JP5400601B2 - Detergent composition around rolling mill - Google Patents

Description

  The present invention relates to a detergent composition for rolling mills. The cleaning composition of the present invention is used in a cleaning operation for scum-like soil containing a large amount of metal powder adhered and deposited around a machine that performs rolling, cutting and grinding.

  In factories where rolling, cutting and grinding are performed, in order to reduce the risk of fire and improve the work environment, remove dirt around the mills and other machines, such as mill floors and scum-like dirt that contains a lot of metal powder. Cleaning work is carried out regularly. Conventionally, hydrocarbon solvents such as kerosene, emulsion type cleaners, and alkaline cleaners have been used for these cleaning operations. The emulsion-type cleaning agent is obtained by emulsifying and dispersing a hydrocarbon solvent such as kerosene in water with a surfactant, and the alkaline cleaning agent has a pH of 10 or more mainly composed of a surfactant and an alkali builder. . However, hydrocarbon solvents such as kerosene have problems such as low flash point and high risk of fire, and alkaline cleaners have workability problems such as wearing protective equipment for cleaning work. In addition, the emulsion type cleaning agent has problems such as insufficient cleaning performance.

  In order to satisfy such a problem, various industrial water-soluble cleaning compositions have been proposed (Patent Documents 1 and 2). Patent Document 1 proposes an industrial water-soluble detergent composition that uses polyoxyethylene alkylamines having different HLBs, contains a sequestering agent and water in a predetermined ratio, and does not contain an organic solvent. Patent Document 2 proposes a nonflammable emulsion cleaning agent in which an organic solvent having a flash point of 100 ° C. or higher and water are mixed in the presence of an emulsifier.

Japanese Patent Laid-Open No. 04-013799 JP 60-0667600

  However, the industrial water-soluble cleaning compositions of Patent Documents 1 and 2 have solved the problems associated with danger, workability, etc. associated with flammability, but with regard to cleaning performance, cleaning performance of factory floors and the like. However, the cleaning effect around the machine where a large amount of scum-like dirt containing a large amount of metal powder adhered and deposited was not fully satisfied. Therefore, even when the industrial water-soluble cleaning composition is used, it is necessary to separately perform cleaning with a hydrocarbon solvent such as kerosene.

  The present invention exhibits an excellent cleaning effect in a cleaning operation around a machine (especially around a rolling mill using a rolling oil containing fats and oils) on which a large amount of scum-like dirt containing a large amount of metal powder adheres and accumulates. An object of the present invention is to provide a rolling mill cleaning composition that has a low risk of being easy to clean and can efficiently improve the working environment. Another object of the present invention is to provide a method for cleaning around a rolling mill using the cleaning composition for rolling around the rolling mill.

That is, the present invention
(A) 30-68.5% by weight of a petroleum solvent having a flash point of 40-100 ° C.
(B) 0.5 to 5% by weight of a nonionic amine surfactant,
(C) 5 to 10% by weight of a nonionic surfactant (excluding the component (b)),
(D) 5 to 10% by weight of an anionic surfactant,
(E) 1 to 5% by weight of a rust inhibitor, and
(F) water, 20-58.5 wt%,
A rolling mill composition with a weight ratio of component (b) to component (c) (component (c) / component (b)) of 2 to 8 and a pH of 8 to 10 Things.

  The present invention also relates to a method for cleaning around a rolling mill, which includes a step of cleaning dirt around the rolling mill, which is an object to be cleaned, with the cleaning composition for rolling mill.

  Since the cleaning composition of the present invention does not detect the flash point, the risk of fire is low, and even if mixed with rolling oil or the like, it does not affect the properties of the rolling oil (particle diameter of the rolling oil emulsion, etc.) The dirt around the rolling mill can be washed and removed with good cleaning efficiency. In addition, according to the cleaning composition of the present invention, around a machine where a large amount of scum-like soil containing a large amount of metal powder, oil, metal soap and water adheres and accumulates, especially around a rolling mill using rolling oil containing fats and oils. In this cleaning operation, an excellent cleaning effect can be exhibited, the cleaning operation can be easily performed, and improvement of the work environment can be efficiently achieved.

  The rolling mill cleaning composition of the present invention contains the components (a) to (f) in a predetermined amount and a predetermined weight ratio of the components (b) and (c).

  As the component (a), a petroleum solvent having a flash point of 40 to 100 ° C. is used. Component (a) acts as a solubilizing agent for scum-like soil, and may be used alone or as a mixture of two or more depending on the soil. The flash point of the petroleum-based solvent is preferably 50 to 100 ° C., more preferably 60 to 90 ° C., from the viewpoint of fire risk and detergency against rolling mill contamination. Examples of the petroleum solvent include various solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Specific examples of the petroleum solvent related to component (a) include kerosene and light oil.

  The content ratio of the component (a) is 30 to 68.5% by weight, preferably 40 to 67% by weight, and more preferably 50 to 65% by weight with respect to the total amount of the cleaning composition. It is preferable to adjust the content ratio of the component (a) to the above-mentioned range from the viewpoint of fire risk and detergency of rolling mill stains.

  As the component (b), a nonionic amine-based surfactant is used. The component (b) mainly acts as a dispersant for the metal powder present in the scum-like dirt, and can be used alone or in combination of two or more, and relates to the component (c) described later. In combination with other nonionic surfactants, the cleaning property of rolling mill stains is improved. Moreover, 8-16 are preferable from a dispersible viewpoint of metal powder, and, as for HLB of the nonionic amine surfactant which is a component (b), 10-15 are more preferable.

  The nonionic amine-based surfactant has at least one linear, branched or cyclic alkyl group or alkenyl group and at least one polyoxyalkylene group as three substituents bonded to the N atom. It is. The number of carbon atoms of the alkyl group or alkenyl group is preferably 6 to 20, and the total number of carbon atoms of the hydrocarbon group (when there is one hydrocarbon group, the number of carbon atoms of the hydrocarbon group, when there are two hydrocarbon groups) The sum is preferably 6 to 40, more preferably 10 to 36.

  Examples of the alkylene group related to the polyoxyalkylene group include alkylene groups having 2 to 4 carbon atoms. The polyoxyalkylene group may be formed of one kind of oxyalkylene group, but may be a block form of two or more kinds of oxyalkylene groups, or may be a random form. The polyoxyalkylene group is preferably a polyoxyethylene group from the viewpoint of detergency. Moreover, 5-20 are preferable from a viewpoint of washability, 6-15 are more preferable, and, as for the average addition mole number of a polyoxyalkylene group, 7-12 are more preferable.

Examples of the nonionic amine surfactant include at least one alkyl group and / or alkenyl group and at least one polyoxyalkylene group as the three substituents bonded to the N atom. 1):

[Wherein, X is —H, —R ² or — (AO) _m —H, R ¹ and R ² are alkyl groups and / or alkenyl groups, A is an alkylene group, and n and m are averages of oxyalkylene groups. A polyoxyalkylene alkyl (and / or alkenyl) amine represented by the formula (1) indicates the number of moles added. Specific examples of the polyoxyalkylene alkyl (and / or alkenyl) amine represented by the general formula (1) include, for example, polyoxyethylene lauryl amine, polyoxyethylene stearyl amine, polyoxyethylene oleyl amine, and polyoxyethylene stearyl. Examples include propylene diamine, polyoxyethylene N-cyclohexylamine, and polyoxyethylene coconut amine. Among the polyoxyalkylene alkyl (and / or alkenyl) amines represented by the general formula (1), polyoxyethylene lauryl amine and polyoxyethylene coconut amine are preferable from the viewpoint of the detergency of scum-like soil. In particular, polyoxyethylene laurylamine, which is a polyoxyalkylene alkylamine, is preferable from the viewpoint of detergency of scum-like dirt.

  The content ratio of the component (b) is 0.5 to 5% by weight with respect to the total amount of the detergent composition, and is preferably 1 to 4% by weight from the viewpoint of a balance between emulsifiability and dispersibility. Weight percent is more preferred.

  As the component (c), a nonionic surfactant other than the nonionic amine surfactant according to the component (b) is used. The component (c) acts as a water solubilizer and an emulsifier for rolling mill soil, and can be used alone or in combination of two or more. Moreover, HLB of a component (c) is from the viewpoint of water-solubilization property, the washing | cleaning property of a rolling mill stain | pollution | contamination, and the property stability of the processing oil emulsion at the time of making cleaning composition contact processing oil, such as rolling oil, 6-18 are preferable and 10-14 are more preferable.

  Specific examples of the nonionic surfactant according to the component (c) include, for example, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, Examples thereof include polyoxyalkylene alkyl (and / or alkenyl) ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene castor oil, polyoxyethylene polyoxypropylene polymer, and the like.

  Among the components (c), polyoxyalkylene alkyl (and / or alkenyl) ether is preferable from the viewpoint of detergency of rolling mill stains. Examples of the alkyl (and / or alkenyl) group include a linear or branched alkyl group and / or alkenyl group having 8 to 22, preferably 10 to 20, and more preferably 12 to 18 carbon atoms. Examples of the alkylene group related to the polyoxyalkylene group include an alkylene group having 2 to 4 carbon atoms. The polyoxyalkylene group may be formed of one kind of oxyalkylene group, but may be a block form of two or more kinds of oxyalkylene groups, or may be a random form. The polyoxyalkylene group is preferably a polyoxyethylene group from the viewpoint of detergency. Moreover, 2-18 are preferable from a viewpoint of detergency, and, as for the average addition mole number of a polyoxyalkylene group, 6-10 are more preferable.

  Specific examples of the polyoxyalkylene alkyl (or alkenyl) ether include polyoxyethylene oleyl ether, polyoxyethylene dodecyl ether, and polyoxyethylene lauryl ether.

  The content ratio of the component (c) is 5 to 10% by weight with respect to the total amount of the detergent composition, and is 6 to 6 from the viewpoint of water solubilization property, cleaning property of rolling mill stains, and property stability of the processing oil emulsion. 10 weight% is preferable and 7 to 10 weight% is more preferable.

  Further, the component (b) and the component (c) have a weight ratio (component (c) / component (b)) of 2 to 8, preferably 2 to 6, more preferably 3 to 5. Used. By using the component (b) and the component (c) together in the weight ratio, it is possible to improve the detergency of rolling mill stains related to scum-like stains.

  The anionic surfactant which is the component (d) acts as a water solubilizer and can be used alone or in combination of two or more. Specific examples of the anionic surfactant according to component (d) include, for example, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, Examples include fatty acid salts. Component (d) is preferably an alkylbenzene sulfonate from the viewpoint of water solubilization, and more preferably dodecylbenzene sulfonate.

  Examples of the salt include alkali or alkaline earth metal salts and / or amine salts. From the viewpoint of water solubilization, alkali or alkaline earth metal salts are preferable, and specific examples thereof include sodium salts and potassium salts. , Calcium salts and the like are preferable. Examples of amine salts include salts with at least one selected from the group consisting of alkanolamines, primary amines, secondary amines, and tertiary amines. For example, examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Examples of the primary amine include methylamine, ethylamine, propylamine, butylamine, and pentylamine. Examples of the secondary amine include Piperidine, piperazine and the like can be mentioned, and examples of the tertiary amine include trimethylamine and triethylamine. 8-20 are preferable and, as for carbon number of an alkyl group, 10-18 are more preferable. The alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain.

  The content of component (d) is 5 to 10% by weight with respect to the total amount of the detergent composition, preferably 6 to 10% by weight, more preferably 7 to 10% by weight from the viewpoint of water solubilization.

  The rust preventive agent which is the said component (e) is used from a viewpoint of iron rust prevention property. A component (e) can be used individually by 1 type or in combination of 2 or more types. Specific examples of the component (e) include amine-based rust preventives, carboxylic acid-based rust preventives, and ester-based rust preventives. An amine or amine salt is mentioned as an amine type antirust agent. Examples of the amine include alkanolamines, and specifically include monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and diethylethanolamine. Examples of the amine salt include a salt of the amine and a compound having a carboxyl group. Examples of the compound having a carboxyl group include paranitrobenzoic acid and paramethylbenzoic acid among aromatic carboxylic acids, and aliphatic groups. Among carboxylic acids, C12-18 aliphatic carboxylic acids such as oleic acid and lauric acid, and alkenyl succinic acids having 12 to 18 alkenyl groups such as hexadecenyl succinic acid and dodecenyl succinic acid can be mentioned. . From the viewpoint of iron rust prevention, aliphatic carboxylic acids are preferable, and oleic acid is more preferable. Examples of the carboxylic acid-based rust preventive include aromatic carboxylic acids used in the amine salts and alkenyl succinic acids having an alkenyl group having 12 to 18 carbon atoms. Examples of the ester-based rust preventive include esterified products such as sorbitan monooleate. In addition, the salt compound such as an alkanolamine salt can be used by blending a salt compound in the preparation of the cleaning composition. In addition, the carboxylic acid and the alkanolamine are blended when preparing the cleaning composition. Thus, a salt can be formed with the preparation of the detergent composition.

  The content ratio of the component (e) is 1 to 5% by weight with respect to the total amount of the detergent composition, and from the viewpoint of rust prevention and property stability of the processing oil emulsion when contacting the detergent composition. 1.5 to 4% by weight is preferred, and 2 to 3% by weight is more preferred.

  As water which is a component (f), ion-exchange water and pure water are preferable, and ion-exchange water is more preferable. The content ratio of the component (f) is 20 to 58.5% by weight, preferably 20 to 40% by weight, based on the total amount of the cleaning composition so as not to give the cleaning composition a flash point. More preferred is ˜35% by weight.

  Regarding the component (a) and the component (f), the weight ratio (component (a) / component (f)) is 1 to 3.3 in order to prevent the scum-like dirt from being washed and to prevent the composition from having a flash point. Is preferable, and 2.5 to 3.2 is more preferable.

  The rolling mill cleaning composition of the present invention contains the component (a) to the component (f) in the predetermined amount, and the component (b) and the component (c) in a predetermined weight ratio, Furthermore, the pH is adjusted to 8-10. It is preferable to control the pH of the cleaning composition within a range from the viewpoints of cleaning properties, rust prevention properties, and workability. The pH of the cleaning composition is preferably 8.5 to 10 from the viewpoint of detergency, preferably 8 to 9.5, and more preferably 8 to 9 from the viewpoint of workability.

  In addition to the above components, known additives such as antioxidants and antiseptics can be added to the cleaning composition for rolling mills of the present invention as necessary. For example, antioxidants such as 2,4-ditert-butyl-p-cresol and phenyl-α-naphthylamine, antiseptic / antifungal agents such as 1,2-benzisothiazolin-3-ol and 2-hydroxymethylaminoethanol Can be used. The proportion of these additives is preferably 3% by weight or less based on the total amount of the cleaning composition.

  With the detergent composition for rolling mills according to the present invention, dirt around the rolling mill can be efficiently cleaned and removed. When using the cleaning composition for rolling mills of the present invention, the stock solution can be directly applied to the object to be cleaned, but it can also be used after diluted with component (f): water. Even when diluted with water, the diluted solution is adjusted so that the diluted solution satisfies the ratios of the components (a) to (f). The dirt is preferably removed by washing the article to be cleaned by applying the cleaning composition and allowing it to stand for a while, and then wiping with a mop or the like or rinsing with a water spray or the like.

Examples 1-10 and Comparative Examples 1-6
Each component shown in Table 1 was mixed at 25 ° C. for 10 to 30 minutes with a magnetic stirrer (length 40 mm stirrer, rotation speed 500 rpm) to prepare 1 liter of a cleaning composition. About each obtained cleaning composition, (1) Measurement of pH, (2) Measurement of flash point, (3) Detergency, (4) Emulsion stability shown below were evaluated. The results are shown in Table 1.

(1) Measurement of pH While stirring each cleaning composition at 25 ° C. (length 20 mm stirrer, rotation speed 60 rpm), the pH was adjusted using a pH meter (HM-30) manufactured by Toa Denpa Kogyo Co., Ltd. It was measured.

(2) Measurement of flash point The flash point of each cleaning composition was measured by the JIS method (JIS K2265). In Table 1, “-” in the flash point column indicates that the flash point is not detected.

(3) Detergency <Test Example 1 (Cleaning Test)>
Under the following cleaning conditions, the test piece coated with dirt was immersed in a cleaning solution, and the cleaning ability of the rolling mill dirt was evaluated based on the dirt removal rate shown below. Each cleaning solution was tested three times. The average value is shown in Table 1. If the soil removal rate shows a high value, the cleaning property of the rolling mill soil is good.
≪Cleaning conditions≫
Test piece: SPCC-D material (50 mm width × 100 mm length × 0.5 mm thickness)
Dirty type: Scum accumulated around rolling mill (metal content = 30% by weight, oil content = 20% by weight, metal soap = 10% by weight, moisture = 40% by weight. (This ratio is an analysis of the collected soil.)
Application amount: 1000 g / m ² (After uniform application, dry for 3 days at room temperature)
Cleaning solution: Undiluted solution of cleaning composition Immersion conditions: 25 ° C., standing (without stirring), 30 minutes Evaluation method: weight of test piece before applying dirt (T), weight before cleaning of test piece (W1) The weight after washing (W2) was measured, and the stain removal rate (%) was calculated from the following formula. Dirt removal rate (%) = {(W1-W2) / (W1-T)} × 100

(4) Emulsification stability <Test Example 2 (Emulsification test)>
To the rolling oil emulsion prepared below, a cleaning liquid (stock solution of the cleaning composition) was mixed so that the ratio to the rolling oil emulsion was 0.1% by weight. The volume average particle diameter of the rolling oil emulsion before and after mixing the cleaning liquid was measured with the following Coulter counter, and the emulsion stability was evaluated from the amount of change in particle diameter before and after that (difference in particle diameter). If the change amount of the particle diameter shows a small value, the emulsion stability is good.
≪Preparation of rolling oil emulsion≫
A commercially available cold rolled oil for ester steel sheet is diluted with pure water so as to have a concentration of 4% by weight, and then at a liquid temperature of 60 ° C., using an M-type homomixer (manufactured by Primics) at 9000 rpm for 30 minutes. By stirring, 1 liter of a dispersion of rolling oil emulsion particles having a volume average particle diameter of 10 μm was prepared. Table 1 shows the absolute value of the difference between the volume average particle diameter of the mixture of the rolling oil emulsion and the cleaning liquid and the volume average particle diameter of the rolling oil emulsion particles in the rolling oil emulsion.
≪Particle size measurement conditions≫
Measuring instrument: Coulter counter multisizer (manufactured by BECKMAN COULTER)
Measurement temperature: 25 ° C
Aperture diameter: 100 μm
Measurement liquid conditions: About 30 μl of a rolling oil emulsion or a mixture of a rolling oil emulsion and a washing liquid was used and diluted to 100 ml with a blood diluent (reagent, manufactured by Wako Pure Chemical Industries, Ltd.).

In Table 1, the solvent according to component (a), the nonionic amine surfactant (oil-soluble dispersant) according to component (b), the nonionic surfactant according to component (c), the component The anionic surfactant according to (d), the rust inhibitor according to component (e), and other additives mean the following. In addition, ion-exchange water was used for the water which concerns on a component (f). Note that EO represents an oxyethylene group.
Solvent A ... kerosene (flash point: 44 ° C) (manufactured by Wako Pure Chemical Industries, reagent)
Solvent B ... Mixed hydrocarbon (flash point: 64 ° C) (Maruzen Petrochemical Co., Ltd., Swazol 1500)
Solvent C: Mixed hydrocarbon (flash point: 82 ° C.) (Maruzen Petrochemical Co., Ltd., Swazol 1800)
Oil-soluble dispersant A: polyoxyethylene laurylamine (EO average addition mole number = 7, HLB = 12.1) (Aoki Yushi Kogyo Co., Ltd., BLAUNON L-207)
Oil-soluble dispersant B: polyoxyethylene laurylamine (EO average addition mole number = 10, HLB = 13.6) (Aoki Oil & Fats Industrial Co., Ltd., BLAUNON L-210)
Oil-soluble dispersant C: polyoxyethylene coconut amine (EO average added mole number = 12, HLB = 14.0) (manufactured by SINO-JAPAN CHEMICAL, SINOPOL 412)
Nonionic surfactant A: polyoxyethylene oleyl ether (EO average addition mole number = 8, HLB = 10.0) (manufactured by Kao Corporation, Emulgen 408)
Nonionic surfactant B: polyoxyethylene dodecyl ether (EO average added mole number = 7, HLB = 12.1) (manufactured by Kao Corporation, Emulgen 707)
Nonionic surfactant C: polyoxyethylene lauryl ether (EO average addition mole number = 9, HLB = 13.6) (manufactured by Kao Corporation, Emulgen 109P)
Anionic surfactant A: calcium dodecylbenzenesulfonate (solid content = 70% by weight) (Naoperex C-70, manufactured by Kao Corporation)
Anionic surfactant B ... sodium dodecylbenzenesulfonate (solid content = 65% by weight) (Naoperex G-65, manufactured by Kao Corporation)
Antirust agent A ... Triethanolamine salt of oleic acid Antirust agent B ... Triethanolamine Antirust agent C ... Hexadecenyl succinic acid (L-ASA manufactured by Kao Corporation)
*: Rust preventive agent A and rust preventive agent B are oleic acid (manufactured by Kao Corporation, Lunac OP) and triethanolamine (manufactured by Wako Pure Chemical Industries, Ltd., reagent) in a 1: 1 ratio. The total amount of oleic acid triethanolamine salt and triethanolamine in the product was 2 wt% (1.53 wt% oleic acid triethanolamine salt and 0.47 wt% triethanolamine) and mixed. Additive A: Antioxidant (2,6-di-tert-butyl-p-cresol) (manufactured by API Corporation, Yoshinox BHT)
Additive B ... Sodium hydroxide (Wako Pure Chemical Industries, Reagent)
Additive C: Sodium ethylenediaminetetraacetate (Wako Pure Chemical Industries, Reagent)

  The HLB value is based on the standard of the Griffin method.

  From the results of Table 1, the cleaning composition of the present invention has a low flash point, a low risk of fire, a high dirt removal rate, a small change in particle diameter, and a large amount of metal powder. It is recognized that excellent cleaning performance is satisfied in the cleaning operation around the machine on which the scum-like dirt is deposited and accumulated. On the other hand, since the cleaning composition of the comparative example does not satisfy each component, content or specific ratio of the cleaning composition of the present invention, the flash point is detected, the soil removal rate is low, the particle size There is nothing that satisfies the low risk and cleanability because the amount of change is large.

Claims (5)

(A) 30-68.5% by weight of a petroleum solvent having a flash point of 40-100 ° C.
(B) 0.5 to 5% by weight of a nonionic amine surfactant,
(C) 5 to 10% by weight of a nonionic surfactant (excluding the component (b)),
(D) 5 to 10% by weight of an anionic surfactant,
(E) 1 to 5% by weight of a rust inhibitor, and
(F) 20 to 58.5% by weight of water,
A rolling mill composition with a weight ratio of component (b) to component (c) (component (c) / component (b)) of 2 to 8 and a pH of 8 to 10 object.   The cleaning composition for rolling mills according to claim 1, wherein the weight ratio of component (a) to component (f) (component (a) / component (f)) is 1 to 3.3. Component (b) is represented by the following general formula (1):

[Wherein, X is —H, —R ² or — (AO) _m —H, R ¹ and R ² are alkyl groups and / or alkenyl groups, A is an alkylene group, and n and m are oxyalkylene groups. The cleaning composition for rolling mills according to claim 1 or 2, represented by the formula:   The cleaning composition for rolling mills according to any one of claims 1 to 3, wherein the component (c) is a polyoxyalkylene alkyl (and / or alkenyl) ether.   A cleaning method around a rolling mill, comprising a step of cleaning dirt around the rolling mill, which is an object to be cleaned, with the detergent composition for rolling mill according to any one of claims 1 to 4.