EP0000769B1 - Polymers containing polyalkylpiperidines and use thereof as stabilizers - Google Patents

Polymers containing polyalkylpiperidines and use thereof as stabilizers Download PDF

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Publication number
EP0000769B1
EP0000769B1 EP78100573A EP78100573A EP0000769B1 EP 0000769 B1 EP0000769 B1 EP 0000769B1 EP 78100573 A EP78100573 A EP 78100573A EP 78100573 A EP78100573 A EP 78100573A EP 0000769 B1 EP0000769 B1 EP 0000769B1
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EP
European Patent Office
Prior art keywords
group
formula
carbon atoms
polymer
hydrogen atom
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
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EP78100573A
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German (de)
English (en)
French (fr)
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EP0000769A3 (en
EP0000769A2 (en
Inventor
Nobuo Soma
Syoji Morimura
Takao Yoshioka
Tomoyuki Kurumada
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Sankyo Co Ltd
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Sankyo Co Ltd
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Publication date
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Publication of EP0000769A2 publication Critical patent/EP0000769A2/en
Publication of EP0000769A3 publication Critical patent/EP0000769A3/xx
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Publication of EP0000769B1 publication Critical patent/EP0000769B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0688—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polyquinolines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the present invention relates to novel polymers containing sterically hindered polyalkylpiperidines and which are useful as stabilizers for synthetic polymers, and synthetic polymer compositions stabilized against light- and heat-deterioration containing said novel polymers.
  • polyalkylpiperidine derivatives in which the 1- and/or 4-positions are substituted are effective polymer stabilizers against light- or heat-induced degradation thereof.
  • 4- spirohydantoins of 2,2,6,6-tetramethylpiperidine or 2,6-diethyl-2,3,6-trimethylpiperidine are disclosed in U.S. Patents nos. 3,542,729, 3,705,126, 3,941,744, 4,005,094 and 3,898,303 and German Offentechnischsschrift no. 2,623,464; amino derivatives are disclosed in U.S. Patents nos. 3,684,765 and 3,904,581 and German Offenlegungsschrift no.
  • the invention provides polymers in which groups containing polyalkylpiperidines represented by the general formulae: wherein R, represents a hydrogen atom or a methyl group, are linked in the main chain via bridging members containing groups having the formula or derivatives thereof.
  • the new polymers show improved stabilizing effect in various polymeric materials against light-and heat-degradation thereof, with less sublimation and exudation therefrom.
  • polymers of the present invention containing polyalkylpiperidines are represented by the following formula (I):
  • 1 represents an integer of from 2 to 50, preferably 2-10, and most preferably 2-6.
  • Both m, and M2 represent 0, or one of them represents 1 and the other represents 0.
  • X represents a group of formula
  • R' represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • n represents an integer of from 1 to 10, preferably 1.
  • n 2 represents 0 or an integer of from 1 to 10, preferably 0.
  • W represents a group of formula
  • n 3 represents an integer of from 1 to 10, preferably 4 to 10, most preferably 4.
  • groups may be mentioned, for example, the malonyl, succinyl, adipoyl, suberoyl, sebacoyl or decane-1,10-dicarbonyl group.
  • W further represents a group of formula e.g. isophthaloyl or terephthaloyl, preferably phthaloyl, or a group of formula e.g. cyclohexane-1,2-dicarbonyl.
  • a group of formula e.g. isophthaloyl or terephthaloyl, preferably phthaloyl, or a group of formula e.g. cyclohexane-1,2-dicarbonyl.
  • Y represents, when both m 1 and m 2 are 0, one of the following formulae (II) to (IV): in which R 1 represents a hydrogen atom or a methyl group, preferably a hydrogen atom, and R 2 represents a hydrogen atom or an alkyl group having from 1 to 18 carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, octyl, dodecyl or octadecyl, particularly methyl.
  • R 2 is a hydrogen atom.
  • R 1 has the meaning given above.
  • R 1 has the meaning defined above
  • R 3 represents a group of formula or
  • R 4 represents the methyl or ethyl group.
  • Y represents, when one of m 1 and m 2 is 1 and the other is 0, a group of the following formulae (V) to (XI): in which:
  • A represents an alkylene group having from 2 to 12, preferably 2 to 6, and most preferably 6 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably p-xylylene; a group of formula a group of formula ⁇ CH 2 COO ⁇ R 5 ⁇ OCOCH 2 ⁇ in which R 5 is an alkylene group having from 2 to 8 carbon atoms, e.g.
  • R s represents a hydrogen atom, a methyl group or a phenyl group, preferably a hydrogen atom
  • R 7 represents an aliphatic, aromatic or alicyclic diacyl group having up to 12 carbon atoms, for example, an alkanedicarbonyl group having from 4 to 12 carbon atoms and which is optionally interrupted by sulfur, such as malonyl, succinyl, adipoyl, sebacoyl, decane-1,10-dicarbonyl or 3,3'-thiodipropionyl, phthaloyl, isophthaloyl, terephthaloyl or cyclohexane-1,4-dicarbonyl; or a group of formula in which p is 0 or 1, preferably 1, R s has the same meaning as the above-defined X
  • B represents an alkylene group having from 2 to 10, preferably 2 to 6 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene or decamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably p-xyiylene; a group of formula a group of formula ⁇ CH 2 COO ⁇ R 5 ⁇ OCOCH 2 ⁇ in which R 5 has the meaning defined above; a group of formula in which R s and R 7 have the meanings defined above; or a group of formula in which R s and p have the meanings given above and Z has the meaning defined below. in which:
  • D represents an aliphatic, aromatic, araliphatic or alicyclic diacyl group having up to 36 carbon atoms, for example diacyl groups as described under R 7 , an alkanedicarbonyl group having from 4 to 12 carbon atoms and which is optionally interrupted by sulfur, phthaloyl, isophthaloyl, terephthaloyl or cyclohexane-1,4-dicarbonyl, or a diacyl group derived from a dimeric acid, or a group of formula in which R 13 represents an alkyl group having from 1 to 4 carbon atoms, a benzyl group or a 3,5-di-tert-butyl-4-hydroxybenzyl group and R 14 has the same meaning as R 13 or represents a hydrogen atom; or a group of formula ⁇ CONH ⁇ R 10 ⁇ NHCO ⁇ in which R 10 represents an alkylene group having from 2 to 10, preferably 6 carbon atoms, e.g.
  • ethylene tetramethylene, hexamethylene, octamethylene or decamethylene
  • a phenylene group optionally substituted with methyl, e.g. o-, m- or p-phenylene, particularly 2,4-tolylene
  • a naphthylene group e.g. 1,5-naphthylene
  • a xylylene group e.g. p-xylylene
  • a cyclohexylene group optionally substituted with methyl, e.g.
  • 1,4-cyclohexylene or methyl-2,4-cyclohexylene a group of formula in which R 11 represents an oxygen atom or a methylene group, a group of formula a group of formula CH 2 . or a group of formula in which:
  • G has the same meaning as the above-defined D, or it represents an alkylene group having from 3 to 10, preferably 4 to 6 carbon atoms, e.g. trimethylene, tetramethytene, hexamethylene, octamethylene or decamethylene, a xylylene group, e.g. o-, m- or p-xylylene, preferably p-xylylene; a group of formula or a group of formula in which R 8 has the meaning defined above and Z has the meaning defined below.
  • R i has the meaning defined above.
  • R has the meaning defined above. in which R, has the meaning defined above.
  • All of Z in the molecule represent a hydrogen atom; an alkyl group having from 1 to 18 carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, octyl, dodecyl or octadecyl, particularly methyl; an aliphatic, aromatic, araliphatic or alicyclic acyl group having up to 18 carbon atoms, for example as described under R 9 , an alkanoyl group having from 2 to 18, preferably 2 to 4 carbon atoms, benzoyl, toluoyl or 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl; a group of formula ⁇ CONHR 12 in which R 12 is an alkyl group having from 1 to 18, preferably 1 to 4 carbon atoms, a phenyl group or a cyclohexyl group.
  • a part of Z in the molecule may represent hydrogen atoms while the remaining Z represent above-defined groups other than hydrogen.
  • all of Z in the molecule represent hydrogen atoms, acetyl or benzoyl groups, or a part of Z in the molecule are hydrogen atoms and the remaining Z are acetyl or benzoyl groups.
  • terminal groups may be present as groups of formula which impart a similar stabilizing effect and are included within the scope of the polymers of the invention.
  • the polymers of the invention having formula (I) may be either homopolymers or copolymers.
  • each of W, X and Y may be all the same, partly different, or all different in their structures.
  • copolymers give better physical and/or stabilizing properties than homopolymers.
  • Polymers having the above-mentioned recurring units wherein a part or all of the hydroxy groups of the polymer are etherified, esterified or converted into carbamate groups are also representative polymers of the invention.
  • Preferred such polymers with Z * hydrogen are, e.g. methyl ethers, ethyl ethers, acetates, propionates, benzoates, N-methyl carbamates, N-ethyl carbamates, N-phenyl carbamates and N-cyclohexyl carbamates.
  • the polymers of formula (I) according to the invention may be prepared by any one of the following methods which are performed under conditions known per se.
  • the reaction is performed preferably by heating the starting compound (XII) at 60 to 230°C in the presence or absence of an inert solvent.
  • suitable solvents are, e.g., ethers such as dioxane or diethyleneglycol dimethyl ether, dialkylamides such as dimethylformamide or dimethylacetamide; chlorinated or non-chlorinated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene or p-dichlorobenzene; and alcohols or mixtures thereof with water such as methanol, ethanol, n- or tert-butanol, n-octanol, aqueous methanol or aqueous ethanol.
  • a catalyst In performing the reaction, there may be employed a catalyst, if necessary.
  • Suitable catalysts are for instance those used for curing epoxy resins, e.g. tertiary amines such as triethylamine, triethanolamine or 1,5-diazabicyclo-[5.4.0]undecene-5 (DBU) or Lewis acids such as boron trifluoride or zinc borofluoride.
  • tertiary amines such as triethylamine, triethanolamine or 1,5-diazabicyclo-[5.4.0]undecene-5 (DBU)
  • Lewis acids such as boron trifluoride or zinc borofluoride.
  • the starting compounds (XII) may be prepared by reacting a compound of formula H-Y,-H with one mole equivalent of an epihalohydrin.
  • reaction is performed under similar conditions as in the aforementined process variant 1).
  • the starting compounds (XIV) may be prepared by reacting a compound of formula H ⁇ Y 2 ⁇ H with two mole equivalents of an epihalohydrin.
  • polymers of formula (I) according to the invention can effectively stabilize a wide variety of synthetic polymers, such as:
  • the amount of stabilizers of the invention needed for effective stabilization of organic polymers will depend on a variety of factors, such as the type and properties of the polymer concerned, its intended use, and the presence of other stabilizers. It is generally satisfactory to use from 0.01 to 5.0% by weight of the stabilizers of the invention, based on the weight of the polymer, but the most effective range will vary with the type of the polymer; viz.
  • polymeric stabilizers of the invention may be used together.
  • the polymeric stabilizers of the invention may readily be incorporated into synthetic polymers to be stabilized by conventional techniques at any convenient stage prior to the manufacture of shaped articles therefrom.
  • the polymeric stabilizer may be mixed with the polymer to be stabilized in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer to be stabilized.
  • the stabilized polymeric composition of the invention may optionally also contain one or more of various additives conventionally used in polymer technology, such as the additives listed in British Patent Specification no. 1,401,924, at pages 11-13. in the following Examples the mean molecular weight was measured by the vapour pressure depression method.
  • Acetate of compound no. 2 A mixture of 1.0 g of the pale yellow powder obtained according to Example 2 and 10 g of acetic anhydride was heated at 100-1 10°C for 5 hours under a nitrogen stream. The reaction mixture was poured into ice-water, neutralized with aqueous ammonia and extracted with ethyl acetate. The organic phase was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate was removed by evaporation under reduced pressure, yielding the desired compound (Compound no. 3) softening at 103-106 0 C. Examination of the compound by infrared and NMR spectrometry revealed that all of the hydroxy groups of the compound were acetylated.
  • Benzoate of Compound no. 10 2.0 g of the white powder obtained according to Example 8 and 8.0 g of benzoic anhydride were heated to 150°C for 15 hours under argon. The reaction mixture was dissolved in ethyl acetate, washed with 5% aqueous potassium carbonate solution and water, and dried over sodium sulfate. The residue obtained by removing the solvent was purified by column chromatography. At first, elution with ethyl acetate gave a white powder (Compound no. 11) softening at 115-120°C. The NMR spectrum of the compound showed that the benzoylation rate was 95%.
  • the above-mentioned starting material was heated to 200-220°C for 3 hours in the absence of a solvent and then treated and purified in a similar manner as described above, giving a white powder (Compound no. 15) softening at 150-160°C and having a mean molecular weight of 6,000 from the first eluate, and a white powder (Compound no. 16) softening at 120-130°C and having a mean molecular weight of 2,650 from the second eluate.
  • the film was cut into test specimens of 50 x 120 mm.
  • the test specimens were exposed to light in a Sunshine Weather Meter at a black panel temperature of 63 ⁇ 3°C and examined periodically to determine the percentage of elongation at break. From the test results the ratio of the time required for the test specimens containing stabilizer to reach 50% elongation at break was determined, to the time required for an unstabilized test specimen to reach 50% elongation at break. The results are summarized in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Hydrogenated Pyridines (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Epoxy Resins (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
EP78100573A 1977-08-08 1978-08-02 Polymers containing polyalkylpiperidines and use thereof as stabilizers Expired EP0000769B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP94808/77 1977-08-08
JP9480877A JPS5429400A (en) 1977-08-08 1977-08-08 Polymer comprising polyalkylpiperidine and its use as stabilizers

Publications (3)

Publication Number Publication Date
EP0000769A2 EP0000769A2 (en) 1979-02-21
EP0000769A3 EP0000769A3 (en) 1979-03-07
EP0000769B1 true EP0000769B1 (en) 1981-08-05

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EP78100573A Expired EP0000769B1 (en) 1977-08-08 1978-08-02 Polymers containing polyalkylpiperidines and use thereof as stabilizers

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US (1) US4265803A (enrdf_load_stackoverflow)
EP (1) EP0000769B1 (enrdf_load_stackoverflow)
JP (1) JPS5429400A (enrdf_load_stackoverflow)
DE (1) DE2860899D1 (enrdf_load_stackoverflow)
IT (1) IT1097576B (enrdf_load_stackoverflow)

Families Citing this family (18)

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Publication number Priority date Publication date Assignee Title
JPS56167736A (en) * 1980-05-30 1981-12-23 Adeka Argus Chem Co Ltd Stabilizer for synthetic resin
IT1168110B (it) * 1981-03-16 1987-05-20 Montedison Spa Polimeri della piperidina e loro impiego come stabilizzanti
JPS5832642A (ja) * 1981-08-20 1983-02-25 Adeka Argus Chem Co Ltd 安定化された合成樹脂組成物
AU567702B2 (en) * 1983-10-13 1987-12-03 Ford Motor Company Of Canada Limited Polymeric light stabilizers containing polyalkylpiperidine group.
DE3379171D1 (en) * 1983-10-13 1989-03-16 Du Pont Polymeric light stabilizers containing polyalkylpiperidine groups
US4629769A (en) * 1985-09-30 1986-12-16 Texaco Inc. 4,4,6-trimethylhexahydropyrimidine as an epoxy curing agent
IT1212123B (it) * 1986-02-21 1989-11-08 Ciba Geigy Spa Nuovi composti polimerici contenenti gruppi piperidinici, utilizzabili come stabilizzanti per polimeri sintetici.
US4822833A (en) * 1986-03-10 1989-04-18 Ciba-Geigy Corporation Stabilized rigid polyvinyl chloride compositions
US4863918A (en) * 1987-02-06 1989-09-05 Boc, Inc. Enamine quaternary compounds, methods of making and their use as muscle relaxants
DE3920325C2 (de) * 1988-06-24 2001-04-12 Sunstar Engineering Inc Maskierte Polyisocyanuratverbindung und sie enthaltende Plastisolzusammensetzung
DE4229760A1 (de) * 1992-09-05 1994-03-10 Basf Ag UV-stabilisierte Polyoxymethylenformmassen
TW270126B (enrdf_load_stackoverflow) * 1993-07-13 1996-02-11 Ciba Geigy
TW267178B (enrdf_load_stackoverflow) * 1993-07-13 1996-01-01 Ciba Geigy
EP1391490A1 (en) * 2002-08-23 2004-02-25 Vantico Gmbh Modified epoxy resins for triboelectric coating processes
US8821907B2 (en) 2005-03-11 2014-09-02 Auburn University Office Of Technology Transfer Biocidal N-halamine epoxides
AT510488B1 (de) 2010-09-29 2012-09-15 Ke Kelit Kunststoffwerk Gmbh Antimikrobielles mittel für polymere
JP6772685B2 (ja) * 2016-09-06 2020-10-21 三菱ケミカル株式会社 エポキシ化合物、エポキシ化合物の製造方法、エポキシ化合物含有組成物及びその硬化物
CN114014845B (zh) * 2021-11-18 2023-06-02 波米科技有限公司 一种含环氧基化合物、液晶取向剂及其制备方法和应用

Family Cites Families (18)

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US3542729A (en) * 1968-03-19 1970-11-24 Sankyo Co Stabilization of synthetic polymers
US3640928A (en) * 1968-06-12 1972-02-08 Sankyo Co Stabilization of synthetic polymers
US3705126A (en) * 1969-06-20 1972-12-05 Sankyo Co Stabilization of synthetic polymers
US3684765A (en) * 1970-01-08 1972-08-15 Sankyo Co Stabilization of synthetic polymers
NL154241C (enrdf_load_stackoverflow) * 1971-01-29 1900-01-01
US3941744A (en) * 1971-06-05 1976-03-02 Sankyo Company Limited Piperidine derivatives and their use as stabilizers
US4005094A (en) * 1971-07-02 1977-01-25 Sankyo Company Limited Piperidine-spiro-hydantoin derivatives
US4021432A (en) * 1971-11-30 1977-05-03 Ciba-Geigy Corporation Piperidine derivatives
US3898303A (en) * 1972-05-31 1975-08-05 Sankyo Co Piperidine-spiro-hydantoin derivatives and their use as stabilizers
JPS554133B2 (enrdf_load_stackoverflow) * 1972-07-27 1980-01-29
JPS557861B2 (enrdf_load_stackoverflow) * 1972-10-04 1980-02-28
JPS5420977B2 (enrdf_load_stackoverflow) * 1972-10-26 1979-07-26
US4061616A (en) * 1973-06-15 1977-12-06 Sankyo Company Limited Stabilization of synthetic polymers
US3974127A (en) * 1973-09-17 1976-08-10 E. I. Du Pont De Nemours And Company Alkylene oxide condensates of tetramethylpiperidine alcohols or glycols
CH589056A5 (enrdf_load_stackoverflow) * 1973-12-10 1977-06-30 Ciba Geigy Ag
JPS5848580B2 (ja) * 1975-05-28 1983-10-29 三共株式会社 ゴウセイコウブンシザイリヨウヨウアンテイザイ
GB1489849A (en) * 1975-08-08 1977-10-26 Sankyo Co 4,4'-bi-piperidylidene derivatives and their use as polymer stabilizers
CH626109A5 (enrdf_load_stackoverflow) * 1976-05-11 1981-10-30 Ciba Geigy Ag

Also Published As

Publication number Publication date
US4265803A (en) 1981-05-05
JPS5429400A (en) 1979-03-05
EP0000769A3 (en) 1979-03-07
EP0000769A2 (en) 1979-02-21
IT7826310A0 (it) 1978-07-31
DE2860899D1 (en) 1981-11-05
JPS6332782B2 (enrdf_load_stackoverflow) 1988-07-01
IT1097576B (it) 1985-08-31

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