EP3222702A1 - Zylinder schmierölzusammensetzung für mit schrubber ausgestattete kreuzkopfdieselmotoren - Google Patents

Zylinder schmierölzusammensetzung für mit schrubber ausgestattete kreuzkopfdieselmotoren Download PDF

Info

Publication number
EP3222702A1
EP3222702A1 EP15861457.8A EP15861457A EP3222702A1 EP 3222702 A1 EP3222702 A1 EP 3222702A1 EP 15861457 A EP15861457 A EP 15861457A EP 3222702 A1 EP3222702 A1 EP 3222702A1
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
mass
component
scrubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15861457.8A
Other languages
English (en)
French (fr)
Other versions
EP3222702A4 (de
EP3222702B1 (de
Inventor
Shigeki Takeshima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
JXTG Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014234045A external-priority patent/JP6386348B2/ja
Priority claimed from JP2014234046A external-priority patent/JP6297477B2/ja
Application filed by JXTG Nippon Oil and Energy Corp filed Critical JXTG Nippon Oil and Energy Corp
Publication of EP3222702A1 publication Critical patent/EP3222702A1/de
Publication of EP3222702A4 publication Critical patent/EP3222702A4/de
Application granted granted Critical
Publication of EP3222702B1 publication Critical patent/EP3222702B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/047—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and macromolecular compounds
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • 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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02—Specified values of viscosity or viscosity index
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • 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
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/245—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid used as base material
    • 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
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • C10N2030/041—Soot induced viscosity control
    • 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
    • C10N2030/24—Emulsion properties
    • 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
    • C10N2030/52—Base number [TBN]
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • 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
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Definitions

  • the present invention relates to a cylinder lubricating oil composition for a crosshead diesel engine equipped with a scrubber, and specifically relates to a cylinder lubricating oil composition suitable for use in a crosshead diesel engine equipped with a scrubber.
  • Crosshead diesel engines are used a lot for main engines of large ships. Thus, it can be said that large part of the effect of ship operations on the environment is from emission matter of crosshead diesel engines.
  • NOx nitrogen oxides
  • SOx sulfur oxides
  • Patent Literatures 1 to 4 EGR (Exhaust Gas Recirculation) scrubbers
  • options to reduce SO x emission amount considered are to reduce the sulfur components in fuels (use of low-sulfur fuels), and to make the amounts of sulfur oxide emitted from conventional high-sulfur fuels same as the amounts of sulfur oxide emitted from low-sulfur fuels of no more than 0.5 % in sulfur component, by means of exhaust gas aftertreatment apparatuses. The latter option is more focused on because low-sulfur fuels are expensive.
  • Patent Literature 5 There is a suggestion of a de-SO x treatment by means of a scrubber as an exhaust gas aftertreatment apparatus
  • a scrubber generally means a device to separate harmful substances (e.g. harmful gases and dusts) in exhaust gases, by collecting the harmful substances into liquid drops and liquid films of absorption liquids (e.g. water). For example, separation of SO x by absorbing it into an aqueous solution such as sodium hydroxide aqueous solution and separation of soot by density difference after the soot is collected in water phase are considered.
  • harmful substances e.g. harmful gases and dusts
  • absorption liquids e.g. water
  • exhaust gases from diesel engines include hydrocarbon-based substances such as unburnt fuel and lubricant mist.
  • hydrocarbon-based substances do not dissolve in water, and may emulsify by strong mixing with water. If these hydrocarbon-substances and water are emulsified, the soot component in the exhaust gases are wrapped inside the emulsion to form scums, and the scums accumulate at the upper portion of the absorption liquid, as a result, the separation becomes difficult.
  • Cylinder oils for crosshead diesel engines are once-through type lubricating oils, that is, they are not cleaned by centrifugal purifiers or repeatedly used, and do not contact with water in centrifugal purifiers. Therefore, water separation property was not previously required of cylinder oils for crosshead diesel engines.
  • An object of the present invention is to provide a cylinder lubricating oil composition for a crosshead diesel engine equipped with a scrubber, by which it is possible to improve water separation property and to reduce or inhibit generation of scums from hydrocarbon-based substances, soots and moisture in the scrubber.
  • a first aspect of the present invention is A cylinder lubricating oil composition for a crosshead diesel engine equipped with a scrubber, including:
  • crosshead diesel engine equipped with a scrubber means a crosshead diesel engine provided with a structure of purifying gases emitted from cylinders by at least one scrubber.
  • the scrubber may be an EGR scrubber with which the gases that passed through the scrubber are guided to the inlet side of the cylinders (for example see Patent Literatures 1 to 4), and may be an exhaust gas scrubber with which the gases that passed through the scrubber are not guided to the inlet side of the cylinders (for example see Patent Literature 5).
  • Cross diesel engine is typically a two-stroke crosshead diesel engine.
  • a first embodiment of the first aspect of the present invention is a cylinder lubricating oil composition for a crosshead diesel engine equipped with a scrubber, including:
  • the lubricating oil composition includes (C) a nitrogen-containing ashless dispersant may be given for example.
  • the lubricating oil composition optionally includes:
  • a configuration in which the component (B) is one or more polyether compound may be given for example.
  • the number average molecular weight of the component (B) is no less than 500.
  • polyether compound means a compound having a polyether part, and the polyether part may be further modified by an ester bond and the like for example.
  • a configuration in which the component (A) is a Ca phenate may be given for example.
  • a second embodiment of the first aspect of the present invention is A cylinder lubricating oil composition for a crosshead diesel engine equipped with a scrubber, including:
  • the lubricating oil composition includes the component (C) in an amount of greater than 0 mass% and no more than 0.015 mass% in terms of nitrogen on the basis of the total mass of the composition may be given for example.
  • a configuration in which the component (A2) is a Ca sulfonate and/or a Ca salicylate may be given for example.
  • a second aspect of the present invention is a method of lubricating a cylinder of a crosshead diesel engine equipped with a scrubber, including:
  • the purifying in the scrubber may include contacting the gas introduced into the scrubber with water and/or a basic aqueous solution.
  • a cylinder oil for a crosshead diesel engine equipped with a scrubber by which it is possible to reduce or inhibit generation of scums from hydrocarbon-based substances, soots and moisture in the scrubber.
  • a to B regarding numerical values A and B means “A or more and B or less”.
  • the unit given to the numerical value B is applied as the unit of the numerical value A.
  • At least one selected from the group consisting of mineral oils and synthetic oils may be used.
  • the mineral oil is not particularly limited.
  • General examples of the mineral oil include: a product made by fractional distillation of an atmospheric residue obtained by atmospheric distillation of a crude oil, by carrying out desulfuration and hydrogenolysis to have a desirable viscosity grade; and a product made by solvent dewaxing or contact dewaxing of the above-described atmospheric residue, on which a solvent extraction and hydrogenation are further carried out if necessary.
  • the basic production process of these isomerized wax lubricating base oils are the same as the production process of a hydrogenolysis base oil.
  • synthetic oils used as general lubricating base oils may be used without particular limitations.
  • Specific examples include: polybutenes and hydrides thereof; oligomers such as 1-octene, 1-decene and dodecene, and poly ⁇ -olefines and hydrides thereof which are oligomers and the like of mixtures of the above-mentioned oligomers; diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; polyolesters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythrytol-2-ethylhexanoate, pentaerythritol pelargonate; copolymers of dicarboxylic acids such as dibutyl maleate and
  • the kinematic viscosity at 100°C of the base oil is preferably no less than 10 mm 2 /s, more preferably no less than 14 mm 2 /s, and preferably no more than 25 mm 2 /s and more preferably no more than 20 mm 2 /s.
  • the kinematic viscosity at 100°C of the base oil is preferably no less than 10 mm 2 /s, more preferably no less than 14 mm 2 /s, and preferably no more than 25 mm 2 /s and more preferably no more than 20 mm 2 /s.
  • the kinematic viscosity at 100°C means a kinematic viscosity at 100°C defined in ASTM D-445.
  • Examples of a preferable embodiment of the base oil include a mixture base oil of a base oil having a kinematic viscosity at 100°C of 10 to 14 mm 2 /s and a base oil having a kinematic viscosity at 100 ° C of 20 to 40 mm 2 /s.
  • the viscosity index of the base oil is preferably no less than 85, more preferably no less than 90, and especially preferably no less than 95. By having such lower limit values or more of the viscosity index of the base oil, the viscosity at a low temperature may be held down, and good startability may be obtained.
  • the viscosity index means a viscosity index measured in conformity with JISK2283-1993.
  • the content of saturated component of the base oil based on the total amount of the base oil is preferably no less than 50 mass%, more preferably no less than 55 mass%, and preferably no more than 90 mass% and more preferably no more than 75 mass%.
  • the saturated component means a saturated component measured by the method described in ASTM D 2007-93.
  • component (A) is a so-called metallic detergent generally used in lubricating oils.
  • component (A) include phenate detergents, sulfonate detergents, and salicylate detergents. These metallic detergents may be used alone or in combination.
  • phenate detergents may be especially preferably used.
  • the phenate detergents include alkaline earth metal salts of compounds having a structure represented by the following formula (1), basic salts thereof, and overbased salts thereof.
  • the alkaline earth metal salts include magnesium, barium, and calcium. Among them, magnesium and calcium are preferable, and calcium is especially preferable.
  • the component (A) may be used alone or in combination.
  • R 1 is a linear or branched, saturated or unsaturated C 6 -C 21 alkyl or alkenyl group
  • m is a polymerization degree shown by an integer of 1 to 10
  • A is a sulfide (-S-) group or methylene (-CH 2 -) group
  • x is an integer of 1 to 3.
  • R 1 may be a combination of two or more different groups.
  • the carbon number of R 1 in the formula (1) is preferably 9 to 18, and more preferably 9 to 15. If the carbon number of R 1 is less than 6, the solubility to the base oil may degrade. If the carbon number of R 1 is more than 21, manufacturing is difficult, and the heat resistance may degrade.
  • the polymerization degree m in the formula (1) is preferably 1 to 4. By having the polymerization degree m within this range, the heat resistance may be improved.
  • the base number of the phenate detergent is preferably no less than 60 mg KOH/g, and more preferably no less than 100 mg KOH/g, and preferably no more than 350 mg KOH/g, and more preferably no more than 300 mg KOH/g.
  • the base number is measured by perchloric acid method.
  • the sulfonate detergent include alkaline earth metal salts of alkyl aromatic sulfonc acids obtained by sulfonation of alkyl aromatic compounds, basic salts thereof, and overbased salts thereof.
  • the weight average molecular weight of the alkyl aromatic compound is preferably 400 to 1500, and more preferably 700 to 1300.
  • alkaline earth metal include magnesium, barium, and calcium. Magnesium and calcium are preferable, and calcium is especially preferable.
  • the alkyl aromatic sulfonic acid include a so-called petroleum sulfonic acid and synthetic sulfonic acid.
  • a sulfonated alkyl aromatic compound of lubricating oil distillate of a mineral oil, and a so-called mahogany acid which is a by-product of white oil manufacturing may be given for example.
  • the synthetic sulfonic acid sulfonated alkylbenzene having a linear or brunched alkyl group, obtained by recovery of by-product in alkylbenzene manufacturing plant, the alkylbenzene being a raw material of cleansers, or by alkylation of benzene with polyolefin, may be given.
  • sulfonated alkylnaphthalenes such as sulfonated dinonylnaphthalene may be given.
  • the sulfonating agent used in sulfonation of these alkyl aromatic compounds is not particularly limited, and fuming sulfuric acid and anhydrous sulfate may be used for example.
  • the base number of the sulfonate detergent is preferably no less than 10 mgKOH/g, more preferably no less than 150 mgKOH/g, and more preferably no less than 250 mgKOH/g, and preferably no more than 500 mgKOH/g, and more preferably no more than 450 mgKOH/g.
  • good acid neutralizing property may be obtained.
  • good detergent property may be obtained.
  • the salicylate detergent include metal salicylates, basic salts thereof, and overbased salts thereof.
  • metal salicylate a compound represented by the following formula (2) may be given for example.
  • R 2 independently is a C 14 -C 30 alkyl or alkenyl group
  • M is an alkaline earth metal
  • n is 1 or 2.
  • M is preferably calcium or magnesium, and especially preferably calcium.
  • n is 1.
  • R 2 may be a combination of different groups.
  • the method for manufacturing the alkaline earth metal salicylate is not particularly limited, and a known method for manufacturing a mono alkyl salicylate may be employed.
  • the alkaline earth metal salicylate may be obtained by reacting monoalkyl salicylic acid and the like with metal base such as oxides and hydroxides of alkaline earth metals, or by once changing the monoalkyl salicylic acid and the like to be alkaline metal salts such as sodium salts and potassium salts, then metal-exchanging them with alkaline earth metal salts.
  • the monoalkyl salicylic acid and the like are obtained from phenol as a starting raw material, by carrying out an alkylation on the phenol with olefin thereafter carrying out a carboxylation with carbon dioxide, or from salicylic acid as a starting raw material, by carrying out an alkylation on the salicylic acid with the olefin.
  • the method for obtaining a basic salt of the alkaline earth metal salicylate is not particularly limited.
  • the basic salt may be obtained by heating the alkaline earth metal salicylate and excess alkaline earth metal salt or excess alkaline earth metal basic salt (hydroxide or oxide of alkaline earth metal) in presence of water.
  • the method for obtaining an overbased salt of the alkaline earth metal salicylate is not particularly limited.
  • the overbased salt may be obtained by reaction of the alkaline earth metal salicylate and the base of the hydroxide of the alkaline earth metal and the like, in presence of carbon dioxide, boric acid, or borate salt.
  • the base number of the salicylate detergent is preferably no less than 60 mgKOH/g, more preferably no less than 100 mgKOH/g, and preferably no more than 350 mgKOH/g, and more preferably no more than 300 mgKOH/g.
  • good acid neutralizing property may be obtained.
  • good detergency may be obtained.
  • the metal ratio of the component (A) is a value calculated according to the following formula, and preferably no less than 1, more preferably no less than 3, and preferably no more than 50 and more preferably no more than 30.
  • Metal ratio of component A metal content of component A mol / soap base content of component A mol
  • metal content of the component (A) (mol) is the total of the mol amounts of all metals included in the component (A).
  • soap base content of the component (A) (mol) is the total of mol amounts of all soap bases included in the component (A).
  • one or more calcium detergent selected from the group consisting of Ca phenate detergents, Ca sulfonate detergents, and Ca salicylate detergents may be preferably used.
  • the Ca phenate detergents are the above-described phenate detergents in which calcium is used as the alkaline earth metal. That is, the Ca phenate detergent means a calcium salt, basic salt, or overbased salt of alkylphenol sulfide.
  • the Ca sulfonate detergents are the above-described detergents in which calcium is used as the alkaline earth metal. That is, the Ca sulfonate detergent means a calcium salt, basic salt, or overbased salt of an alkyl aromatic sulfonic acid.
  • the Ca salicylate detergents are the above-described salicylate detergents in which calcium is used as the metal. That is, the Ca salicylate detergent means calcium salicylate, or, a basic salt or overbased salt thereof.
  • the content thereof is preferably 0.50 to 4.3 mass% in terms of calcium on the basis of the total mass of the lubricating oil composition.
  • the second embodiment of the lubricating oil composition of the present invention includes, as the component (A), (A1) a Ca phenate detergent and (A2) a metallic detergent other than any Ca phenate detergent.
  • component (A1) a calcium salt, basic salt, or overbased salt of a compound having a structure represented by the above formula (1) may be given.
  • component (A1) one kind may be used alone, or two or more kinds may also be used in combination.
  • a preferable embodiment of the component (A1) is as described above regarding the phenate detergent.
  • component (A2) Metallic detergent other than any Ca phenate detergent (hereinafter referred to as “component (A2)”) is preferably a metallic detergent other than any phenate detergent.
  • a metallic detergent include sulfonate detergents and salicylate detergents. These metallic detergents may be used alone or in combination.
  • the above-described sulfonate detergents may be used.
  • the preferable embodiment of the sulfonate detergent is as described above.
  • salicylate detergent As the salicylate detergent, the above-described salicylate detergent may be used.
  • the preferable embodiment of the salicylate detergent is as described above.
  • the component (A2) is a Ca sulfonate detergent and/or a Ca salicylate detergent.
  • the base number of the Ca sulfonate detergent is preferably no less than 10 mgKOH/g, more preferably no less than 150 mgKOH/g, and further preferably no less than 250 mgKOH/g, and preferably no more than 500 mgKOH/g, and more preferably no more than 450mgKOH/g.
  • good acid neutralizing property may be obtained.
  • good detergent property may be obtained.
  • the base number of the Ca salicylate detergent is preferably no less than 60 mgKOH/g, and more preferably no less than 100 mgKOH/g, and preferably no more than 350 mgKOH/g, and more preferably 300 mgKOH/g.
  • good acid neutralizing property may be obtained.
  • good detergent property may be obtained.
  • component (B) demulsifier (hereinafter referred to as "component (B)" in the first embodiment of the lubricating oil composition of the present invention
  • demulsifiers which are commercially available may be used without particular limitations.
  • polyether compounds may be preferably used.
  • polyether compound that may be preferably used as the component (B)
  • polyether compounds including propylene oxide unit are especially preferable, such as: polyoxypropylene glycol monoalkyl ethers such as polypropylene glycol butyl ether and polypropylene glycol stearyl ether; and polyoxyethylene polyoxypropylene alkyl ether (ethylene oxide-propylene oxide copolymer).
  • the molecular weight of the component (B) is not particularly limited, and preferably no less than 350, more preferably no less than 500, and further preferably no less than 1000, and preferably no more than 30000, more preferably no more than 10000, and further preferably no more than 5000, by number average molecular weight. By having such lower limit values or more of the number average molecular weight of the component (B), good demulsibility may be obtained.
  • the HLB (hydrophile-lipophile balance) value of the component (B) is not particularly limited as long as it shows demulsification function (emulsion destabilization function), and preferably no less than 13, and more preferably no less than 14.5.
  • the HLB value must be no more than 20 by definition, and preferably no more than 19.5 in view of affinity with the base oil.
  • the content of the component (B) in the first embodiment of the lubricating oil composition of the present invention is 0.02 to 5 mass% on the basis of the total mass of the composition.
  • the content is preferably no less than 0.03 mass%, more preferably no less than 0.04 mass%, and preferably no more than 4 mass%, and more preferably no more than 3 mass%.
  • the first embodiment of the lubricating oil composition of the present invention may include (C) a nitrogen-containing ashless dispersant (hereinafter referred to as "component (C)").
  • component (C) a nitrogen-containing ashless dispersant
  • component (C) for example one or more compound selected from the following (C-1) to (C-3) may be used.
  • (C-1) a succinimide having at least one alkyl or alkenyl group in a molecule thereof, or a derivative thereof (hereinafter referred to as "component (C-1)");
  • component (C-2) a benzylamine having at least one alkyl or alkenyl group in a molecule thereof, or a derivative thereof (hereinafter referred to as "component (C-2)");
  • component (C-3) a polyamine having at least one alkyl or alkenyl group in a molecule thereof, or a derivative thereof (hereinafter referred to as "component (C-3)").
  • the component (C) may be especially preferably used.
  • the succinimide having at least one alkyl group or alkenyl group in a molecule thereof of the component (C-1) include a compound represented by the following formula (3) or (4).
  • R 3 is a C 40 -C 400 alkyl or alkenyl group
  • h is an integer of 1 to 5, preferably 2 to 4.
  • the carbon number of R 3 is preferably no less than 60 and preferably no more than 350.
  • R 4 independently, same or different, is a C 40 -C 400 alkyl or alkenyl group.
  • R 4 is especially preferably a polybutenyl group.
  • i is an integer of 0 to 4, preferably of 1 to 3.
  • the carbon number of R 4 is preferably no less than 60 and preferably no more than 350.
  • the alkyl or alkenyl group (R 3 , R 4 ) in the formulas (3) and (4) may be linear or branched.
  • Preferable examples thereof include oligomers of olefins such as propylene, 1-butene and isobutene, and a branched alkyl or alkenyl group derived from a co-oligomer of ethylene and propylene.
  • a branched alkyl or alkenyl group derived from an oligomer of isobutene idiomatically called as polyisobutylene, and a polybutenyl group are most preferable.
  • a preferable weight-average molecular weight of the alkyl or alkenyl group (R 3 , R 4 ) in the formulas (3) and (4) is 800 to 3500.
  • the succinimide having at least one alkyl or alkenyl group in a molecule thereof includes a so-called mono-type succinimide represented by the formula (3), in which succinic anhydride is added only to one end of the polyamine chain, and a so-called bis-type succinimide represented by the formula (4), in which succinic anhydride is added to both ends of the polyamine chain.
  • the lubricating oil composition of the present invention may include either one of the mono-type succinimide and the bis-type succinimide, and may include a mixture of the mono-type and bis-type succinimides.
  • the production method of the succinimide having at least one alkyl or alkenyl group in a molecule thereof is not particularly limited.
  • it may be obtained by reaction of polyamine and an alkyl or alkenyl succinic acid obtained by reaction of a compound having a C 40 -C 400 alkyl or alkenyl group and maleic anhydride at 100 to 200°C.
  • examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
  • Examples of the benzylamine having at least one alkyl or alkenyl group in a molecule thereof of the component (C-2) include a compound represented by the following formula (5).
  • R 5 is a C 40 to C 400 alkyl or alkenyl group
  • j is an integer of 1 to 5, preferably 2 to 4.
  • the carbon number of R 5 is preferably no less than 60 and preferably no more than 350.
  • the production method of the component (C-2) is not particularly limited.
  • the method of reacting a propylene oligomer, polybutene or polyolefin such as ethylene- ⁇ -olefin copolymer with phenol to make an alkylphenol, thereafter reacting the alkylphenol with formaldehyde and a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by Mannich reaction may be given.
  • Examples of the polyamine having at least one alkyl or alkenyl group in a molecule thereof of the component (C-3) include a compound represented by the following formula (6).
  • R 6 is a C 40 to C 400 alkyl or alkenyl group, and k is an integer of 1 to 5, preferably 2 to 4.
  • the carbon number of R 6 is preferably no less than 60 and preferably no more than 350.
  • the production method of the component (C-3) is not particularly limited.
  • a method of: chlorinating a propylene oligomer, polybutene or polyolefin such as ethylene- ⁇ -olefin copolymer; thereafter reacting the chlorinated product with a polyamine such as ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine may be given.
  • a modified compound by an oxygen-containing organic compound in which some or all of the remaining amino group and/or imino group is neutralized or amidated by a function of C 1 -C 30 monocarboxylic acid such as fatty acid, C 2 -C 30 polycarboxylic acid (e.g.
  • oxalic acid, phthalic acid, trimellitic acid, and pyromellitic acid anhydrides or ester compounds thereof, C 2 -C 6 polyalkylene oxide, or hydroxyl(poly)oxyalkylenecarbonate to the above-described succinimide having at least one alkyl or alkenyl group in a molecule thereof (hereinafter referred to as "above-described nitrogen-containing compound");
  • a phosphoric-acid modified compound in which some or all of the remaining amino group and/or imino group is neutralized or amidated by a function of phosphoric acid to the above-described nitrogen-containing compound;
  • the molecular weight of the component (C) is not particularly limited, and a preferable weight-average molecular weight the component (C) is from 1000 to 8000.
  • the content of the component (C) when contained is preferably no less than 0.02 mass%, more preferably no less than 0.04 mass%, and further preferably no less than 0.07 mass%, and preferably no more than 0.2 mass% and more preferably no more than 0.12 mass%, in terms of nitrogen on the basis of the total mass of the lubricating oil composition.
  • By having the above-described upper limit values or less of the content of the component (C) it is possible to obtain good separation property of impurities in a centrifugal cleaner and to improve water separation property to inhibit the scum generation in the scrubber.
  • the second embodiment of the lubricating oil composition of the present invention optionally includes (C-1') a succinimide having at least one alkyl or alkenyl group in a molecule thereof, or a borated derivative thereof (hereinafter may be referred to as "component (C-1')").
  • component (C-1') a succinimide having at least one alkyl or alkenyl group in a molecule thereof, or a borated derivative thereof.
  • component (C-1') a succinimide having at least one alkyl or alkenyl group in a molecule thereof, or a borated derivative thereof.
  • succinimide having at least one alkyl or alkenyl group in a molecule thereof examples include the compounds represented by the above formulas (3) or (4) described above regarding the component (C-1) in the first embodiment.
  • the preferable embodiments of these compounds are as described above.
  • borated derivative of the succinimide having at least one alkyl or alkenyl group in a molecule thereof include a so-called boron modified compound in which some or all of the remaining amino group and/or imino group is neutralized or amidated by reaction of boric acid with the above-described succinimide having at least one alkyl or alkenyl group in a molecule thereof.
  • the molecular weight of the component (C-1') is not particularly limited, and a preferable weight-average molecular weight thereof is from 1000 to 8000.
  • the lubricating oil composition of the present invention may further contain any additives generally used in lubricating oils, depending on the intended use.
  • additives include zinc dithiophosphates, antioxidants, defoaming agents, pour point depressants, metal inactivators, and extreme pressure agents.
  • ZnDTP zinc dithiophosphate
  • R 7 independently, the same or different, is a C 1 -C 24 hydrocarbon group.
  • the C 1 -C 24 hydrocarbon group include a linear or branched C 1 -C 24 alkyl group.
  • the carbon number of R 7 is preferably no less than 3, and preferably no more than 12, and more preferably no more than 8.
  • the alkyl group as R 7 may be any one of a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.
  • the alkyl group as R 7 is preferably a primary alkyl group or a secondary alkyl group or a mixture thereof, and most preferably a primary alkyl group.
  • zinc dithiophosphate examples include: zinc dialkyldithiophosphates having a linear or branched C 3 -C 18 , preferably C 3 -C 10 alkyl group (primary, secondary or tertiary, preferably primary or secondary), such as zinc dipropyl dithiophosphate, zinc dibutyl dithiophosphate, zinc dipentyl dithiophosphate, zinc dihexyl dithiophosphate, zinc diheptyl dithiophosphate, and zinc dioctyl dithiophosphate; zinc di((alkyl)aryl)dithiophosphates having a C 6 -C 18 , preferably C 6 -C 10 aryl or alkyaryl group, such as zinc diphenyl dithiophosphate and zinc ditolyl dithiophosphate; and a mixture of two or more thereof.
  • the production method of the above zinc dithiophosphate is not particularly limited.
  • it may be synthesized by making a reaction of an alcohol having an alkyl group corresponding to R 7 with phosphorus pentasulfide to synthesize a dithiophosphoric acid, and neutralizing the dithiophosphoric acid by zinc oxide.
  • the content of the zinc dithiophosphate is preferably 0.03 to 1.0 mass%, more preferably 0.05 to 0.5 mass%, and especially preferably 0.01 to 0.3 mass% on the basis of the total mass of the composition.
  • the zinc dithiophosphate is desirably contained in such a manner that the phosphorus component in the lubricating oil composition is preferably 25 to 700 mass ppm, more preferably no less than 40 mass ppm, further preferably no less than 50 mass ppm, and especially preferably no less than 80 mass ppm, and more preferably no more than 500 mass ppm, further preferably no more than 300 mass ppm, and especially preferably no more than 250 mass ppm.
  • the phosphorus component derived from the zinc dithiophosphate in the lubricating oil composition is no less than 25 mass ppm, it is possible to secure necessary oxidation stability, and if it is no more than 700 mass ppm, it is possible to prevent the base number from lowering due to hydrolysis of the zinc dithiophosphate.
  • the antioxidant examples include ashless antioxidants such as phenol-based antioxidants, amine-based antioxidants, and metallic antioxidants. Among them, phenol-based antioxidants and/or amine-based antioxidants are preferably used, in view of maintaining high temperature detergent performance.
  • the content thereof is preferably no less than 0.05 mass%, and more preferably no less than 0.1 mass%, on the basis of the total mass of the composition, and when the antioxidant is an amine-based antioxidant, the content is especially preferably no less than 0.3 mass%, and when the antioxidant is a phenol-based antioxidant, the content is especially preferably no less than 0.15 mass%, on the basis of the total mass of the composition.
  • the upper limit of the content of the antioxidant is not particularly limited, and preferably no more than 5 mass% and more preferably no more than 2 mass% on the basis of the total mass of the composition.
  • defoaming agent examples include silicone oils, derivatives of alkenyl succinic acid, esters of aliphatic polyhydroxy alcohol and a long-chain fatty acid, methyl salicylate and o-hydroxybenzyl alcohol, aluminum stearate, potassium oleate, N-dialkyl-allylaminenitroaminoalkanol, aromatic amine salts of isoamyl octyl phosphate, alkylalkylenediphosphate, metal derivatives of thioethers, metal derivatives of disulfides, fluorine compounds of aliphatic hydrocarbons, triethylsilane, dichlorosilane, alkylphenyl polyethylene glycol ethersulfide, and fluoroalkylether.
  • the content thereof is normally 0.0005 to 1 mass% on the basis of the total mass of the composition.
  • the defoaming agent includes silicon
  • the defoaming agent is preferably included in such a manner that the Si component in the lubricating oil composition is 5 to 50 mass ppm.
  • pour point depressant examples include polymethacrylate-based polymers that conform to the lubricating base oil to be used.
  • the content thereof may be normally 0.005 to 5 mass% on the basis of the total mass of the composition.
  • the metal deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazolepolysulfide, 1,3,4-thiadiazolyl-2,5-bisdialkyldithiocarbamate, 2-(alkyldithio)benzoimidazole, and ⁇ -(o-carboxybenzylthio)propionitrile.
  • the content thereof is normally 0.005 to 1 mass% on the basis of the total mass of the composition.
  • the extreme-pressure agent examples include sulfur-based, phosphorus-based, and sulfur-phosphorus-based extreme-pressure agents. Specific examples thereof include phosphorous esters, thiophosphorous esters, dithiophosphorous esters, trithiophosphorous esters, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metallic salts thereof, derivatives thereof, dithiocarbamate, zinc dithiocarbamate, molybdenum dithiocarbamate, disulfides, polysulfides, olefin sulfides, and sulfurized oils and fats.
  • the content thereof is not particularly limited, and normally 0.01 to 5 mass% on the basis of the total mass of the composition.
  • the base number of the lubricating oil composition of the present invention is 15 to 125 mgKOH/g, preferably no less than 20 mgKOH/g, more preferably no less than 30 mgKOH/g, and further preferably no less than 40 mgKOH/g, and preferably no more than 120 mgKOH/g, more preferably no more than 105 mgKOH/g, and further preferably no more than 100 mgKOH/g. If the base number of the lubricating oil composition is less than 15 mgKOH/g, the detergency might be insufficient.
  • the base number of the lubricating oil composition is more than 125 mgKOH/g, excessive base components accumulate on the piston to obstruct formation of oil film, which results in a potential bore polish and scuffing. Therefore it is not preferable that the base number of the lubricating oil composition is less than 15 mgKOH/g or more than 125 mgKOH/g.
  • the kinematic viscosity at 100°C of the lubricating oil composition of the present invention is 10 to 30 mm 2 /s, preferably no less than 12 mm 2 /s, more preferably no less than 12.5 mm 2 /s, further preferably no less than 16.3 mm 2 /s, and especially preferably no less than 18.0 mm 2 /s, and preferably no more than 27 mm 2 /s, more preferably no more than 26.1 mm 2 /s, further preferably no more than 21.9 mm 2 /s, and especially preferably no more than 21.0 mm 2 /s.
  • the kinematic viscosity at 100°C of the lubricating oil composition is less than 10 mm 2 /s, the performance of oil formation is insufficient, which might results in searing of ring and liner. Therefore, it is not preferable that the kinematic viscosity at 100°C of the lubricating oil composition of the present invention is less than 10 mm 2 /s. If the kinematic viscosity at 100°C of the lubricating oil composition is more than 30 mm 2 /s, which is a high viscosity, the starting performance might degrade. Therefore it is not preferable that the kinematic viscosity at 100°C of the lubricating oil composition of the present invention is more than 30 mm 2 /s.
  • the Ph value represented by the following formula (1) is no more than 20 ⁇ 10 -3 , preferably no more than 19 ⁇ 10 -3 , and more preferably no more than 18 ⁇ 10 -3 .
  • Ph value C Ca ⁇ 2 / r M ⁇ 40.08 (in the formula (1), C Ca represents calcium content (mass%) derived from the component (A1), and r M represents a metal ratio of the component (A1).)
  • the calcium content (mass%) derived from the component (A1) mentioned here means a value of the content of calcium derived from the Ca phenate detergent of the component (A1) in the lubricating oil composition of the present invention, show by mass% on the basis of the total mass of the lubricating oil composition.
  • the metal ratio of the component (A1) mentioned here is a value calculated according to the following formula, regarding the Ca phenate detergent which is the component (A1).
  • Metal ratio of component (A1) calcium content (mass%) in Ca phenate detergent which is component (A1) / calcium content (mass%) derived from soap base in Ca phenate detergent which is component (A1)
  • the method of lubricating a cylinder of a crosshead diesel engine equipped with a scrubber according to the second aspect of the present invention includes: (i) operating the crosshead diesel engine while supplying the lubricating oil composition according to the first aspect of the present invention to the cylinder of the crosshead diesel engine equipped with a scrubber; and (ii) purifying at least a part of gas exhausted from the cylinder in the scrubber.
  • crosshead diesel engine equipped with a scrubber known crosshead diesel engines equipped with scrubbers may be used without particular limitations (for example, see Patent Literatures 1 to 5).
  • the method of supplying the lubricating oil composition according to the first aspect of the present invention to the crosshead diesel engine is not particularly limited, and known methods for supplying lubricating oils to crosshead diesel engines may be used.
  • the scrubber may be an EGR scrubber, may be a scrubber that does not send back the gases that passed through the scrubber to the inlet side but releases them to the environment, and may be a combination thereof.
  • a scrubber that purifies gasses guided in the scrubber by making the gasses into contact with water and/or a basic aqueous solution is preferable.
  • a basic aqueous solution an aqueous solution in which salts such as alkali metal hydroxides and alkali metal carbonates are dissolved may be used for example, and seawater may be preferably used.
  • lubricating oil compositions of compounding formulations shown in Tables 1 and 2 were prepared and a high-speed emulsification test was carried out thereon. The results are shown in Tables 1 and 2.
  • the amounts of the base oils are the contents on the basis of the total amount of the base oils
  • the amounts of additives are the contents on the basis of the total amount of the composition.
  • the calcium content of the commercially available cylinder oil was 2.60 mass% in terms of calcium on the basis of the total mass of the commercially available cylinder oil.
  • the nitrogen content of the commercially available cylinder oil was 0.03 mass% in terms of nitrogen on the basis of the total mass of the commercially available cylinder oil.
  • This test was a model examination simulating a process of oil-water separation after stirring in a scrubber.
  • 10 g of the sample oil were collected.
  • the measuring cylinder was set on a homogenizer (POLYTRON PT10-35, generator shaft PT36/4K manufactured by KINEMATICA), and stirred for 5 minutes at 15,000 rpm. After that, the homogenizer was pulled upward from the measuring cylinder and allowed to stand for 5 minutes, to collect the wet, oil and emulsion attached to the homogenizer to the measuring cylinder.
  • the measuring cylinder after the test was allowed to stand for 1 week at a room temperature. From the separated oil amount, the separation performance was judged as follows.
  • the lubricating oil compositions of Examples 1 to 11 showed good separation performances on the high-speed emulsification test (Table 1).
  • the compositions of Comparative Examples 1 and 5 to 7 that did not include the component (B), the composition of Comparative Example 2 including the component (B) by less than 0.02 mass%, and the compositions of Comparative Examples 3 and 4 including surfactants that did not have demulsification function instead of the component (B) each got mark 0 (rejected) in the high-speed emulsification test, which meant they were inferior in separation performance (Table 2).
  • Comparative Example 1 that is, the commercially available cylinder oil itself
  • Comparative Example 1 which marked 0 on the high-speed emulsification test
  • Example 1 Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 Example 11
  • Commercially available cylinder oil mass% 99.95 99.9 99.5 99 98 99.5 99.5 99.5 - - - Base oil 1 mass% 41.2 39.3 43.2
  • Ca phenate mass% 14 14 20
  • Ca sulfonate mass% 1.3 8.8 12.5
  • Nitrogen-containing ashless dispersant mass% 2.7 2.7 2.7 B-1 mass%
  • 0.05 0.1
  • 1 2 0.3 B-2 mass%
  • 0.5 0.3 B-4 mass% 0.5
  • Solbitan monooleate mass% Methyloleate mass%
  • lubricating oil compositions of the compounding formulations shown in Tables 3 to 5 were prepared, and a high-speed emulsification test was carried out in the same way as above. The results are shown in Tales 3 to 5.
  • the amounts of the base oils are the contents on the basis of the total amount of the base oils
  • the amounts of additives are the contents on the basis of the total amount of the composition.
  • the lubricating oil compositions of Examples 12 to 26 showed good separation property at the high-speed emulsification test (Tables 1 and 2).
  • the lubricating oil compositions of Examples 24 to 26 showed sufficient demulsification property even though each composition contained the component (C), which functioned as a dispersant, in an amount of no more than 0.015 mass% in terms of nitrogen on the basis of the total mass of the composition.
  • the compositions of Comparative Examples 8 to 10, whose Ph value was over 20 ⁇ 10 -3 each marked 0 (rejected) at the high-speed emulsification test, which meant they were inferior in separation property.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)
EP15861457.8A 2014-11-18 2015-11-18 Zylinder schmierölzusammensetzung für mit schrubber ausgestattete kreuzkopfdieselmotoren Active EP3222702B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014234045A JP6386348B2 (ja) 2014-11-18 2014-11-18 スクラバー搭載クロスヘッド型ディーゼル機関用シリンダ潤滑油組成物
JP2014234046A JP6297477B2 (ja) 2014-11-18 2014-11-18 スクラバー搭載クロスヘッド型ディーゼル機関用シリンダ潤滑油組成物
PCT/JP2015/082411 WO2016080441A1 (ja) 2014-11-18 2015-11-18 スクラバー搭載クロスヘッド型ディーゼル機関用シリンダ潤滑油組成物

Publications (3)

Publication Number Publication Date
EP3222702A1 true EP3222702A1 (de) 2017-09-27
EP3222702A4 EP3222702A4 (de) 2018-08-01
EP3222702B1 EP3222702B1 (de) 2022-01-05

Family

ID=56013975

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15861457.8A Active EP3222702B1 (de) 2014-11-18 2015-11-18 Zylinder schmierölzusammensetzung für mit schrubber ausgestattete kreuzkopfdieselmotoren

Country Status (6)

Country Link
US (1) US20170321141A1 (de)
EP (1) EP3222702B1 (de)
KR (1) KR102420190B1 (de)
CN (1) CN107001977B (de)
SG (1) SG11201703848XA (de)
WO (1) WO2016080441A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577853A (zh) * 2018-06-11 2019-12-17 Jxtg能源株式会社 双循环十字头型柴油发动机用系统润滑油组合物和其用途

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK170217B1 (da) * 1993-06-04 1995-06-26 Man B & W Diesel Gmbh Stor trykladet forbrændingsmotor og fremgangsmåde til drift af en køler til afkøling af en sådan motors indsugningsluft.
DK170218B1 (da) 1993-06-04 1995-06-26 Man B & W Diesel Gmbh Stor trykladet dieselmotor
US6339051B1 (en) * 1998-06-11 2002-01-15 Mobil Oil Corporation Diesel engine cylinder oils
US20050003972A1 (en) * 2003-06-13 2005-01-06 Laurent Chambard Lubricant composition
US20080153723A1 (en) * 2006-12-20 2008-06-26 Chevron Oronite Company Llc Diesel cylinder lubricant oil composition
US20090203559A1 (en) * 2008-02-08 2009-08-13 Bera Tushar Kanti Engine Lubrication
JP5313709B2 (ja) * 2009-01-28 2013-10-09 Ｊｘ日鉱日石エネルギー株式会社 クロスヘッド型ディーゼル機関用シリンダー潤滑油組成物
JP5483329B2 (ja) * 2009-12-24 2014-05-07 Ｊｘ日鉱日石エネルギー株式会社 クロスヘッド型ディーゼル機関用シリンダー潤滑油組成物
JP4997336B2 (ja) 2010-01-29 2012-08-08 エムエーエヌ・ディーゼル・アンド・ターボ・フィリアル・アフ・エムエーエヌ・ディーゼル・アンド・ターボ・エスイー・ティスクランド 排ガス再循環システムを備える大型２サイクルディーゼル機関
JP2011157960A (ja) 2010-01-29 2011-08-18 Man Diesel & Turbo Filial Af Man Diesel & Turbo Se Tyskland 排ガス再循環制御システムを備える大型２サイクルディーゼル機関
JP5650586B2 (ja) 2011-05-26 2015-01-07 エムエーエヌ・ディーゼル・アンド・ターボ・フィリアル・アフ・エムエーエヌ・ディーゼル・アンド・ターボ・エスイー・ティスクランド 排気ガススクラバーを備える大型２サイクルディーゼルエンジン
DK2986694T3 (da) * 2013-04-17 2020-03-30 Lubrizol Corp Fremgangsmåde til smøring af cylinder og stempel i en intern to-taktsforbrændingsmotor

Also Published As

Publication number Publication date
CN107001977B (zh) 2021-02-05
KR20170084105A (ko) 2017-07-19
WO2016080441A1 (ja) 2016-05-26
SG11201703848XA (en) 2017-06-29
US20170321141A1 (en) 2017-11-09
EP3222702A4 (de) 2018-08-01
EP3222702B1 (de) 2022-01-05
KR102420190B1 (ko) 2022-07-12
CN107001977A (zh) 2017-08-01

Similar Documents

Publication Publication Date Title
JP7212106B2 (ja) 船舶用ディーゼルシリンダー潤滑油組成物
JP4778154B2 (ja) 内燃機関用潤滑油組成物
WO2014158435A1 (en) Engine lubricants containing a polyether
CN100347277C (zh) 润滑油添加剂以及润滑油组合物
JP2015227454A (ja) 潤滑油組成物
JP6559974B2 (ja) 潤滑油組成物
JP6736037B2 (ja) 内燃機関用潤滑油組成物
JP5930905B2 (ja) 潤滑油組成物
JP2019089938A (ja) 潤滑油組成物
JP5714529B2 (ja) 内燃機関用潤滑油組成物
JP2015227453A (ja) 潤滑油組成物
EP3222702B1 (de) Zylinder schmierölzusammensetzung für mit schrubber ausgestattete kreuzkopfdieselmotoren
EP3504307B1 (de) Zylinderölzusammensetzungen für schiffsdieselmotoren
JP2001348591A (ja) エンジン用潤滑油組成物
JP2017538843A (ja) 潤滑油組成物
JP6386348B2 (ja) スクラバー搭載クロスヘッド型ディーゼル機関用シリンダ潤滑油組成物
JP6297477B2 (ja) スクラバー搭載クロスヘッド型ディーゼル機関用シリンダ潤滑油組成物
JP5930904B2 (ja) 潤滑油組成物
WO2013046755A1 (ja) クロスヘッド型ディーゼル機関用シリンダー潤滑油組成物
JP5952183B2 (ja) クロスヘッド型ディーゼル機関用システム潤滑油組成物
WO2018109126A1 (en) Ether-based lubricant compositions, methods and uses
JP2024143642A (ja) ガスエンジン用潤滑油組成物
JP2018048220A (ja) ガスエンジン油組成物

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170511

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602015076325

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C10M0171020000

Ipc: C10M0169040000

A4 Supplementary search report drawn up and despatched

Effective date: 20180629

RIC1 Information provided on ipc code assigned before grant

Ipc: C10N 20/04 20060101ALI20180625BHEP

Ipc: C10N 20/02 20060101ALI20180625BHEP

Ipc: C10N 10/04 20060101ALI20180625BHEP

Ipc: C10M 169/04 20060101AFI20180625BHEP

Ipc: C10N 20/00 20060101ALI20180625BHEP

Ipc: C10N 40/25 20060101ALI20180625BHEP

Ipc: C10N 30/00 20060101ALI20180625BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210909

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1460603

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015076325

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1460603

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220505

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220405

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220505

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015076325

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

26N No opposition filed

Effective date: 20221006

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602015076325

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20221118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221130

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221118

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221118

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220105

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20251119

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20251119

Year of fee payment: 11