 1 minute at 8000 rpm using a homogenizer (manufactured by Nippon Seiki Co., Ltd.), allowed to stand for 30 seconds, 100 ml of the lower layer was collected and the oil content was measured. A lower layer oil content of less than 1.0 ml was accepted (◯), and 1.0 ml or more was rejected (x).
合成エステル油：トリメチロールプロパントリオレート
硫化油脂：フェロジャパン製ＳＰ−１１０
ポリサルファイド：ジーターシャリードデシルポリサルファイド
ホスホロチオエート：トリフェニルホスホロチオエート
乳化剤１：ポリオキシエチレンアルキルエーテル（ＨＬＢ＝５）
乳化剤２：ポリオキシエチレンアルキルエーテル（ＨＬＢ＝１０）
Synthetic ester oil: trimethylolpropane trioleate sulfurized oil: SP-110 manufactured by Ferro Japan
Polysulfide: Jeter Charide Decyl Polysulfide Phosphorothioate: Triphenyl phosphorothioate Emulsifier 1: Polyoxyethylene alkyl ether (HLB = 5)
Emulsifier 2: Polyoxyethylene alkyl ether (HLB = 10)
成分２のカチオン性高分子化合物と成分３の硫黄系、リン−硫黄系又はリン系の極圧剤を含む本発明の実施例１〜１５の組成物は、優れた耐焼き付き性及び油水分離性を示すことがわかる。
これに対して、成分３の硫黄系、リン−硫黄系又はリン系の極圧剤を含まない比較例１〜３の組成物は、油水分離性は優れているが耐焼き付き性が劣っており、成分２のカチオン性高分子化合物を含まない比較例４〜６の組成物は、耐焼き付き性は優れているが、油水分離性が劣っている。
The compositions of Examples 1 to 15 including the cationic polymer compound of Component 2 and the sulfur-based, phosphorus-sulfur-based, or phosphorus-based extreme pressure agent of Component 3 have excellent seizure resistance and oil-water separation properties. It can be seen that
On the other hand, the compositions of Comparative Examples 1 to 3 that do not contain the sulfur-based, phosphorus-sulfur-based, or phosphorus-based extreme pressure agent of Component 3 are excellent in oil / water separation but poor in seizure resistance. The compositions of Comparative Examples 4 to 6 that do not contain the cationic polymer compound of Component 2 are excellent in seizure resistance but poor in oil-water separation.
Claims (8)
成分１：鉱油、合成エステル油及び動植物油からなる群から選ばれる少なくとも１種の基油、
成分２：下記Ａ群から選ばれる少なくとも１種のカチオン性モノマーのホモポリマー又はコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、又は
Ａ群から選ばれる少なくとも１種のカチオン性モノマーと、下記Ｂ群から選ばれる少なくとも１種のモノマーとのコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、及び
成分３：硫黄系化合物及びリン−硫黄系化合物からなる群から選ばれる少なくとも１種の極圧剤。
Ａ群：下記式（１）、（２）又は（３）で表される化合物。
Ｂ群：側鎖にアルキル基又はアルケニル基を有するアクリル酸又はメタクリル酸のエステル又はアミド、ビニルアルコール誘導体、フマル酸エステル及びマレイン酸エステル。
式（１）
（式中、Ｒ1及びＲ2は、独立して水素原子又はメチル基を示す。）
式（２） ＣＨ2＝ＣＲ3−ＣＯ−ＮＨ−（ＣＨ2）mＮＲ4Ｒ5
（式中、Ｒ3は、水素原子又はメチル基を示し、Ｒ4及びＲ5は独立して炭素原子数１〜４のアルキル基を示し、ｍは１〜５の整数を示す。）
式（３） ＣＨ2＝ＣＲ6−ＣＯ−Ｏ−（ＣＨ2）nＮＲ7Ｒ8
（式中、Ｒ6は、水素原子又はメチル基を示し、Ｒ7及びＲ8は独立して炭素原子数１〜４のアルキル基を示し、ｎは１〜５の整数を示す。） A cold rolling oil composition comprising the following components 1 to 3.
Component 1: at least one base oil selected from the group consisting of mineral oil, synthetic ester oil and animal and vegetable oils,
Component 2: A homopolymer or copolymer of at least one cationic monomer selected from the following group A, a cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, or at least one cation selected from group A A cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, and Component 3: a sulfur compound and a phosphorus-sulfur compound. At least one extreme pressure agent selected from the group consisting of:
Group A: A compound represented by the following formula (1), (2) or (3).
Group B: Acrylic or methacrylic acid ester or amide, vinyl alcohol derivative, fumaric acid ester and maleic acid ester having an alkyl group or alkenyl group in the side chain.
Formula (1)
(In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
Equation (2) CH 2 = CR 3 -CO-NH- (CH 2) m NR 4 R 5
(In the formula, R 3 represents a hydrogen atom or a methyl group, R 4 and R 5 independently represent an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 5).
Equation (3) CH 2 = CR 6 -CO-O- (CH 2) n NR 7 R 8
(In the formula, R 6 represents a hydrogen atom or a methyl group, R 7 and R 8 independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 5).
成分１：鉱油、合成エステル油及び動植物油からなる群から選ばれる少なくとも１種の基油、
成分２：下記Ａ群から選ばれる少なくとも１種のカチオン性モノマーのホモポリマー又はコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、又は
Ａ群から選ばれる少なくとも１種のカチオン性モノマーと、下記Ｂ群から選ばれる少なくとも１種のモノマーとのコポリマーであって、数平均分子量が3,000〜1,000,000のカチオン性高分子化合物、及び
成分３：硫黄系化合物、リン−硫黄系化合物及びリン系化合物からなる群から選ばれる少なくとも１種の極圧剤。
Ａ群：下記式（１）、（２）又は（３）で表される化合物。
Ｂ群：側鎖にアルキル基又はアルケニル基を有するアクリル酸又はメタクリル酸のエステル又はアミド、ビニルアルコール誘導体、フマル酸エステル及びマレイン酸エステル。
式（１）
（式中、Ｒ1及びＲ2は、独立して水素原子又はメチル基を示す。）
式（２） ＣＨ2＝ＣＲ3−ＣＯ−ＮＨ−（ＣＨ2）mＮＲ4Ｒ5
（式中、Ｒ3は、水素原子又はメチル基を示し、Ｒ4及びＲ5は独立して炭素原子数１〜４のアルキル基を示し、ｍは２〜５の整数を示す。）
式（３） ＣＨ2＝ＣＲ6−ＣＯ−Ｏ−（ＣＨ2）nＮＲ7Ｒ8
（式中、Ｒ6は、水素原子又はメチル基を示し、Ｒ7及びＲ8は独立して炭素原子数１〜４のアルキル基を示し、ｎは３〜５の整数を示す。） A cold rolling oil composition comprising the following components 1 to 3.
Component 1: at least one base oil selected from the group consisting of mineral oil, synthetic ester oil and animal and vegetable oils,
Component 2: A homopolymer or copolymer of at least one cationic monomer selected from the following group A, a cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, or at least one cation selected from group A A cationic polymer compound having a number average molecular weight of 3,000 to 1,000,000, and component 3: a sulfur compound, a phosphorus-sulfur compound, and a copolymer of a functional monomer and at least one monomer selected from the following group B: At least one extreme pressure agent selected from the group consisting of phosphorus compounds;
Group A: A compound represented by the following formula (1), (2) or (3).
Group B: Acrylic or methacrylic acid ester or amide, vinyl alcohol derivative, fumaric acid ester and maleic acid ester having an alkyl group or alkenyl group in the side chain.
Formula (1)
(In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group.)
Equation (2) CH 2 = CR 3 -CO-NH- (CH 2) m NR 4 R 5
(In the formula, R 3 represents a hydrogen atom or a methyl group, R 4 and R 5 independently represent an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 2 to 5).
Equation (3) CH 2 = CR 6 -CO-O- (CH 2) n NR 7 R 8
(In the formula, R 6 represents a hydrogen atom or a methyl group, R 7 and R 8 independently represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 3 to 5)
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| CN109735388A (en) * | 2018-12-29 | 2019-05-10 | 广州科卢斯流体科技有限公司 | A kind of environment protection water-based aluminium foil punching press liquid |
| JP2021172718A (en) * | 2020-04-23 | 2021-11-01 | 日本製鉄株式会社 | Pretreatment composition for cold rolling and cold rolling method |
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| JPH10231494A (en) * | 1996-12-20 | 1998-09-02 | Nippon Steel Corp | Lubricating oil for water-dispersed steel-sheet cold-rolling mill lubricant and method for steel-sheet cold rolling |
| JP2000328088A (en) * | 1999-05-17 | 2000-11-28 | Kyodo Yushi Co Ltd | Rolling mill lubricant composition and rolling method |
| JP2003301191A (en) * | 2002-04-09 | 2003-10-21 | Jfe Steel Kk | Cold-rolling oil composition and cold-rolling method |
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