GB1168411A - Lubricating Oil Compositions - Google Patents

Lubricating Oil Compositions

Info

Publication number
GB1168411A
GB1168411A GB01175/68A GB1117568A GB1168411A GB 1168411 A GB1168411 A GB 1168411A GB 01175/68 A GB01175/68 A GB 01175/68A GB 1117568 A GB1117568 A GB 1117568A GB 1168411 A GB1168411 A GB 1168411A
Authority
GB
United Kingdom
Prior art keywords
lubricating oil
calcium
product
mole ratio
alkyl
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.)
Expired
Application number
GB01175/68A
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.)
Texaco Development Corp
Original Assignee
Texaco Development 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
Application filed by Texaco Development Corp filed Critical Texaco Development Corp
Publication of GB1168411A publication Critical patent/GB1168411A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024Propene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088Neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089Overbased salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2221/00Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2221/02Macromolecular compounds obtained by reactions of monomers involving only carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C10M2225/041Hydrocarbon polymers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04Siloxanes with specific structure
    • C10M2229/041Siloxanes with specific structure containing aliphatic substituents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

1,168,411. Lubricants. TEXACO DEVELOPMENT CORP. 7 March, 1968 [20 March, 1967], No. 11175/68. Heading C5F. A lubricant comprises a hydrocarbon lubricating oil containing 0À1-90 wt. per cent of a 20-70% hydrolysed overbased sulphurized calcium alkylphenolate having a calcium metal ratio of from 1À1 to 3À5 wherein said hydrolysed product is prepared by contacting in a hydrocarbon lubricating oil (a) a sulphurized normal calcium C 4 -C 100 alkylphenolate having a sulphur content of 0À1-10 wt. per cent and a calcium metal ratio of 1 with (b) a calcium alkoxy-alkoxide of formula Ca(OAOR<SP>1</SP>) 2 where A is a C 1 -C 6 alkylene radical and R<SP>1</SP> is C 1 -C 25 alkyl, at 10-200‹ C. in a mole ratio of (b) : (a) of 1 : 0À1 to 1 : 2À5 and thereafter contacting the product with water at 10-250‹ C. in the mole ratio of water: (b) of 100 : 1 to 0À2 : :1 until 20-70% of the overbased product is hydrolysed and thereafter removing any residual water. The lubricating oil may be mineral or synthetic, e.g. polypropylene or polyisobutylene. The sulphurized normal calcium alkyl phenolate may be prepared by contacting in said lubricating oil (c) a C 4 -C 100 alkyl-phenol with (b) above in a mole ratio of (c) : (b) of about 2 : 1 at 10-250‹ C. and thereafter reacting the product with sulphur in a mole ratio of sulphur: (c) of 0À15 : 1 to 8:1 at 75-250‹ C. The lubricating oil compositions may also contain the ethylene oxide reaction product of polybutene thiophosphonic acid, zinc di-C 10 -C 12 alkylbenzene dithiophosphate, zinc isopropyl 1,3-dimethylbutyl dithiophosphate, overbased calcium alkyl benzene sulphonate, a copolymer of dodecyl and octadecyl methacrylates and dimethyl silicone.
GB01175/68A 1967-03-20 1968-03-07 Lubricating Oil Compositions Expired GB1168411A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US62419367A 1967-03-20 1967-03-20
US64036267A 1967-05-22 1967-05-22
US85575869A 1969-09-05 1969-09-05

Publications (1)

Publication Number Publication Date
GB1168411A true GB1168411A (en) 1969-10-22

Family

ID=27417349

Family Applications (2)

Application Number Title Priority Date Filing Date
GB01175/68A Expired GB1168411A (en) 1967-03-20 1968-03-07 Lubricating Oil Compositions
GB01176/68A Expired GB1164417A (en) 1967-03-20 1968-03-07 Sulphurized Calcium Alkylphenolate Lubricant Compositions

Family Applications After (1)

Application Number Title Priority Date Filing Date
GB01176/68A Expired GB1164417A (en) 1967-03-20 1968-03-07 Sulphurized Calcium Alkylphenolate Lubricant Compositions

Country Status (4)

Country Link
US (3) US3474035A (en)
BE (2) BE712521A (en)
DE (2) DE1769011A1 (en)
GB (2) GB1168411A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0417962A1 (en) * 1989-09-15 1991-03-20 Texaco Development Corporation Process for the preparation of sulfurized overbased phenate detergents

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3474035A (en) * 1967-03-20 1969-10-21 Texaco Inc Lubricating oil containing overbased sulfurized calcium alkylphenolate
US3741896A (en) * 1970-12-11 1973-06-26 Chevron Res Basic alkylene amine and sulfur bridged alkylphenoxides for use in lubricating oils
US3793201A (en) * 1970-12-28 1974-02-19 Lubrizol Corp Stabilized basic magnesium sulfonate compositions
US3755170A (en) * 1971-05-17 1973-08-28 Continental Oil Co Preparation of highly basic alkylphenates and sulfurized alkyphenates
US3897352A (en) * 1973-12-21 1975-07-29 Texaco Inc Sulfurized nitrated alkylphenol salts and lubricant compositions thereof
US3969235A (en) * 1974-08-26 1976-07-13 Texaco Inc. Sulfurized calcium alkylphenolate compositions
IT1059547B (en) * 1975-12-24 1982-06-21 Liquichimica Robassomero Spa PROCEDURE FOR THE PREPARATION OF ADDITIVES FOR LUBRICANT OILS
US4171269A (en) * 1976-12-27 1979-10-16 Texaco Inc. Sulfurized lubricant composition
US4171270A (en) * 1976-12-27 1979-10-16 Texaco Inc. Sulfurized overbased calcium alkylphenolate lubricant composition
US4169799A (en) * 1976-12-27 1979-10-02 Texaco Inc. Lubricating oil composition
US4320016A (en) * 1979-09-24 1982-03-16 Texaco Inc. Carbon dioxide-blown overbased calcium alkylphenolate lubricating compositions
US4282107A (en) * 1979-09-26 1981-08-04 Texaco Inc. Diesel crankcase lubricant composition
US4608184A (en) * 1985-07-12 1986-08-26 Amoco Corporation Phenate process and composition improvement
US5256319A (en) * 1989-03-30 1993-10-26 Institut Francais Du Petrole New thiophosphoretted compounds, their preparation and their use as additives for lubricants
FR2645168B1 (en) * 1989-03-30 1993-02-05 Inst Francais Du Petrole NOVEL THIOPHOSPHORUS COMPOUNDS, THEIR PREPARATION AND THEIR USE AS LUBRICANT ADDITIVES
US8198225B2 (en) * 2007-11-29 2012-06-12 Chevron Oronite Company Llc Sulfurized metal alkyl phenate compositions having a low alkyl phenol content
WO2015153160A1 (en) * 2014-04-04 2015-10-08 The Lubrizol Corporation Method for preparing a sulfurized alkaline earth metal dodecylphenate

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2289795A (en) * 1938-10-14 1942-07-14 Standard Oil Dev Co Lubricant
US2680096A (en) * 1951-02-12 1954-06-01 California Research Corp Process for preparing sulfurized polyvalent metal phenates
US2870134A (en) * 1956-12-12 1959-01-20 Texas Co Preparation of calcium phenolates and sulfurized derivatives thereof
US2916454A (en) * 1957-02-18 1959-12-08 Socony Mobil Oil Co Inc Preparation of complex carbonated metal salts of alkyl phenol sulfides and mineral oil fractions containing the same
IT630213A (en) * 1959-05-11
US3150088A (en) * 1962-03-23 1964-09-22 Continental Oil Co Highly basic calcium-containing additive agent
US3425941A (en) * 1966-09-26 1969-02-04 Texaco Inc Method of preparing calcium alkylphenolates
US3474035A (en) * 1967-03-20 1969-10-21 Texaco Inc Lubricating oil containing overbased sulfurized calcium alkylphenolate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0417962A1 (en) * 1989-09-15 1991-03-20 Texaco Development Corporation Process for the preparation of sulfurized overbased phenate detergents

Also Published As

Publication number Publication date
US3474035A (en) 1969-10-21
DE1769012C3 (en) 1975-06-12
DE1769012B2 (en) 1974-10-24
GB1164417A (en) 1969-09-17
US3549534A (en) 1970-12-22
DE1769012A1 (en) 1972-05-04
DE1769011A1 (en) 1971-06-09
BE712522A (en) 1968-09-20
BE712521A (en) 1968-09-20
US3528917A (en) 1970-09-15

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee