WO1981000012A1 - Irradiation of polyacrylate compositions in air - Google Patents

Irradiation of polyacrylate compositions in air Download PDF

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Publication number
WO1981000012A1
WO1981000012A1 PCT/US1980/000611 US8000611W WO8100012A1 WO 1981000012 A1 WO1981000012 A1 WO 1981000012A1 US 8000611 W US8000611 W US 8000611W WO 8100012 A1 WO8100012 A1 WO 8100012A1
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WIPO (PCT)
Prior art keywords
group
hydrogen
formula
carbon atoms
independently
Prior art date
Application number
PCT/US1980/000611
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English (en)
French (fr)
Inventor
L Wendling
J Covington
Original Assignee
Minnesota Mining & Mfg
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 Minnesota Mining & Mfg filed Critical Minnesota Mining & Mfg
Priority to DE8080901347T priority Critical patent/DE3066940D1/de
Priority to BR8008722A priority patent/BR8008722A/pt
Publication of WO1981000012A1 publication Critical patent/WO1981000012A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to processes for polymerizing polyacrylate functional compositions and in particular to processes for the curing in air of certain polyacrylate functional materials by irradiation.
  • compositions are useful for coatings and inks that can be cured in the presence of oxygen, these compositions are not satisfactory for coatings that are transparent and where discoloration is undesirable since the use of large amounts of photoinitiator leads to yellowing of the cured coating.
  • U.S. Patent 3,968,305 describes acrylic compositions comprising an aliphatic compound having three or more methacryloxy groups that can be polymerized to a crosslinked mar resistant coating.
  • U.S. Patent 4,014,771 teaches that by the addition of 1) 30 to 95 percent of the adduct of methacrylic acid and 2) either a polyglycidyl ether of an aromatic polyhydric compound or a polyglycidyl ester of an aromatic or aliphatic polycarboxylic acid to a polymethacryloyloxy compound such as that described in U.S. Patent 3,968,305, there is obtained a composition which evidently can be polymerized without the necessity of excluding air during the polymerization.
  • U.S. Patent No. 3,821,098 shows certain heterocyclic diacrylates and triacrylates included in the present invention to be polymerizable by irradiation.
  • U.S. Patent No. 3,808,226 shows certain heterocyclic diacrylates included within the description of the present invention which can be cured by irradiation. The only curing conditions shown are those within a metal mold in which the polymerizable mass fills the mold cavity, probably excluding any air. Disclosure of Invention
  • heterocyclic polyacrylate materials and compositions can be cured by irradiation in the presence of oxygen, even at normal atmospheric levels, without essential modification of the compositions. Irradiation of these materials and compositions in the presence of at least two percent atmospheric oxygen with substantially complete cure to a solid non-tacky state is surprising for an acrylate material. The fact that these materials and compositions can be so cured in the presence of atmospheric levels of oxygen ( 21%) is quite remarkable.
  • These acrylates are generally characterized by containing at least one heterocyclic ring (Z) of the formula:
  • X is the divalent radical necessary to complete a 5- or 6-membered heterocyclic ring.
  • Attached to the at least two ring nitrogen atoms shown in Z are ethylenically unsaturated aliphatic groups, preferably with acryloyloxy or methacryloyloxy unsaturation on the groups, although allyloxy and vinyl unsaturation is also useful.
  • heterocyclic polyacrylate materials useful in the practice of the process of the present invention include both novel compounds and known compounds not heretofore known to be oxygen insensitive for radiation curing.
  • novel compounds useful in the present invention disclosed and claimed in Applicant's copending application S.N. 51,876 , filed the same day as this application, bearing Attorney's Docket No. FN 31,224 and entitled "Poly(Ethylenically Unsaturated Alkoxy) Heterocyclic Compounds" can be described by the formula:
  • a 1 - Z - A 2 in which A 1 and A 2 independently are alkoxyalkyl groups having terminal ethylenic unsaturation and having the general formula:
  • R-O- is a monovalent residue (formed by removal of the active hydrogen from an -OH group) of an aliphatic terminally unsaturated primary alcohol, ROH, R having the formula: or preferably
  • E is or a and c are independently an integer of 1 to 6, b is zero or an integer of 1 to 6,
  • R 1 and R 4 are independently hydrogen or methyl
  • R 2 is preferably hydrogen but can be or wherein R 6 is preferably alkenyl but can be alkyl
  • R 7 is hydrogen, an aliphatic group (of up to eight carbon atoms, e.g., alkyl) or aromatic group
  • R 7 is most preferably an acryloyloxyalkyl or a methacryloyloxyalkyl group
  • R 3 is an alkylene group having 1 to 6 carbon atoms and optionally one catenary oxygen atom; and n is 2 or 3;
  • Z is a heterocyclic group of the formula:
  • X is a divalent group which is required to complete a
  • X can be wherein R 8 , R 9 , R 10 , and R 11 are independently hydrogen or lower alkyl (of 1 to 12 carbon atoms), cycloalkyl (of 3 to 6 carbon atoms) or phenyl group
  • a 3 is an alkoxyalkyl group as defined above for A 1 and A 2 , and A 1 , A 2 , and A 3 are independently preferably
  • R 28 is hydrogen or methyl
  • R 29 is the residue of an aliphatic polyol having
  • the preferred compounds of Formula I are those wherein E is m is 2 to 5, and
  • R 12 and R 13 each independently represent a hydrogen atom or the methyl group
  • R 14 stands for a hydrogen atom, an alkyl group, an alkyl group interrupted by oxygen atoms, or a phenyl group
  • m stands for a whole number from 1 to 30, preferably from
  • n denotes the number 2 or 3
  • A represents an organic radical containing at least once the grouping:
  • X' represents a divalent radical which is necessary for the completion of a five-or six-membered, unsubstituted or substituted, heterocyclic ring.
  • the radical X' in the N-heterocyclic grouping of formula I can be, e.g. a radical of the formulae: wherein R 15, R 16 , R 17 and R 18 can each independently represent a hydrogen atom or an alkyl group, preferably a lower alkyl group having 1-12 carbon atoms, an alkenyl group, preferably a lower alkylene group having 1-12 carbon atoms, a cycloalkyl group (preferably of 3 to 8 carbon atoms), or an unsubstituted or substituted phenyl group.
  • the valence of the nitrogen atom on the last group may be satisfied by hydrogen, aliphatic, or aromatic groups R 19 , preferably of no more than eight carbon atoms.
  • the aliphatic groups may be alkyl groups for example, and the aromatic group may be phenyl or alkylphenyl or phenylalkyl groups, for example.
  • the materials useful in the process of the present invention also include those of the following formula from U.S. Patent No. 3,808,266:
  • R 20 i.s hydrogen or methyl
  • R 21 is hydrogen or methyl, n is 2 or 3, and
  • A is as defined above for the materials of U.S. Patent No. 3,821,098 which is the same as A above.
  • the materials of the present invention can be represented by the formula A 4 -Z-A 5 wherein A 4 and A 5 are groups having the formula
  • R 22 and R 25 are independently hydrogen or methyl
  • R 23 is an aliphatic group of 1 to 15 carbon atoms (preferably alkylene group of 1 to 15 carbon atoms) which may have up to 2 non-adjacent catenary oxygen
  • R 24 is selected from hydrogen or -OR 27 in which
  • R 27 is selected from hydrogen, and with R 6 and R 7 as defined above.
  • R 26 is an alkylene group of from 1 to 6 carbon atoms and optionally 1 catenary oxygen atom, e and g are independently 0 or 1, d is always 1 except when e and g are 0 and then d is 0.
  • f is an integer of from 1 to 5
  • h is an integer of from 1 to 30 (and preferably
  • Z is as defined above. It is preferred that when R 24 i.s hydrogen, then e and g are both zero, and f and l are one; and when R 24 is -OR 27 at least one of e and g are zero and f is one, or e and g are 1 and f is 1 to 5.
  • group is used in the definition of a term (as in alkyl group versus alkyl), the term connotes the possibility of substitution recognized by the act as not affecting the functional nature of the chemical term.
  • backbone chains for example, is recognized as being substantially equivalent to and included within the term "alkyl group”.
  • terminal groups of the formula are recognized as substantially equivalent to wherein group Q represents moieties substituting for a terminal hydrogen.
  • Q might be halogen, amino, nitro, etc., without affecting the functional ability of the compound. This is readily understood by the ordinarly skilled artisan.
  • the process of the present invention comprises the curing of these materials or the curing of compositions comprising at least 15% by weight of these materials by exposure to electromagnetic radiation or electron beam radiation in an atmosphere containing at least 2% oxygen.
  • Compositions used in the practice of the present invention preferably comprise at least 30 to 100% by weight of these heterocyclic polyacrylate materials and more preferably comprise from 45 to 85% by weight of these heterocyclic polyacrylate materials. The percent by weight is based upon polymerizable components and does not include essentially inert fillers.
  • compositions used in the process of the present invention may be diluted with up to 85% by weight of any ethylenically unsaturated monomer.
  • the majority of comonomers are at least diethylenically unsaturated monomers.
  • Generic classes include the acrylates, methacrylates, acrylic anhydrides, ethylenically unsaturated anhydrides, olefinic compounds, acrylamides, ethylenically unsaturated amides and urethanes, vinyl esters, vinyl ethers, vinyl halides, vinyl epoxy resins, vinyl silanes and siloxanes, vinyl heterocycles, and prepolymers and polymers these materials.
  • Particularly suitable ethylenically unsaturated monomers include methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, styrene, butadiene, 2-chlorostyrene, 2,4-dichlorostyrene, acrylic acid, acrylamide, acrylonitrile, t-butyl acrylate, methyl acrylate, butyl acrylate, N-vinyl pyrrolidone,2-(N-butylcarbamyl)ethyl methacrylate and 2-(N-butyl-carbamyl)ethyl methacrylate and 2-(N-ethylcarbamyl)ethyl methacrylate.
  • copolymerizable components Preferably 35 to 80% and most preferably 45 to 60% by weight of copolymerizable components comprise the heterocyclic agents of the present invention.
  • Other diluting monomers that can be incorporated into the composition of the invention include 1,4-butylene dimethacrylate or acrylate, ethylene dimethacrylate, hexamethylene diacrylate or dimethacrylate, glyceryl diacrylate or methacrylate, glyceryl triacrylate or trimethacrylate, pentaerythritol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or tetramethacrylate, diallyl phthalate, dipentaerythritol pentaacrylate, neopentylglycol triacrylate and 1,3,5-tri(2-methacryloyloxyethyl)-s-triazine.
  • Polymerization initiators suitable for use in the comopsitions of the invention are compounds which liberate or generate a free-radical on addition of energy.
  • Such initiators include peroxy, azo, and redox systems each of which are well known and are described frequently in polymerization art, e.g. Chapter II of Photochemistry, by Calvert and Pitts, John Wiley & Sons (1966).
  • free-radical initiators include the conventional heat activated initiators such as organic peroxides and organic hydroperoxides; examples are benzoyl peroxide, tertiary-butyl perbenzoate, cumene hydroperoxide, azobis(isobutyronitrile) and the like.
  • the preferred initiators are photopolymerization initiators which facilitate polymerization when the composition is irradiated. Included among such initiators are acyloin and derivatives thereof, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and ⁇ -methylbenzoin; diketones such as benzil and diacetyl, etc.; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, decyl phenyl sulfide, and tetramethylthiuram monosulfide; S-acyl dithio- carbamates, such as S-benzoyl-N,N-dimethyldithiocarbamate; phenones such as acetophenone, ⁇ , ⁇ , ⁇ -tribromaceto ⁇ henone, ⁇ , ⁇ -diethoxyactophen
  • the initiator is used in amounts ranging from about 0.01 to 5% by weight of the total polymerizable composition. When the quantity is less than 0.01% by weight, the polymerization rate becomes extremely low. If the initiator is used in excess of 5% by weight, no correspondingly improved effect can be expected. Thus, addition of such greater quantity is economically unjustified. Preferably, about 0.25 to 1.0% of initiator is used in the polymerizable compositions.
  • compositions used in the process of the present invention can also contain a viscosity modifier or binder.
  • a compatible polymer is used.
  • the polymer is an acrylic polymer such as poly(acrylic acid), a ⁇ oly(meth- acrylic acid), poly(methyl methacrylate), poly(vinyl chloride), poly(vinyl acetate, poly(vinyl butyral) and the like.
  • Other polymers include polyethers, polyesters, poly- lactones, polyamides, polyurethanes, cellulose derivatives, polysiloxanes and the like.
  • compositions used in preparing coatings of the invention can also include a variety of addenda utilized for their known purpose, such as stabilizers, inhibitors, lubricants, flexibilizers, pigments, carbon black, dyes, reinforcing fillers such as finely divided silica, non-reinforcing fillers such as diatomaceous earth, metal oxides, asbestos, fiberglass, glass bubbles, talc, etc.
  • Fillers can generally be used in proportions up to about 200 percent by weight of the curable components but preferably are used up to about 50 percent by weight. Where the polymerizing energy is radiation, it is desirable that the addenda be transparent to the radiation.
  • compositions used in preparing coatings of the invention are prepared by simply mixing (under "safe light” conditions if the composition is to be sensitized to visible light) the polymerization initiator and sensitizer (where used), the heterocyclic polyacrylate materials, diluting monomers, binders and addenda.
  • Inert solvents may be employed if desired when effecting this mixture. Examples of suitable solvents are methanol, ethanol, acetone, acetonitrile and includes any solvent which does not react with the components of the mixture.
  • compositions may be applied to the substrates before curing in any conventional fashion. Roller coating, spray coating, knife-edge coating, dip-coating, sputter coating, bar coating and any other conventional process for the application of liquids to substrates may be used.
  • the coatings of the present invention find application useful on substantially any solid substrate. Because the coatings of the present invention can be cured by radiation, even highly temperature sensitive substrates can be coated.
  • the substrates may be in substantially any form, such as sheets, films, fibers, fabrics and shaped solid objects.
  • polymeric resins including both thermoplastic and thermoset resins (e.g., polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polyacrylates, polyolefins, polyvinyls, cellulosesters, epoxy resins, polysiloxanes, etc.), ceramic substrates, including glass, fused ceramic sheeting, and fibers, metals and metallized surfaces, natural cellulosic materials, including wood and paper, natural resins, including rubber and gelatin and other various solid surfaces.
  • thermoplastic and thermoset resins e.g., polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polyacrylates, polyolefins, polyvinyls, cellulosesters, epoxy resins, polysiloxanes, etc.
  • ceramic substrates including glass, fused ceramic sheeting, and fibers, metals and metallized surfaces, natural cellulosic materials, including wood and paper, natural resins, including rubber and gelatin and other various solid surfaces.
  • primer compositions comprising single ingredients or blends of materials, may be used to improve the bond of the coating to the substrate. Texturizing, chemical, or physical treatment of the surface may also be used to improve bonding.
  • Particularly useful substrates for application of the coatings of the present invention would be those requiring transparent protective coatings. Finished photographic prints and films, paintings, transparencies, car windshields, painted surfaces, instant film (i.e., film which does not require external application of developing chemistry), photothermographic and thermographic paper and film, photoconductive substrates, opthalmic lenses, motion picture film, street and traffic signs, reflective surfaces, retroreflective surfaces, traffic lights, and many other substrates are usefully coated according to the practice of the present invention. Where the polymerization catalyst is a photoinitiator, the composition can be a composition for in situ curing because of this insensitivity to oxygen.
  • the photopolymerizable compositions with at least three acrylate functionalities are particularly suitable for applications in the field of protective coatings and graphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metals, metal oxides, plastics, rubber, glass, paper, wood, and ceramics; their excellent resistance to most solvents and chemicals; their excellent flexibility and weatherability; and their capability for forming high resolution images.
  • Curing are particularly suitable for applications in the field of protective coatings and graphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metals, metal oxides, plastics, rubber, glass, paper, wood, and ceramics; their excellent resistance to most solvents and chemicals; their excellent flexibility and weatherability; and their capability for forming high resolution images.
  • the photopolymerization of the compositions of the invention occurs on exposure of the compositions to any source of radiation emitting actinic radiation at a wavelength within the ultraviolet and visible spectral regions.
  • Suitable sources of radiation include mercury, xenon, carbon arc and tungsten filament lamps, sunlight, etc. Exposures may be from less than about 1 second. to 10 minutes or more depending upon the amounts of the particular polymerizable materials and photopolymerization initiator being utilized and depending upon the radiation source, distance from the source, and the thickness of the coating to be cured.
  • the compositions may also be polymerized by exposure to electron beam irradiation. Generally speaking, the dosage necessary is from less than 1 megarad to 100 megarad or more.
  • One of the major advantages with using electron beam curing is that highly pigmented compositions can be effectively cured at a faster rate than by mere exposure to actinic radiation.
  • Example 1 One of the major advantages with using electron beam curing is that highly pigmented compositions can be effectively cured at a faster rate than
  • Example 2 A solution containing 2.3g of compound 1 from
  • Example 1 2.3g acetone, and 0.033g diethoxyacetophenone was coated onto a 12 m polyethylene sheet with a #14 Meyer bar. The layer was dried and placed in a mounting for a Perkin Elmer Model No. 257 infrared spectrophotometer. The absorbances at 1630 cm -1 and 810 cm -1 , characteristic of acrylate unsaturation, were recorded. The mounting was removed from the spectrophotometer and passed through a UV processor as described in Example 1 at 50 ft/min. The mounting was returned to the spectrophotometer and the absorbances at 1630 cm -1 and 810 cm -1 were recorded and compared to the initial absorbances. This experiment showed that 70-80% of the acrylate functionality was consumed under the curing conditions. Five additional passes of this film at 50 ft/min in the UV processor failed to show any significant decrease in the acrylate infrared absorbances.
  • TMPTA requires 10 minutes to reach insolubility and that with the addition of 17% .of Compound 1 (from Example 1) the cure time is reduced to 80 seconds and with increasing amounts of 1, the composition cures faster until at 100% 1, the composition under the stated conditions cures in only 10 seconds. Comparable results can be obtained with Compound 2.
  • One part polyacrylic acid, one part compound 1 from Example 1, five parts water, five parts ethanol and 0.02 parts of 2,2-dimethoxy-2-phenyl-acetophenone were mixed together to form a solution.
  • a layer 5.0 m in thickness of this solution was coated onto 12 m polyester as described in Example 1.
  • a patterned template was placed over the layer and exposed by a Hanovia 3D690 mercury arc lamp in air at a distance of 6 cm for two minutes. The exposed sheet was developed with cold water leaving an image having excellent resolution.
  • Examples 9-16 Coatings about 5 m thick were prepared by coating using a #20 Meyer bar onto about 12 m polyethylene film primed with polyvinylidene chloride 50% solutions in ethyl acetate (other solvents such as ketones and lower alcohols are equally suitable) and drying mixtures of Compound 1 of Example 1, zero to 100% of Compound 2 of Example 1, and pentaerythritol triacrylate (PTA) based on total weight of Compounds 1, 2 and PTA.
  • PTA pentaerythritol triacrylate
  • Table 3 shows that coatings prepared from the hexaacryloyloxyhydantoin.
  • Compound 1 and up to more than 50% of the diacryloyloxyhydantoin.
  • Compound 2 have excellent resistance to abrasion as measured by Taber, falling sand and steel wool procedures. At up to about 30% Compound 2, abrasion resistance is superior.
  • coatings were prepared as for Examples 3-10 but using photoinitiator concentrations from 0.4 to 3% and tested, similar abrasion resistance and cross-hatch adhesion was obtained.
  • reaction flask was heated to 75 C and 55.2 g (0.40 m epoxy equivalency) 1,3-bis(2,3-epoxy- propyl)-5,5-dimethyl-2,4-imidizo- lidinedione in 20 ml chloroform was added dropwise over one hour. After the addition, the reaction flask temperature was raised to 88 C and stirred for 18.0 hours. At this time, titration of an aliquote for unreacted epoxide indicated the reaction was greater than 99% complete.
  • the volatiles were removed by vacuum distillation leaving a viscous liquid which contains a mixture of bis(triacryloyl)-,bis(monoacryloyl)-, and the unsymmetrical monoacryloyl-triacryloyl-imidizolidinedione, and impurities, introduced with the pentaerythritol triacrylate.

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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)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
PCT/US1980/000611 1979-06-25 1980-05-22 Irradiation of polyacrylate compositions in air WO1981000012A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8080901347T DE3066940D1 (en) 1979-06-25 1980-05-22 Irradiation of polyacrylate compositions in air
BR8008722A BR8008722A (pt) 1979-06-25 1980-05-22 Irradiacao de composicoes de poliacrilato em ar

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/051,888 US4306954A (en) 1979-06-25 1979-06-25 Process for polymerizing acrylic substituted hydantoins in air
US51888 2002-01-17

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WO1981000012A1 true WO1981000012A1 (en) 1981-01-08

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PCT/US1980/000611 WO1981000012A1 (en) 1979-06-25 1980-05-22 Irradiation of polyacrylate compositions in air

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US (1) US4306954A (en, 2012)
EP (1) EP0030968B1 (en, 2012)
JP (1) JPH0237923B2 (en, 2012)
AU (1) AU543438B2 (en, 2012)
BE (1) BE884001A (en, 2012)
BR (1) BR8008722A (en, 2012)
CA (1) CA1143329A (en, 2012)
CH (1) CH663312GA3 (en, 2012)
DE (1) DE3066940D1 (en, 2012)
IT (1) IT1145377B (en, 2012)
MX (1) MX156015A (en, 2012)
WO (1) WO1981000012A1 (en, 2012)
ZA (1) ZA803751B (en, 2012)

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AU543438B2 (en) 1985-04-18
BR8008722A (pt) 1981-04-28
EP0030968A4 (en) 1981-07-09
ZA803751B (en) 1982-02-24
CA1143329A (en) 1983-03-22
IT8049060A0 (it) 1980-06-24
MX156015A (es) 1988-06-16
CH663312GA3 (en, 2012) 1987-12-15
EP0030968B1 (en) 1984-03-14
JPH0237923B2 (en, 2012) 1990-08-28
IT1145377B (it) 1986-11-05
US4306954A (en) 1981-12-22
DE3066940D1 (en) 1984-04-19
EP0030968A1 (en) 1981-07-01
AU6122980A (en) 1981-01-14
JPS56500747A (en, 2012) 1981-06-04
BE884001A (fr) 1980-12-29

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