EP1862530A1 - Zweikomponenten-blockierungsinhibitor für die heissbearbeitung von kunststoff und dessen verwendung in einem verfahren zur herstellung eines nahtlosen rohrs - Google Patents

Zweikomponenten-blockierungsinhibitor für die heissbearbeitung von kunststoff und dessen verwendung in einem verfahren zur herstellung eines nahtlosen rohrs Download PDF

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EP1862530A1
EP1862530A1 EP06713423A EP06713423A EP1862530A1 EP 1862530 A1 EP1862530 A1 EP 1862530A1 EP 06713423 A EP06713423 A EP 06713423A EP 06713423 A EP06713423 A EP 06713423A EP 1862530 A1 EP1862530 A1 EP 1862530A1
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Prior art keywords
aqueous solution
mass
water
production example
soluble
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French (fr)
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EP1862530A4 (de
EP1862530B1 (de
Inventor
Sumio c/o Sumitomo Metal Industries Ltd. Iida
Masami c/o SUMITOMO METAL INDUSTRIES LTD. IMAMURA
Yuuji c/o SUMITOMO METAL INDUSTRIES LTD. TANAKA
Kazuhiro c/o SUMITOMO METAL INDUSTRIES LTD. SHIMODA
Hirofumi c/o SUMITOMO METAL INDUSTRIES LTD. HORI
Akira c/o PALACE CHEMICAL CO. LTD. MOTOKI
Shizuo c/o Palace Chemical Co. Ltd. MORI
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Nippon Steel Corp
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Palace Chemical Co Ltd
Sumitomo Metal Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B19/00—Tube-rolling by rollers arranged outside the work and having their axes not perpendicular to the axis of the work
    • B21B19/02—Tube-rolling by rollers arranged outside the work and having their axes not perpendicular to the axis of the work the axes of the rollers being arranged essentially diagonally to the axis of the work, e.g. "cross" tube-rolling ; Diescher mills, Stiefel disc piercers or Stiefel rotary piercers
    • B21B19/04—Rolling basic material of solid, i.e. non-hollow, structure; Piercing, e.g. rotary piercing mills
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/081—Inorganic acids or salts thereof containing halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Definitions

  • the present invention relates to a two-component anti-seizure agent for hot metal working process for inhibiting seizing between guide shoes and a pipe or a tube (hereinafter, refer to "a pipe” as “a pipe or a tube”.) in a piercing-rolling process of seamless pipe production using a piercing-rolling mill having disk-roll type guide shoes, particularly a piercing-rolling mill having transverse disk-roll type guide shoes of which rotational axis is vertical to the surface of the earth. Also, the present invention relates to a method of manufacturing seamless pipe using the anti-seizure agent.
  • Patent document 1 discloses a piercing-rolling method where a mixed liquid type coating material (which is provided by adding sodium silicate (water glass) as a binder to metal oxide particles such as iron oxide) is applied onto the circumferential surface of guide shoes.
  • Patent document 2 discloses lubricants for hot process composed of an aqueous solution containing an iron oxide, a sodium silicate, a starch, and a xanthan gum.
  • Patent document 3 discloses a hot-rolling method to form a coating onto guide shoes and so on by applying a coat-forming solution mainly containing aqueous polymer salt prepared by non-aqueous polymeric acid and a coat-forming supplementary solution containing strong acid or aluminum salt thereof as the main component to make coating component in the polymer salt deposit from the coat-forming solution.
  • an object of the present invention is to provide an anti-seizure agent which is capable not to be easily washed away once adhered to the contact surface between a pipe material and guide shoes; not to adhere to the rolls, for the anti-seizure agent which adhered to the contact surface between a pipe material and guide shoes; and to inhibit occurrence of flaws without causing slippage between the rolls and a pipe material.
  • Another object of the present invention is to provide a method of manufacturing seamless pipe using the anti-seizure agent.
  • the first aspect of the present invention is a two-component anti-seizure agent for hot metal working process comprising the first aqueous solution and the second aqueous solution, wherein the first aqueous solution contains 10 ⁇ 30 mass % of sodium silicate equivalent to anhydride to total mass (100 mass %) of the first aqueous solution, and the second aqueous solution contains at least one kind selected from a group consisting of: an organic acid and water-soluble amine salts thereof, an inorganic acid and water-soluble amine salts thereof, a water-soluble amine, a water-soluble alcohol, and a water-soluble metal chloride.
  • two-component means a type of anti-seizure agent to be used in the following procedure.
  • the first aqueous solution and the second aqueous solution are not mixed but separately stored.
  • the anti-seizure agent is used, the first aqueous solution and the second aqueous solution are respectively applied onto the guide shoes; these two aqueous solutions then contact each other for the first time.
  • the first aqueous solution may contain 10 ⁇ 30 mass % of sodium silicate equivalent to anhydride, 10 ⁇ 60 mass % of iron oxide, 0 ⁇ 5 mass % of modified starch, and 0 ⁇ 1 mass % of shear-rate dependent viscosity reducer, to total mass (100 mass %) of said first aqueous solution.
  • shear-rate dependent viscosity reducer means a generic name of compounds having the following property. That is, a solution, which dissolved this particular compound in a solvent such as water, has the property such that when shear force is given with increasing shear-rate, the viscosity of the solution is reduced, and when the shear force is removed, the viscosity of the solution recovers.
  • the shear-rate dependent viscosity reducer is preferably a xanthan gum.
  • the second aspect of the invention is a method of manufacturing seamless pipe using a piercing-rolling mill having disk-roll type guide shoes, the method comprising the steps of: the first process for applying the first aqueous solution to the circumferential surface of the disk-roll type guide shoes, and the second process for applying the second aqueous solution to the circumferential surface of the disk-roll type guide shoes to form the water-proof coating on the circumferential surface, wherein the first aqueous solution contains 10 ⁇ 30 mass % of sodium silicate equivalent to anhydride to total mass (100 mass %) of the first aqueous solution, and the second aqueous solution contains at least one kind selected from a group consisting of: an organic acid and water-soluble amine salts thereof, an inorganic acid and water-soluble amine salts thereof, a water-soluble amine, a water-soluble alcohol, and a water-soluble metal chloride.
  • the first aqueous solution preferably contains 10 ⁇ 30 mass % of sodium silicate equivalent to anhydride, 10 ⁇ 60 mass % of iron oxide, 0 ⁇ 5 mass % of modified starch, and 0 ⁇ 1 mass % of shear-rate dependent viscosity reducer, to total mass (100 mass %) of said first aqueous solution.
  • the shear-rate dependent viscosity reducer is preferably a xanthan gum.
  • the anti-seizure agent applied to the disk-roll type guide shoes is provided to the circumferential surface of the disk-roll type guide shoes being a contact surface between a pipe material and guide shoes and is maintained on the circumferential surface. Further, the anti-seizure agent is not washed away by rolls' cooling water, it does not run off to adhere to the rolls. Furthermore, according to the method of manufacturing seamless pipe using this anti-seizure agent, the rolls and a pipe material do not cause slippage each other, thereby it is capable to carry out piercing-rolling of the pipe material. Therefore, it is capable to manufacture a seamless pipe which does not have seizing flaw thereby the pipe is excellent in the surface quality.
  • FIG.1 is a diagrammatic view showing a test method for evaluation of seizing.
  • the two-component anti-seizure agent for hot metal working process of the present invention is composed of two solutions, i.e. the first aqueous solution and the second aqueous solution.
  • the first aqueous solution is applied to the portion where guide shoes and a pipe material contact each other, then the second aqueous solution is applied thereon so as to form a water-proof coating in this portion. Thereby it is capable to inhibit seizing of the pipe material.
  • the first aqueous solution contains 10 ⁇ 30 mass % of sodium silicate equivalent to anhydride to total mass (100 mass %) of the first aqueous solution.
  • Sodium silicate is commercially available in a form of water glass in which sodium silicate is combined with water and which usually contains 45 ⁇ 70 mass % of water. Sodium silicate becomes hardened when it reacts with the second aqueous solution described below to form a water-proof coating.
  • Content of sodium silicate is, to the total mass (100 mass %) of the first aqueous solution, preferably 10 ⁇ 30 mass %, more preferably 15 ⁇ 25 mass % equivalent to anhydride. Because, when the content of sodium silicate is too small, curing reaction is not sufficiently proceeded; therefore seizing cannot be inhibited sufficiently. On the other hand, when the content of sodium silicate is too large, excess sodium silicate causes too much lubricity. The friction coefficient declines, thus there is a fear of occurrence of roll slippage.
  • kind of sodium silicate is not specifically limited.
  • common water glass such as water glass of JIS (Japanese Industrial Standards) No.1 (Na 2 O ⁇ 2SiO 2 ), water glass of JIS No.3 (Na 2 O ⁇ 3SiO 2 ), water glass of JIS No.4 (Na 2 O ⁇ 4SiO 2 ) can be used.
  • JIS Japanese Industrial Standards
  • No.3 water glass of JIS No.3
  • water glass of JIS No.4 Na 2 O ⁇ 4SiO 2
  • the two-component anti-seizure agent for hot metal working process of the invention can realize the designed performance.
  • the first aqueous solution may contain 10 ⁇ 60 mass % of iron oxide, 0 ⁇ 5 mass % of modified starch, and 0 ⁇ 1 mass % of shear-rate dependent viscosity reducer, to total mass (100 mass %) of the first aqueous solution.
  • Iron oxide is contained in order to realize a function as an anti-seizure agent.
  • Such anti-seizure agent needs to exhibit favorable storage stability and sprayability; the particle diameter of iron oxide is preferably 0.1 ⁇ 10 ⁇ m. Because, when the particle diameter of iron oxide is too large, the storage stability and sprayability are deteriorated. While, the particle diameter of the same is too small, seizing cannot be inhibited sufficiently.
  • Content of iron oxide is, to the total mass (100 mass %) of the first aqueous solution, preferably 10 ⁇ 60 mass %, more preferably 20 ⁇ 40 mass %.
  • content of iron oxide is too small, seizing cannot be inhibited sufficiently.
  • content of the same is too large, density and viscosity of the anti-seizure agent become too high, thereby sprayability thereof is deteriorated.
  • Kind of iron oxide may be any one of hematite (Fe 2 O 3 ), magnetite (Fe 3 O 4 ), or wüstite (FeO); these may be used alone or in combination of two or more thereof.
  • Modified starch has a property of thermal gelatinization at high temperatures (usually 80°C or more). This property contributes to prevent running off of the first aqueous solution applied to the surface of guide shoes being hot. However, when the second aqueous solution is applied before the first aqueous solution to run off, addition of the modified starch is not necessary.
  • the content is, to the total mass (100 mass %) of the first aqueous solution, preferably 5 mass % or less, more preferably within the range of 1 ⁇ 4 mass %. Because, when the content of modified starch is too large, friction coefficient of the anti-seizure agent declines, thus there is a fear of occurrence of roll slippage.
  • modified starch for example, there may be dextrin, oxidized starch, soluble starch, etherified starch, and esterified starch. These may be used alone or in combination with two or more thereof.
  • xantham gum is preferably used as the shear-rate dependent viscosity reducer.
  • Xantham gum is a polysaccarides of about 2 million molecular weight having two glucoses, two mannoses, and two glucuronic acids as the constituent unit.
  • the glucuronic acid is usually salt of K (potassium), Na (sodium), or Ca (calcium).
  • K potassium
  • Na sodium
  • Ca calcium
  • Xantham gum becomes high viscosity because of the entanglement of the molecule chains when the solution is in a static state; on the contrary, xantham gum has thixotropic property where it becomes low viscosity because of the relaxation of entanglement of the molecule chains when the solution is in a kinetic status.
  • Depends on the addition thereof to the first aqueous solution it is possible to control the viscosity of the first aqueous solution in a kinematical way. In other words, when the first aqueous solution is stored or is located in an area such as inner area of piping of a spray apparatus before spray application to guide shoes, the first aqueous solution is in a static status and is high viscosity. Therefore it is stable.
  • the content thereof is preferably 1 mass % or less, more preferably within the range of 0.05 ⁇ 0.8 mass %. If the content of the shear-rate dependent viscosity reducer is excessive, the viscosity thereof becomes too high and spray cannot be appropriately applied.
  • total amount of water including water contained in water glass and another water to be added is, to total mass of the first aqueous solution (100 mass %), preferably 24.0 ⁇ 84.5 mass %, more preferably 40 ⁇ 70 mass %.
  • the second aqueous solution contains at least one kind selected from a group consisting of: an organic acid and water-soluble amine salts thereof, an inorganic acid and water-soluble amine salts thereof, a water-soluble amine, a water-soluble alcohol, and a water-soluble metal chloride.
  • an organic acid it is preferable to use one whose total acid number is 500mgKOH/g or more. Specifically, it is preferable to use a monobasic acid such as formic acid, acetic acid, and lactic acid; a dibasic acid such as oxalic acid, malonic acid, maleic acid, malic acid, and tartaric acid; a tribasic acid such as citric acid.
  • a monobasic acid such as formic acid, acetic acid, and lactic acid
  • a dibasic acid such as oxalic acid, malonic acid, maleic acid, malic acid, and tartaric acid
  • a tribasic acid such as citric acid.
  • total acid number means, as described in JIS K 2501 (Petroleum products and lubricants-Determination of Neutralization number), "value in milligram (mg) of potassium hydroxide necessary for neutralize total acid component contained in 1g of sample”.
  • the second aqueous solution it is possible to use a liquid substance just as it is, or to use a solid substance dissolved in water at a limit concentration. In order to give fire resistance to the second aqueous solution, it is preferable to be used as 5 ⁇ 30 mass % of water solution.
  • Water-soluble amine salts of organic acid are, together with the amine salt of the above-mentioned organic acids, an organic acid of which amine salt is to become water-soluble, for instance, amine salt of dibasic acid such as succinic acid, glutaric acid, adipic acid, phthalic acid; and amine salt of tribasic acid such as trimellitic acid.
  • amine salt of dibasic acid such as succinic acid, glutaric acid, adipic acid, phthalic acid
  • tribasic acid such as trimellitic acid.
  • Examples of amine of water-soluble amine salt of organic acid include: amino alcohol such as monoethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanol amine, triisopropanol amine, N-( ⁇ -aminoethyl) ethanol amine, N-methyl diethanol amine; and ammonia, and so on.
  • amino alcohol such as monoethanol amine, diethanol amine, triethanol amine, monoisopropanol amine, diisopropanol amine, triisopropanol amine, N-( ⁇ -aminoethyl) ethanol amine, N-methyl diethanol amine; and ammonia, and so on.
  • an inorganic acid examples include hydrochloric acid, sulfuric acid, phosphoric acid.
  • As the second aqueous solution it is possible to use a liquid substance just as it is, or to use a solid substance dissolved in water at limit concentrations. In order to secure safety to the human body, these second aqueous solutions are preferably used as 1 ⁇ 20 mass % solution.
  • water-soluble amine salts of an inorganic acid include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, molybdenum acid, and tungsten acid; and salts with amine in water-soluble amine salts of the above organic acids.
  • water-soluble amine there may be amino alcohol shown as amine in water-soluble amine salts of the above organic acids.
  • water-soluble alcohol examples include methyl alcohol, ethyl alcohol, isopropyl alcohol, diethyleneglycol ethylether, ethyleneglycol butylether.
  • metal chloride examples include iron chloride, calcium chloride, magnesium chloride, and aluminum chloride.
  • the water-soluble metal chloride is, from the view point of safety and solvency, desirably used as 5 ⁇ 50 mass % aqueous solution.
  • the second aqueous solution may contain two or more kinds of each of the above component. In that case, an aqueous solution whose total sum of each component adjusted to be 10 ⁇ 50 mass % is desirably used.
  • Method for inhibiting seizing of seamless pipes at a time of piercing-rolling of the present invention in a process of piercing-rolling of a pipe material using tilted-roll piercing-rolling mill having disk-roll type guide shoes, has the first process for applying the first aqueous solution to a circumferential surface of the disk-roll type guide shoes, and the second process for applying the second aqueous solution to the circumferential surface of the disk-roll type guide shoes to have a water-proof coating on the circumferential surface.
  • the first aqueous solution to be used in the first process is same as the first aqueous solution for the above two-component anti-seizure agent for hot metal working process; and second aqueous solution used in the second process is same as the second aqueous solution for the above two-component anti-seizure agent for hot metal working process.
  • the method of inhibiting seizing of the invention can be suitably used specifically for such a piercing-rolling mill having transverse disk-roll type guide shoes.
  • the circumferential surface of the disk-roll type guide shoes onto which the first aqueous solution and the second aqueous solution is applied is a circumferential side surface of disk-shaped disk-roll type guide shoes.
  • this circumferential side surface is half-moon shape in longitudinal section along the shape of pipe materials to be piercing-rolled.
  • the first aqueous solution is applied onto the circumferential surface of the disk-roll type guide shoes so as the amount of application to be 50 ⁇ 500g/m 2 , preferably 100 ⁇ 400g/m 2 .
  • the second aqueous solution is applied onto the above circumferential surface of the disk-roll type guide shoes so as the amount of application to be 30 ⁇ 300g/m 2 , preferably 50 ⁇ 200g/m 2 . Because, if the application amount of the first aqueous solution is too small, component for inhibiting seizing lacks thereby sufficient seizing inhibiting effect cannot be obtained. Further, if the application amount of the first aqueous solution is excessive, the second aqueous solution cannot sufficiently gelatinize the first aqueous solution, therefore favorable water-proof coating cannot be formed.
  • the second aqueous solution of which application amount is a half of that of the first aqueous solution it is desirable to apply the second aqueous solution of which application amount is a half of that of the first aqueous solution. Because, if the application amount of the second aqueous solution is too small, it cannot sufficiently gelatinize the first aqueous solution. On the other hand, if the application amount of the second aqueous solution is excessive, gelatinization effect is saturated, therefore it is economically disadvantageous.
  • the application method of the first aqueous solution and the second aqueous solution is not particularly limited, the method may include brush coating and spray coating. In order to uniformly apply these solutions onto the circumferential surface of the disk-roll type guide shoes, use of spray is preferable.
  • Materials for the seamless pipe, where the method of manufacturing seamless pipe of the invention can be applied is not particularly limited. This method is remarkably effective especially to the materials (like stainless steel) which are easily seized.
  • Iron oxide (chemical formula: Fe 2 O 3 , purity: 98%, average particle diameter: 0.3 ⁇ m), sodium silicate (chemical formula: Na 2 O ⁇ 2SiO 2 ), modified starch (British gum 140, produced by Matsutani Chemical Industry Co,. Ltd.), xantham gum (trade name "KELZAN", produced by CP Kelco), and water were mixed based on the ratio shown in Table 1 to obtain the first aqueous solution.
  • Table 1 the value of each component is represented by mass % to total (100 mass %) of the first aqueous solution.
  • a solution which contains each component shown in Table 2 based on the ratio shown in Table 2 was used as the second aqueous solution.
  • Table 2 the value of each component is represented by mass % to total (100 mass %) of the second aqueous solution.
  • commercially available aqueous solution produced by Taimei Chemicals Co., Ltd., trade name "Taipac" (concentration: 10 ⁇ 11 mass % equivalent to Al 2 O 3 ) was used as it is.
  • a solution which contains each component shown in Table 3 based on the ratio shown in Table 3 was used as the first aqueous solution.
  • Individual material of iron oxide, sodium silicate, modified starch, and xantham gum to be used were the same as those of production example (1-1).
  • ammonium salts of isobutylene maleic acid co-polymer a material such that weight-average molecular weight 80,000 ⁇ 90,000 of an isobutylene maleic acid co-polymer was neutralized with ammonia was used.
  • polyacrylic acid sodium salt a material whose weight-average molecular weight is about 500,000 was used; and as carboxy methylcellose, a sodium salt whose weight-average molecular weight is 10,000 ⁇ 15,000 was used.
  • each component in Table 1 is represented by mass % to total (100 mass %) of the first aqueous solution.
  • ammonium borate was deposited at room temperature; however it was dissolved by heat.
  • a solution which contains each component shown in Table 4 based on the ratio shown in Table 4 was used as the second aqueous solution.
  • the value of each component in Table 4 is represented by mass % to total (100 mass %) of the second aqueous solution.
  • Caproic acid and oleic acid to be used in the Comparative Production example (2-1) and Comparative Production example (2-2) are organic acids of which total acid number is 500mgKOH/g or less.
  • a combination of the first aqueous solution and the second aqueous solution shown in Table 5 was prepared to make it the two-component anti-seizure agent for hot metal working process of the present invention. Then, the evaluation thereof was carried out in terms of curing and seizing resistance. The evaluation results are shown in Table 5.
  • a combination of the first aqueous solution and the second aqueous solution shown in Table 5 was prepared to make it the two-component anti-seizure agent for hot metal working process of the present invention.
  • the first aqueous solution only (Comparative examples 10 and 11), or the second aqueous solution only (Comparative example 17) were also used as the anti-seizure agent for hot metal working process of the invention. Then, the evaluation thereof was done in terms of curing and seizing resistance. The evaluation results are shown in Table 5.
  • Curing was evaluated in accordance with the following procedure. Firstly, about 60g/m 2 of the first aqueous solution was applied onto a glass plate, immediately after that, the glass plate to which the first aqueous solution been applied was dipped in the second aqueous solution for 1 second. Then, the glass plate was taken out from the second aqueous solution, and 1 second later, the surface of the glass plate was wiped off by waste cloth. The obtained glass plates were evaluated in accordance with the following criteria.
  • FIG. 1 is a diagrammatic view showing the test method.
  • two-phase stainless steel (25Cr-7Ni-3Mo steel) member 1 is heated up to 1000°C with use of high-frequency coil 6.
  • the first aqueous solution from nozzle 3 and later the second aqueous solution from nozzle 4 (depending on conditions, either one of the first aqueous solution only or the second aqueous solution only) were applied by spray application on the surface of alloyed cast-iron roll material 2 while the roll material 2 was rotated at 20rpm rotation speed.
  • water was injected from nozzle 5 to the surface of the roll material 2.
  • the member 1 was thrust onto the surface on the roll material 2 at 196N for 3 seconds (the period when the roll material 2 goes into a 360-degree roll). After the thrust, surface condition of the roll material 2 was evaluated in accordance with the following criteria.
  • the two-component anti-seizure agent for hot metal working process of the present invention can be used for inhibiting seizing between guide shoes and a pipe in the piercing-rolling process using a piercing-rolling mill having disk-roll type guide shoes, especially a piercing-rolling mill having transverse disk-roll type guide shoes whose rotational axis is vertical to the surface of the earth.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)
EP06713423.9A 2005-02-09 2006-02-09 Zweikomponenten-blockierungsinhibitor für die heissbearbeitung von kunststoff und dessen verwendung in einem verfahren zur herstellung eines nahtlosen rohrs Active EP1862530B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005033015A JP4597695B2 (ja) 2005-02-09 2005-02-09 二液型熱間塑性加工用焼付防止剤、およびそれを用いた継目無管の製造方法
PCT/JP2006/302280 WO2006085599A1 (ja) 2005-02-09 2006-02-09 二液型熱間塑性加工用焼付防止剤、およびそれを用いた継目無管の製造方法

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EP1862530A1 true EP1862530A1 (de) 2007-12-05
EP1862530A4 EP1862530A4 (de) 2012-01-25
EP1862530B1 EP1862530B1 (de) 2017-12-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8024953B2 (en) 2008-01-11 2011-09-27 Sumitomo Metal Industries, Ltd. Lubricant for hot working and method for producing seamless steel pipe

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JP4969276B2 (ja) * 2007-03-14 2012-07-04 住鉱潤滑剤株式会社 水系２層塗布型塑性加工用潤滑剤及び２層潤滑被膜の形成方法
CN102660367B (zh) * 2012-04-24 2013-08-21 长春工业大学 碳钢薄板冲压用水溶性拉延油的生产方法
CN109396198B (zh) * 2018-11-14 2023-09-19 浙江中达新材料股份有限公司 一种带自动加油的冷轧管装置

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JPH1135967A (ja) * 1997-07-16 1999-02-09 Sumitomo Metal Ind Ltd 熱間加工用潤滑剤及び潤滑方法

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JPH05117684A (ja) * 1991-10-30 1993-05-14 Yushiro Chem Ind Co Ltd プラグ圧延機用の液体潤滑剤
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JPH04288916A (ja) * 1991-03-19 1992-10-14 Kawasaki Steel Corp 熱間圧延方法及び表面処理剤
JPH1135967A (ja) * 1997-07-16 1999-02-09 Sumitomo Metal Ind Ltd 熱間加工用潤滑剤及び潤滑方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8024953B2 (en) 2008-01-11 2011-09-27 Sumitomo Metal Industries, Ltd. Lubricant for hot working and method for producing seamless steel pipe

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Publication number Publication date
EP1862530A4 (de) 2012-01-25
BRPI0606156B1 (pt) 2016-03-29
JP4597695B2 (ja) 2010-12-15
EP1862530B1 (de) 2017-12-13
BRPI0606156A2 (pt) 2009-06-02
WO2006085599A1 (ja) 2006-08-17
CN101142304B (zh) 2012-01-18
JP2006219556A (ja) 2006-08-24
CN101142304A (zh) 2008-03-12

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