EP0000024A1 - Produits oligomères phosphorés et leur utilisation comme apprêts textiles ignifugeants - Google Patents

Produits oligomères phosphorés et leur utilisation comme apprêts textiles ignifugeants Download PDF

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EP0000024A1
EP0000024A1 EP78100036A EP78100036A EP0000024A1 EP 0000024 A1 EP0000024 A1 EP 0000024A1 EP 78100036 A EP78100036 A EP 78100036A EP 78100036 A EP78100036 A EP 78100036A EP 0000024 A1 EP0000024 A1 EP 0000024A1
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iii
acid
anhydrides
anhydride
formula
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EP0000024B1 (en
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Walter Dr. Dürsch
Hans-Jerg Dr. Kleiner
Fritz Dr. Linke
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Hoechst AG
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Hoechst AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/667—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing phosphorus in the main chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3264—Esters with hydroxyalkyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only

Definitions

  • dialkyl phosphonic esters have already been converted into oligomeric phosphonic acid esters by the action of di-haloalkanes at temperatures around 180 ° C., which were optionally post-alkylated (US Pat. No. 3,956,431). This procedure usually results in methyl chloride or methyl bromide as undesirable by-products. Both are highly volatile toxic compounds that have to be absorbed - relatively cumbersome - for environmental reasons and thus make production considerably more difficult.
  • the invention relates to mixtures (I) with a very wide range of variation with regard to their composition and their physical, chemical and flame-retardant properties, consisting of oligomeric phosphorus compounds of the general formulas I Z , I A , I K and I bo .
  • B means "start” in terms of time
  • E is “end” in terms of time
  • A is "outside remainder”
  • S is "pages” -Rest "and K is” Kern-Rest ".
  • formula from only core anhydrides (K) and the oxyalkylating agents (IV) can be reheated to 100 ° to 200 ° C, preferably 130 ° to 170 ° C - optionally, for example in the presence of alkaline catalysts, preferably soda and / or aftertreatment with alkaline catalysts such as, for example preferably sodium methylate at temperatures from 0 ° to 100 ° C., preferably 20 ° to 60 ° C., largely destroyed and converted into substances of the types I Z , I A , I K and / or I bo .
  • the moles of the compounds I Z are generally formulated for 1 to 6-valent alcohols.
  • Z 1 -OH monohydric alcohols
  • n 1
  • b 1
  • n 1
  • II alcohols
  • the 'process according to the invention is, if b> 0, is generally carried out in such a way that the phosphorus anhydrides of the formula III and additionally, if appropriate, volatile alkylene oxides (IV) or alkylene carbonates (IV 1 ), if used, are introduced at room temperature and slowly add the alcohol (II) at a temperature above the dissolving temperature. You can usually also add the alcohols (II).
  • the reaction rates are significantly increased and side reactions suppressed.
  • the reaction times are generally between about 1 and 120 hours, preferably 1 and 20 hours. They are naturally higher with increasing m, especially for m> 3 than for lower m.
  • the chain can grow even further with other molecules of III and IV. If 1 + m is the total number of IV molecules used per growing chain, acids 1,2,3 4 etc. (generally 1 + m + q) are always formed when III q or one mole more than IV (generally 1 + m + q moles of III) to implement.
  • Unsaturated alcohols are e.g. called: n-butene-2-ol-1, 1,4-butene diol and allyl alcohol, 1,4-butene diol being preferred as the dihydric alcohol.
  • reaction products of ethylene oxide and / or ethylene carbonate with mono- or polyhydric alcohols there are also reaction products from mono- and polyhydric alcohols with other 1,2-alkylene oxides and / or 1,2-alkylene carbonates, such as especially 1,2-propylene oxide, 1, 2-propylene carbonate or epichlorohydrin, as well as the reaction products of ethylene oxide and / or ethylene carbonate with poly-1,2-propylene glycols which - as is known - are prepared as surface-active compounds in a wide range of variations.
  • Corresponding poly-1,2-propylene glycols and corresponding adducts of ethylene oxide and / or ethylene carbonate with (poly) -1,2-propylene oxides are particularly worth mentioning.
  • the hydrocarbon chain of aliphatic hydroxyl compounds can also be replaced by other heteroatoms, e.g. be interrupted by the elements N, S and / or P or carboxylic ester groups.
  • These connections can e.g. particularly easily by reacting one or more molecules of 1,2-alkylene oxides and / or 1,2-alkylene carbonates with ammonia, primary or secondary amines, hydrogen sulfide, mercaptans and with oxygen acids of phosphorus, (C2-C6) carboxylic acids or dicarboxylic acids be preserved.
  • n-butane isobutane, 2-ethyl-hexane, n-octane, decane, dodecane, tetradecane-phosphonic acid, but especially on methane, ethane, propane and vinylphosphonic acid and 1,2-ethane - or 1,4-butane-diphosphonic acid, furthermore to mono- or polyvalent dialkylphosphinic acids, such as Methyl-butyl-phosphinic acid, methyl-n-octyl-phosphinic acid, methyl-n-dodecyl-phosphinic acid and especially dimethyl-, ethyl-methyl-, methyl-propyl- and 1,10-decane-bis- (methyl-phosphinic acid) -, Methyl-vinyl-phosphinic acid, ethane-1,2-bis (methyl-phosphinic acid) and also reaction products of 1 to 7 moles of alkylene oxide or
  • hydroxyl compounds with heteroatoms N, S and P which are very easily accessible through oxyalkylation reactions
  • numerous other compounds with hydroxyl groups and optionally these heteroatoms and / or carboxylic ester groups in the hydrocarbon chain are suitable, of which only those are mentioned, for example oligo condensates which are formed by reaction of dicarboxylic acids or dicarboxylic acid anhydrides with polyhydric alcohols, also glycolic acid methyl ester, 2- ' hydroxyethane-carbonate, ethyl ester etc.
  • hydroxymethane-phosphonic acid dimethyl ester 2-hydroxyethane-phosphonic acid diethyl ester, 3-hydroxypropane phosphonic acid di-n-butyl ester etc. and analogous compounds from the phosphinic acid series, such as, for example, methyl hydroxymethyl-methylphosphinate, ethyl 2-hydroxyethyl-methylphosphinate, 2'-ethylhexyl 3-hydroxypropyl-methylphosphinate, hydroxymethyl -dimethyl-phosphine oxide, 2-hydroxyethyl-dimethyl-phosphine oxide.
  • a preferred position among the aromatic compounds is taken by all aromatic compounds with alcoholic hydroxyl groups, such as, for example, benzyl alcohol and all 2-hydroxyalkyl ethers or esters, which by oxalkylations of phenolic hydroxyl groups or of aromatic compounds which contain carboxylic acid, phosphonic acid or phosphinic acid residues , arise with compounds of formula IV or IV 1 .
  • alcoholic hydroxyl groups such as, for example, benzyl alcohol and all 2-hydroxyalkyl ethers or esters, which by oxalkylations of phenolic hydroxyl groups or of aromatic compounds which contain carboxylic acid, phosphonic acid or phosphinic acid residues , arise with compounds of formula IV or IV 1 .
  • aromatic mono- and Dicarboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, the carboxylic acids such as B. the three different hydroxy-benzoic acids, the different naphthol-carboxylic acids, 4,4'-diphenyl-dicarboxylic acid etc. into consideration.
  • aromatic chlorine and especially bromohydroxy compounds can be of special interest, e.g. the oxyalkylation products of 2,4,6-iribromophenol, pentabromophenol, 2,4,6-irichlorophenol or pentachlorophenol and 2,2-bis (4-hydroxy-3,5-dibromophenyl) -propane.
  • Aromatic phosphonic or phosphinic acids such as, for example, benzenephosphonic acid, 1,3- or 1,4-phenylene-diphosphonic acid, phenylmethylphosphinic acid, 1,3- or 1,4-phenylene-bis- (methyl- phosphinic acid) etc. previously converted into the corresponding 2-hydroxyalkyl esters by reaction with the 1,2-alkylene oxides (IV o ) and / or 1,2-alkylene carbonates (IV 1 ).
  • Aromatic phosphonic or phosphinic acids such as, for example, benzenephosphonic acid, 1,3- or 1,4-phenylene-diphosphonic acid, phenylmethylphosphinic acid, 1,3- or 1,4-phenylene-bis- (methyl- phosphinic acid) etc. previously converted into the corresponding 2-hydroxyalkyl esters by reaction with the 1,2-alkylene oxides (IV o ) and / or 1,2-alkylene carbonates (IV 1 ).
  • Suitable aromatic compounds with alcoholic hydroxyl groups can also be obtained by previous reactions of aromatic amines or mercapto compounds with 1,2-alkylene oxides and / or 1,2-alkylene carbonates.
  • the suitable organic phosphoric anhydrides with the general formula III can have, depending on the special meanings R AB1 , R AB2 , r 1 , r 2 , A B , K , h , c K , c A and also R SB , R K , R 12 , f, g, s and i , be very diverse.
  • the possibly additionally suitable compounds III CY therefore include, for example, the clearly cyclic phosphine-carboxylic acid anhydrides of the "phospholane type" (III PL ) such as 2-methyl, 2-ethyl, 2-n-propyl, 2-isobutyl, 2-vinyl, 2-chloromethyl, 2-phenyl, 2,3-dimethyl, 2-methyl 3-ethyl, 2-methyl-3-butyl, 2,4-dimethyl, 2-methyl-4-ethyl, 2-phenyl-4-methyl, 2,3,4-trimethyl, 2, 3,4-triethyl, and especially because of the easy accessibility 2-methyl-2,5-dioxo-1,2-oxa-phospholane.
  • III PL the clearly cyclic phosphine-carboxylic acid anhydrides of the "phospholane type"
  • the phospholanes (III PL ) must never be used as the sole core groups. At least one remainder K P must always be present. In order to be able to characterize the different types of real organic phosphoric anhydrides in a meaningful way, it is advisable to state the values of h, g and i as a subscript. The same applies to the connections from which they arise.
  • the phosphonic anhydrides which are also suitable have the general formula and the characteristic III ho , g o , io .
  • x here and in the following formulas represents the degree of polymerization which is unknown in the above formula. It is believed that these compounds are at room temperature partly as open (III OF ) and partly as cyclic anhydrides (III CY ).
  • methane-phosphonic acid anhydride propane-phosphonic acid anhydride, n-butane-phosphonic acid anhydride, isobutane-phosphonic acid anhydride, n-pentane-phosphonic acid anhydride, chloromethane-phosphonic acid anhydride, 1- chloroethane-phosphonic acid anhydride, 2 - Chloroethane-phosphonic acid anhydride, 2,3-dibromo-propane-phosphonic acid anhydride, vinyl-phosphonic acid anhydride, propene-2-phosphonic acid anhydride, preferably methane-ethane, propane-phosphonic acid anhydride.
  • R K can be either R AF1 , R SF or R AF2 .
  • the metaphosphoric acid esters (III ho, go, i1 ) also contain cyclic structures (III CY ) in addition to open (III OF ). They are thermal, especially if R K is not CH3, far less stable than the phosphonic acid anhydrides. The higher esters decompose above 80 ° - 100 ° C with elimination of olefins. (See US 2 402 703 p. 1, column 1, line 14). The reaction with alcohols (II) and then with alkylene oxides (IV o ), however, proceeds smoothly, for example at 60-90 ° C.
  • metaphosphoric acid isoamyl ester metaphosphoric acid n-butyl ester, metaphosphoric acid n-propyl ester, metaphosphoric acid ethyl ester and metaphosphoric acid methyl ester are suitable as compounds III EC from the corresponding trialkyl phosphates (KED fo, r1, s1 ) and phosphorus pentoxide.
  • Such true mixed anhydrides are thermally as unstable as the metaphosphoric esters because of the ester residues they contain - especially when R is not CH 3 - above 80 ° C. Nevertheless, they are made from 1 mol of phosphorus pentoxide and from, for example, 1 mol of n-butane-phosphonic acid diethyl ester, isobutane-phosphonic acid di-isopropyl ester, n-propane-phosphonic acid diethyl ester, n-propane-phosphonic acid bis- (2-chloroethyl ester) ), dimethyl n-propane-phosphonate, di-n-butyl ethane-phosphonate, diethyl ethane-phosphonate, dimethyl 2-cyano-ethane-phosphonate, bis- (2,3-dibromopropyl) -phosphonate ), Methanephosphonic acid dimethylester etc.
  • suitable 1,10-decane-bis- (methyl-phosphinic acid) anhydride 1,6-hexa-n-bis- (ethyl-phosphinic acid) anhydride, 1,4-butane bis- (methyl-phosphinic acid) anhydride , 1,2-ethane bis (methyl phosphinic acid) anhydride and methane bis (methyl phosphinic acid) anhydride.
  • Suitable Off g angsester type KED f1, r1, s1 are for example 1,6-Hexandi-phosphonic tetraäthylester, 1,4-butane-di-phosphonic acid tetramethylester, 1,2-ethane-di-phosphonic acid tetraäthylester, 1, 2-ethane-di-phosphonic acid tetramethyl ester etc. and preferably methane-di-phosphonic acid tetra-ethyl ester and methane-di-phosphonic acid tetramethyl ester.
  • 1,6-hexane-bis- methyl-phosphinic acid-isobutyl ester
  • 1,2-ethane-bis-methyl-phosphinic acid-n-butyl ester 1,2-ethane-bis- (methyl ethyl phosphinate), ethyl methanephosphate) etc.
  • AD H proton-containing outer group donors
  • EC is the equivalent number of anhydride equivalents of real anhydrides used (III EC )
  • HAZ ADH the hydrogen equivalent number of proton-containing outer group donors (AD H )
  • HAZ ADH 1 to c K
  • EC hydrogen equivalents of proton-containing outer group donors (AD H ) are added to the real anhydrides III EC .
  • AD F proton-free outer group donors
  • the phosphorus pentoxide dissolves more and more poorly in the core ester donors (KED F ) the closer the molar ratio approaches the limit value 1.0, since the viscosity also increases significantly.
  • the MV range preferred in practice is therefore not 1.0, but beica. 1.05 to 1.50, or at c K values from 60 to 6.
  • such mixtures of P 2 0 5 and the core ester donors (KED F ) should be heated to about 60-90 ° C.
  • III AG, F proton-free closed organic phosphoric anhydrides
  • reaction of compounds II, III and IV can be carried out at relatively low temperatures (approx. ⁇ 100 ° C) primary if necessary partly the hydroxyl g rupp free undesirable cyclic diesterartigen reaction products of type (K IV) formed.
  • the corresponding desired reaction compounds (I) result from the ring opening, chain extension and increase in the m-value - recognizable by the disappearance of the corresponding bands, reduction in water sensitivity and increase in viscosity. But even minor residues of cyclic diesters (K IV )) still present in the end product (I) practically do not impair the usability of the end reaction mixtures (I), since anyway for fixing the end compounds (I) to textile material with the aid of, for example, aminoplast precondensates acidic pH values must be available. The aftertreatment can therefore, but does not have to be carried out in all cases.
  • the organic phosphoric anhydrides (III) and the intermediate and final reaction products available from them have different thermal resistance. Whenever the indices r, s and above all s are 1 and R AB and R SB are not hydrogen, at higher temperatures Side reactions occur. Therefore, the use of alkylene oxides (IV 0 ) is recommended in such cases, since these generally react at lower temperatures than the alkylene carbonates (IV 1 ). Alkylene carbonates (IV 1 ) are advantageously used above all when high-melting or higher molecular weight alcohols (II) are used, for safety reasons, for example with ethylene oxide trolls (CO 2 development) is desired.
  • inert solvents or diluents are not necessary. However, e.g. Acetone, methyl ethyl ketone, acetonitrile, 1,2-dichloroethane, benzene, toluene, xylene, chlorobenzene, but especially dioxane if necessary - added without damage as a diluent or solubilizer and still e.g. be removed by distillation before the complete reaction with the oxyalkylating agents (IV) or only at the end of the reaction.
  • the reaction temperatures between the compounds II (b> 0) and .III are between 0 ° and 180 ° C or higher, for example up to 250 ° C, preferably between 20 ° and 150 ° C, in particular 80 ° to 150 ° C.
  • the alkylene oxides (IV 0 ) react between 20 ° and 240 ° C, preferably 60-180 ° C.
  • the reaction can be carried out in stages in such a way that if b> 0 is, initially b moles of alcohols.
  • (II) with n alcoholic groups with b ⁇ n + e anhydride equivalents of the phosphorus anhydrides (III) and then initially at e 0 only b ⁇ n, at e 7 0 at least b ⁇ n + e moles of the oxyalkylating agent (IV) act until the acid number has dropped to practically 0.
  • alkylene carbonates (IV 1 ) the compounds IV can be added to the mixtures of II and III from the start.
  • low-volatile alkylene oxides (IV 0 ) such as epichlorohydrin.
  • Volatile alkylene oxides (IV 0 ) such as propylene oxide or ethylene oxide, on the other hand, are dropped or gassed at the reaction temperatures.
  • b 0 and e> 0, that is to say proton-containing closed phosphoric anhydrides (III AG, H ) but no alcohols (II) are used. However, the implementation of II and III is then omitted.
  • the end products (I) are colorless or more or less yellowish in color and of different consistency.
  • the compounds with long alkyl groups (up to 18 carbon atoms) can also be considered as surfactants because of their surface-active properties.
  • the alcohols (II) were added to the anhydrides (III) at room temperature (25 ° C.) or at the liquefaction temperatures of any solid anhydrides (III), if appropriate with cooling, within 1 ' to 30 minutes.
  • the specified different reaction conditions therefore always relate only to the reaction in the second stage with the oxyalkylating agents (IV).
  • Examples 1-9, 10b, 15, 19 describe the direct method (DV), 20 the multi-stage process (MSV).
  • the manufacturing examples 10a, 11-14, 16-18, in which b 0 and e> 0, respectively, explain the one-step process (EV).
  • the phosphorus-containing polyadducts according to the invention which are distinguished by a very good water solubility or by a good emulsifiability and have a high phosphorus content, can be fixed on textile material with a wide variety of reactive crosslinking agents.
  • the equipment obtained in this way has very good flame-retardant and permanent properties.
  • Polyfunctional N-methylol compounds are suitable as crosslinking agents, e.g. Derivatives of amino-1,3,5-triazines, such as trimethylolmelamine, hexamethylolmelamine, trimethylolmelamine trimethyl ether, hexamethylolmelamine pentamethyl ether, trimethylolmelamine triisobutyl ether, dimethylol-aceto-guanamine, furthermore derivatives of ureas such as dimethylol urea, dimethyl methyl urethane, dimethyl methyl urethane, dimethyl methyl urethane, dimethyl methyl urethane 4-methoxy-5-dimethylpropyleneurea, dimethylol-5-hydroxypropyleneurea, 1,3-dimethylol-4,5-dihydroxy-imidazolidone- (2), 1,3-dimethylol-5-hydroxy-ethylhexahydrotriazine (2), dimethyloluron and Dimethylol carb
  • melamine derivatives e.g. Trimethylolmelamine trimethyl ether or hexamethylol melamine pentamethyl ether.
  • inorganic or organic acids or their salts which are added as catalysts which show their action in the acidic pH range Hydrolysis or by heat treatment release acid, such as sulfuric acid, hydrochloric acid, phosphoric acid, trichloroacetic acid, maleic acid, tartaric acid, citric acid, acetic acid or its salts with ammonia, amines or polyvalent metals, preferably salts of strong or medium strength acids, such as ammonium sulfate, ammonium chloride , Mono- and diammonium oxalate, ammonium nitrate, magnesium chloride, aluminum chloride, zinc chloride, zinc nitrate, zinc fluoroborate, 2-amino-2-methyl-propanol hydrochloride
  • the crosslinking catalysts can be used alone or in mixtures with one another.
  • the textile material on which the flame-retardant and permanent finishes are possible can be varied. Excellent flame retardant effects are achieved on cellulose fiber fabrics, polyester and polyamide fabrics, plastic-bonded or reinforced glass fiber fabrics, on textile wallpapers or textile blinds made of cellulose fibers, polyester or polyamide fibers, glass fibers or their mixtures.
  • Particularly suitable as synthetic or mixed fiber goods are non-woven fabrics, e.g. Needle felts for wall and floor coverings, textile wallpapers, insulation materials and air filters of various types, such as. e.g.
  • the process according to the invention for flame-retardant finishing of the textile goods described above is carried out under application conditions which are known and customary in the textile industry. An additional operation which rbeitsab- the A changed course of the finishing of the said textile material, is not necessary.
  • the fabrics or needle felts are treated with the aqueous finishing liquors on a two-roll or three-roll pad, squeezed off and subjected to a drying or a condensation process.
  • the heat is preferably applied in two stages. Initially is dried above about 50 ° C, preferably at about 100 0 to 120 0 C, to the water to a residual value of about 4-8% to be removed, and then leaves the Kon densation at about 140 ° to 180 0 C for about 7 to 3 minutes.
  • the flame-retardant finishing of needle felt covers can also be carried out according to the two-stage process.
  • the crosslinking is preferably carried out here in a one-stage drying or condensation process at approximately 120 ° to approximately 180 ° C., predominantly at 135 ° to 160 ° C.
  • the heat treatment takes on average approximately 7 to approximately 60, preferably 10 to 30 minutes.
  • the heat is applied in drying chambers, on tenter frames, yard lues or condensation frames.
  • finishing agents such as textile softeners, water repellent products, oleophobicizing products or even antimicrobial finishing products can be added to the finishing liquors.
  • the very good flame retardant effects of the claimed organophosphorus compounds allow pile rugs - woven or tufted rugs - to be applied over the back of the carpet or over the primer.
  • the carpet backing equipment for woven carpets is known to be responsible for the dimensional stability and the primer for the integration of the pile threads in the tufting base fabric.
  • Anchoring the organophosphorus compounds in the carpet backing or in the primer makes a full bath impregnation unnecessary.
  • the pile threads are also brought into contact with the flame retardants, crosslinkers, catalysts and binders based on plastic dispersions.
  • the flame retardants and the other finishing products of the impregnation liquor then lie on or between the pile threads and lead to adhesions.
  • the individual thread of the pile should remain flexible.
  • gluing the pile can lead to increased dirt absorption.
  • the flame retardant products can also be stepped out gradually when walking on the carpets.
  • the pile carpets finished in this way are also characterized by their very good flame-retardant properties, e.g. for shampooing treatments and carpet washing.
  • the basic fabric of the tufted carpets can consist of cotton, jute, cellulose, wool, or synthetic fibers based on polyamide or polyester, polypropylene or in a mixture, or of glass fibers. Needled nonwovens made of polyester or polypropylene fiber are also suitable, excellent as a base fabric for the process according to the invention.
  • fiber material made of wool, polyamide, polyester as well as polyacrylonitrile or their mixtures e.g. Polyacrylonitrile / polyester 80/20.
  • Fiber material made of wool, polyamide or polyester threads with the usual cutting height of 4 to 12 mm is preferred.
  • plastic dispersions polyvinyl acetate are suitable polyvinyl acetate, with plastic plasticizers such as dibutyl phthalate, copolymers of vinyl acetate with dibutyl maleate, copolymers of butyl acrylate with N-methylol acrylamide, copolymers of acrylic acid butyl ester, N-Methylolacylamid and acrylic acid, copolymers of butyl acrylate, N-methylolacrylamide and / or N- Methylol methacrylamide and acrylic acid, copolymers of butyl acrylate, methyl methacrylate and methylol methacrylamide, copolymers of butyl acrylate, acrylonitrile, N-methylol acrylamide and methacrylic acid, copolymers of butyl acrylate, ethyl acrylate.
  • plastic plasticizers such as dibutyl phthalate, copolymers of vinyl acetate with dibutyl male
  • Preferred polymer dispersions are polyvinyl acetate dispersions (50%), copolymers of vinyl acetate with maleic acid dibutyl ester, e.g. in the ratio 77/23 (approx. 50%), copolymers of styrene / butyl acrylate / acrylonitrile / methacrylic acid / acrylamide e.g.
  • the impregnation liquors for both the primer and the back coating for woven carpets also contain thickeners, which are intended to prevent the finishing solution from penetrating into the pile and sticking together.
  • thickeners are water-soluble hydroxyethyl celluloses, methyl celluloses, carboxymethyl celluloses, water-soluble starch products, partially etherified or etherified starch products, polyvinyl alcohols, the sodium or ammonium salts of alginic acid.
  • the primer or the carpet backing for woven carpets can also be filled with chalk as usual.
  • metal oxides can also be used as fillers, such as aluminum oxide, aluminum hydroxide, aluminum oxide hydrate.
  • the method according to the invention for the flame-retardant finishing of pile carpets or woven carpets by means of a back coating is likewise carried out under application conditions as are customary in the textile industry.
  • the primer for tufted carpets or the back finish for woven carpets which contains the flame-retardant compound, the crosslinker, the plastic dispersion and the catalyst, is applied with the help of an air knife, a rubber squeegee or cylinder squeegee. Then, on a tenter, dried or in gelling or 'dry channels or cylinder dryers at 125 ° to 150 ° C cured.
  • the dwell time depends on the thickness of the carpets and is between 5 to 20 minutes, primarily 7 to 10 minutes.
  • tufted carpets there is generally a back coating with natural latex, synthetic latex dispersion, e.g. based on butadiene styrene 40:60 or 60:40.
  • the flame-retardant primer forms a barrier layer against the latex back so that it does not catch fire.
  • the flame retardant process according to the invention is also distinguished by the fact that no aggressive vapors can form in the form of hydrogen halide when exposed to flame, as is the case to a great extent when flame retardant components based on chlorinated paraffin, PVC, inorganic or organic bromine compounds are used.
  • the described flame-retardant systems on the various textile materials are characterized by very good durability.
  • the flame-retardant equipment is easy to grasp when subjected to mechanical stress, such as rolling in the needle felt, the tufted carpets, the woven carpets or even sharp ones Kinks do not break or powder the finish.
  • This elastic behavior of the equipment which also shows no or only very slight swelling in wet treatments, should be partly responsible for the very good wash resistance on the textile goods described and for the excellent integration of the pile threads in the tufting base fabric.
  • the equipment generally also shows good antistatic behavior and in many cases makes it unnecessary to add antistatic agents or carbon black dispersions.
  • the incorporation of antistatic products, textile softeners and oleophobicizing agents is generally not difficult.
  • a coarse-thread needle felt fabric which consists of a polyester fiber core and a polyamide tread in a mixing ratio of 65:35 and has a weight per square meter of approx. 800 g / m 2 , is treated on a two-roll pad with an aqueous solution consisting of the following individual components:
  • the needle felt shows a very good flame retardant effect that lasts several shampoos and washes at 40 - 50 ° C.
  • the flame retardant test is carried out in accordance with DIN 54 333, determination of the flame propagation speed of textiles, or in accordance with motor vehicle safety standard No. 302 (U.S. MVSS 302).
  • the needle felt material equipped according to the invention does not continue to burn after the test flame has been removed. Outside the test section, only an afterglow of 10-15 seconds could be determined. After three fine washes with 2 g / 1 of a commercially available mild detergent (the washing time is 15 minutes at 40 ° C), the needle felt also does not burn.
  • the afterflame time had only increased to 40-60 seconds. After 5 shampoos, the needle felt also does not burn. The afterflame time is 50 seconds.
  • the needle felted goods are equipped with 200 g / 1 of the plastic dispersion listed in the example, the needle felt burns in 3 minutes and 45 seconds after removal in a broad direction.
  • the flame-retardant needle felt is elastic and dimensionally stable.
  • the reaction product of propanephosphonic anhydride, pentaerythritol and ethylene oxide described in Example 1 is used as a flame-retardant component of a primer finish for a tufted article.
  • the primer is applied using a rubber squeegee and dried at 145 ° C for 10 minutes.
  • the order must be controlled so that the dry run is approximately 800 g / m 2 .
  • the treated tufted carpet shows a flexible grip and excellent dimensional stability.
  • the impregnation solution has not penetrated the pile threads.
  • the polyamide pile shows its original mobility.
  • the pile threads are excellently consolidated in the base fabric.
  • a carpet back coating is then applied to a rubber squeegee using the foam process.
  • a section of the tufted described above ware provided with a primer, which contains no flammhemmenden Kompo- n ducks.
  • the pile threads are integrated with a 50% butadiene-styrene dispersion (60:40), chalk and methylol hydroxyethyl cellulose as a thickener. After drying, the smooth foam described above is applied.
  • the flame retardant test according to the Nordtest method No. 7 gives the following finding: The section of carpet that does not contain a flame-retardant primer shows no. 7 no flame protection. After the pile of wood goes out, the section of carpet continues to burn across the dimensional mark of 60 cm. The flame-retardant section of the carpet goes out after the wood pile has burned off and shows a burn-in length of 30 cm, a burn-in width of 12 cm and an after-burn of 10 seconds.
  • the flame-retardant smooth foam back is not affected by the action of the flame.
  • the excellent flame retardant effect is retained even after 6 shampoos or after several wet treatments.
  • the tufted carpet described in Example 2 is treated with a primer impregnation, which has the following composition:
  • the primer is applied again using a rubber squeegee and dried for 12 minutes at 140 ° C.
  • the dry edition is 780 g / m 2 .
  • the tufted carpet equipped in this way has an elastic handle.
  • the carpet pile is not glued because the primer has not penetrated the base fabric.
  • the tufted carpet treated in this way burns after the flame protection test according to the Nordtest method No. 7 for floor coverings after burning the pile of wood no further.
  • the burn-in length is 30 cm, the burn-in width 16 cm. After 3 minutes, afterburn is no longer observed.
  • the flame retardant effect is excellent shampoo resistant and lasts for several wet treatments.
  • a needle felted fabric (700 g / m 2 ), which consists of a fine-thread polypropylene core and a coarse thread tread made of polypropylene threads, is treated on a two-roll pad with an aqueous impregnation solution, which has the following composition:
  • the flame-retardant effect of the very elastic and dimensionally stable needle felt is excellent and lasts for several shampooing treatments.
  • the flame retardant effect is tested in accordance with DIN 54 333 "Determination of the Flame Spread Rate". After the test flame has been removed, the needle felt burns out for 30 seconds outside the test zone. After 3 shampoos the needle felt burns for 60 seconds. The flame does not reach the test zone.
  • the needle felt is only equipped with 200 g / 1 of the plastic dispersion mentioned in the example, this needle felt continues to burn after the test flame has been removed. The flame traverses 10 cm of the test section in 2 minutes and 30 seconds.
  • the squeezing effect is 95%. Drying takes place at 135 ° C for 25 minutes.
  • Example 2 The tufted described in Example 2 is provided mit.einem V orstrich, which consists of the following components:
  • the primer is applied using a rubber squeegee and dried or condensed at 140 ° C for 15 minutes.
  • the dry edition is approx. 780 g / m 2 .
  • the tufted carpet treated in this way shows a flexible grip.
  • the integration of the individual threads in the basic fabric is sufficient draws.
  • the applied finish does not break.
  • the impregnation liquor has not penetrated the pile threads.
  • the same tufting goods are only equipped with the butadiene-styrene dispersion and the 3.0% methylhydroxyethyl cellulose solution.
  • test object of the flame-retardant tufted goods only continues to burn for 15 seconds after the test flame has been removed (the flame does not reach the test section), the test object continues to burn without flame-retardant equipment.
  • the flame traverses a test section of 10 cm in 2 minutes and 50 seconds.
  • the squeezing effect is 95%.
  • the mixture is then dried at 135 ° C for 20 minutes.
  • the needle felt is a very good flame retardant effect, several shampoos' and fine washes at 40 ° C survived.
  • the flame retardant test is carried out in accordance with DIN 54 333.
  • the needle felt test piece does not continue to burn after the test flame has been removed. Only an afterburn of 1.0 seconds outside the test zone could be determined.
  • the needle felt which was washed three times with 2 g / 1 of a commercially available mild detergent, also did not burn after the test flame was removed.
  • the afterburn time is 55 seconds outside the test zone.
  • the flame-retardant needle felt is elastic, lightly filled and dimensionally stable.
  • the needle felt is very well permanently flame retardant.
  • the handle is elastic, slightly filled, but not hardened.
  • a tufted carpet fabric with a square weight of 650 g / m 2 which consists of a 6 mm high polyester pile, tufted on a carrier material made of needled polypropylene nonwoven (100 g / m 2 ) is equipped with a primer of the following composition:
  • the primer is applied using a hand knife and dried at 145 ° C for 10 minutes.
  • the dry edition is approx. 750 g / m 2 .
  • the tufted carpet treated in this way shows a flexible grip and very good dimensional stability.
  • the pile threads are very well consolidated in the base fabric.
  • the tufted carpet treated in this way meets the test standard DIN 54333. After the test flame has been removed, the carpet burns for only 20 seconds. The flame does not reach the test section.
  • a needle felt made of polypropylene fibers, as described in Example 4, is treated with an impregnation solution of the following composition:
  • the needle felt is treated on a 2-roll pad and squeezed off. 100% wet pad.
  • the mixture is then dried at 135 ° C for 25 minutes.
  • the needle felt shows an excellent flame retardant effect according to the US safety standard for motor vehicles No. 302. (U.S. MVSS 302). After the test flame was removed, the needle felt only burned for 5 seconds.
  • the needle felt is elastic and dimensionally stable.
  • Example 1 The needle felt described in Example 1, which consists of a polyester fiber core and a polyamide tread, is treated with an impregnation solution which has the following composition:
  • the needle felt is squeezed off on a two-roll pad.
  • the mixture is then dried or condensed at 140 ° C. for 25 minutes.
  • the needle felt is lightly filled and elastic.
  • the needle felt also shows a very good flame retardant effect that survives several shampooings.
  • the flame retardancy test is carried out in accordance with D IN 54 333 "Determination of the flame propagation speed of textiles". After flame treatment, the needle felt burns for 45 seconds after / without reaching the test section. After 3 shampoos, the needle felt burns 60 seconds after the test flame is removed.
  • Example 2 The tufting carpet described in Example 2 is treated with the following primer impregnation solution using a rubber squeegee:
  • the knife application is controlled so that the dry coating is approximately 750 g / m 2 .
  • the tufted carpet provided with the primer described above shows a flexible handle and very good shape stability after drying.
  • the impregnation solution has not penetrated the pile threads.
  • the pile threads have retained their full mobility and are not glued to the walk-in side.
  • the tufted carpet thus equipped is very well permanently flame retardant.
  • the flame retardant test is carried out in accordance with DIN 54 333, "Determination of the Flame Spread Rate". After the test flame has been removed, the tufting carpet burns for 50 seconds. After three wet treatments with 2 g / 1 of a commercially available mild detergent for 10 minutes at 40 ° C, the tufted carpet burns for 55 seconds after the test flame has been removed without reaching the test section.
  • the tufting carpet described in Example 2 with a square meter weight of 650 g, consisting of a polyamide pile of 6 mm, tufted on polypropylene fleece (approx. 100 g / m 2 ) is provided with a primer with the aid of a laboratory rake.
  • the application must be controlled so that the dry laydown is approx. 780 - 800 g / m 2 . After the doctor blade treatment, it is dried at 145 ° C. for 12-15 minutes.
  • the primer impregnation solution is constructed similarly to that described in Example 2: "burns after" means that the flames of DIN 54 333 do not reach the 1st mark on the test track. (Very good values!
  • test object burns e.g. 10 ", 1 'etc. and then goes out.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Fireproofing Substances (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Polyethers (AREA)
EP78100036A 1977-06-11 1978-06-01 Polyadducts containing phosphorus and their application in the flameproofing of textile materials Expired EP0000024B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2726478 1977-06-11
DE19772726478 DE2726478A1 (de) 1977-06-11 1977-06-11 Phosphor enthaltende polyaddukte und verfahren zu deren herstellung

Publications (2)

Publication Number Publication Date
EP0000024A1 true EP0000024A1 (fr) 1978-12-20
EP0000024B1 EP0000024B1 (en) 1982-06-02

Family

ID=6011358

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100036A Expired EP0000024B1 (en) 1977-06-11 1978-06-01 Polyadducts containing phosphorus and their application in the flameproofing of textile materials

Country Status (6)

Country Link
US (1) US4244893A (fr)
EP (1) EP0000024B1 (fr)
JP (1) JPS545000A (fr)
CA (1) CA1113953A (fr)
DE (2) DE2726478A1 (fr)
IT (1) IT1096712B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0002733A2 (fr) * 1977-12-29 1979-07-11 Hoechst Aktiengesellschaft Procédé de préparation d'anhydrides d'acides phosphiniques et phosphoniques
EP0004323A1 (fr) * 1978-03-17 1979-10-03 Hoechst Aktiengesellschaft Procédé de préparation d'anhydrides d'acides alcanephosphoniques et alcane-bis-alcoylphosphiniques
EP0005329A1 (fr) * 1978-04-20 1979-11-14 Stauffer Chemical Company Procédé de préparation de produits du type poly(oxyorganophosphate/phosphonate), produits obtenus, utilisation de certains de ces produits comme retardateurs de combustion et matériaux traités avec ces produits
EP0009706A1 (fr) * 1978-09-27 1980-04-16 Hoechst Aktiengesellschaft Composés organiques du phosphore contenant des groupes ester d'acides hydroxy-3 alkylphosphiniques, leur préparation et utilisation
WO2008129559A2 (fr) 2007-04-23 2008-10-30 Serum Institute Of India Ltd Polysaccharides antigéniques et procédé pour leur préparation
WO2011148382A1 (fr) 2010-05-28 2011-12-01 Biological E Limited Procédé amélioré de purification de polysaccharides capsulaires de haemophilus influenza - b, neisseria meningitides tels que les sérotypes a, c, y et w-135, et d'autres polysaccharides capsulaires apparentés produits à partir de microorganismes à la fois à gram négatif et à gram positif en utilisant un phosphate d'aluminium avec un alcool.
WO2013087178A1 (fr) * 2011-12-16 2013-06-20 Clariant International Ltd Mélanges d'acides diphosphiniques et d'acides alkylphosphoniques, procédé pour leur préparation et leur utilisation

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4335178A (en) * 1979-09-10 1982-06-15 Stauffer Chemical Company Textiles containing a poly(oxyorganophosphate/phosphonate) flame retardant
DE3007714A1 (de) * 1980-02-29 1981-10-08 Hoechst Ag, 6000 Frankfurt Oligomere phophonsaeureester und deren verwendung als flammhemmitelle
US5756638A (en) * 1993-03-15 1998-05-26 Hoechst Ag Phosphorus-modified epoxy resins, process for the preparation thereof and use thereof
DE19635489C2 (de) * 1996-09-02 1998-11-26 Clariant Gmbh Flammwidrige, ungesättigte Polyesterharze, Verfahren zu deren Herstellung und ihre Verwendung zur Herstellung von Formkörpern, Laminaten oder Beschichtungen
JP4695279B2 (ja) * 2001-03-21 2011-06-08 日華化学株式会社 難燃加工剤、難燃加工方法、及び難燃加工繊維
AU2003215331A1 (en) * 2002-02-22 2003-09-09 University Of Georgia Research Foundation Catalyst system andmethod for preparing flame resistant materials
DE10309570B3 (de) * 2003-03-04 2004-09-02 Clariant Gmbh Modifizierte Polyethylenphosphinsäuren und deren Salze

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1156563B (de) * 1959-02-24 1963-10-31 Hoechst Ag Verfahren zur Herstellung von Polykondensationsprodukten mit oberflaechenaktiven Eigenschaften auf der Basis von Alkylenglykolen
GB1080938A (en) * 1964-08-13 1967-08-31 Kuhlmann Ets Method of preparing phosphorylated polyols,and their application
US3657145A (en) * 1967-12-01 1972-04-18 Petrolite Corp Demulsification with linear polymeric phosphorus-containing esters
US3764640A (en) * 1970-07-23 1973-10-09 Knapsack Ag A process of making phosphorus and halogen containing polyols
US4012463A (en) * 1974-05-28 1977-03-15 Stauffer Chemical Company Method of preparing stable condensation products using a Lewis acid catalyst and products thereof
FR2325658A1 (fr) * 1975-12-16 1977-04-22 Hoechst Ag Procede de preparation de produits de polyaddition renfermant du phosphore

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1156563B (de) * 1959-02-24 1963-10-31 Hoechst Ag Verfahren zur Herstellung von Polykondensationsprodukten mit oberflaechenaktiven Eigenschaften auf der Basis von Alkylenglykolen
GB1080938A (en) * 1964-08-13 1967-08-31 Kuhlmann Ets Method of preparing phosphorylated polyols,and their application
US3657145A (en) * 1967-12-01 1972-04-18 Petrolite Corp Demulsification with linear polymeric phosphorus-containing esters
US3764640A (en) * 1970-07-23 1973-10-09 Knapsack Ag A process of making phosphorus and halogen containing polyols
US4012463A (en) * 1974-05-28 1977-03-15 Stauffer Chemical Company Method of preparing stable condensation products using a Lewis acid catalyst and products thereof
FR2325658A1 (fr) * 1975-12-16 1977-04-22 Hoechst Ag Procede de preparation de produits de polyaddition renfermant du phosphore

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0002733A2 (fr) * 1977-12-29 1979-07-11 Hoechst Aktiengesellschaft Procédé de préparation d'anhydrides d'acides phosphiniques et phosphoniques
EP0002733A3 (fr) * 1977-12-29 1979-07-25 Hoechst Aktiengesellschaft Procédé de préparation d'anhydrides d'acides phosphiniques et phosphoniques
EP0004323A1 (fr) * 1978-03-17 1979-10-03 Hoechst Aktiengesellschaft Procédé de préparation d'anhydrides d'acides alcanephosphoniques et alcane-bis-alcoylphosphiniques
EP0005329A1 (fr) * 1978-04-20 1979-11-14 Stauffer Chemical Company Procédé de préparation de produits du type poly(oxyorganophosphate/phosphonate), produits obtenus, utilisation de certains de ces produits comme retardateurs de combustion et matériaux traités avec ces produits
EP0009706A1 (fr) * 1978-09-27 1980-04-16 Hoechst Aktiengesellschaft Composés organiques du phosphore contenant des groupes ester d'acides hydroxy-3 alkylphosphiniques, leur préparation et utilisation
WO2008129559A2 (fr) 2007-04-23 2008-10-30 Serum Institute Of India Ltd Polysaccharides antigéniques et procédé pour leur préparation
WO2011148382A1 (fr) 2010-05-28 2011-12-01 Biological E Limited Procédé amélioré de purification de polysaccharides capsulaires de haemophilus influenza - b, neisseria meningitides tels que les sérotypes a, c, y et w-135, et d'autres polysaccharides capsulaires apparentés produits à partir de microorganismes à la fois à gram négatif et à gram positif en utilisant un phosphate d'aluminium avec un alcool.
WO2013087178A1 (fr) * 2011-12-16 2013-06-20 Clariant International Ltd Mélanges d'acides diphosphiniques et d'acides alkylphosphoniques, procédé pour leur préparation et leur utilisation

Also Published As

Publication number Publication date
US4244893A (en) 1981-01-13
DE2726478A1 (de) 1978-12-14
JPS545000A (en) 1979-01-16
DE2861871D1 (en) 1982-07-22
EP0000024B1 (en) 1982-06-02
IT7824422A0 (it) 1978-06-09
IT1096712B (it) 1985-08-26
CA1113953A (fr) 1981-12-08

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