EP0602071A1 - Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation. - Google Patents

Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation.

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Publication number
EP0602071A1
EP0602071A1 EP92917518A EP92917518A EP0602071A1 EP 0602071 A1 EP0602071 A1 EP 0602071A1 EP 92917518 A EP92917518 A EP 92917518A EP 92917518 A EP92917518 A EP 92917518A EP 0602071 A1 EP0602071 A1 EP 0602071A1
Authority
EP
European Patent Office
Prior art keywords
acid
leather
oligomers
aqueous
esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92917518A
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German (de)
English (en)
Other versions
EP0602071B1 (fr
Inventor
Ludwig Schieferstein
Huber Rudolf Zauns
Joachim Conradi
Emil Ruscheinsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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.)
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0602071A1 publication Critical patent/EP0602071A1/fr
Application granted granted Critical
Publication of EP0602071B1 publication Critical patent/EP0602071B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the greasing of vegetable and / or mineral-tanned leather or fur skins is an essential process step in the finishing stages for the ready-to-use valuable material based on leather or fur.
  • the shape of the distribution of fat in the skin and the extent of integration of the fat components in the skin substance influence the "properties and the usefulness of the end products critical. It consists extensive expertise to possible interactions between the fatty components on the one hand and the tanned and Rest ⁇ tannins skin containing substance
  • the specific structure of the fatliquoring agents - for example the extent of their lipophilic groups and any reactive groups present for reaction with suitable reactive components in the tanned leather - determine, inter alia, the durability and effect of the fatliquoring equipment in practical use of the leather and fur products.
  • Treatment with substances having a hydrophobic effect for example aluminum, chromium and / or zirconium complexes, silicones or organic fluorine compounds.
  • EP 193832 relates to a process for the production of waterproof leather or furs using sulfosuccinic acid monoesters in combination with impregnating and / or hydrophobic greasing agents, the distinguishing feature of this process being that the leather or furs are subsequently retanned treated in an aqueous liquor with impregnating and / or hydrophobizing fatliquoring agents which contain sulfosuccinic acid onoester salts with Ci2-2 residues and fixed after acidification by adding a chromium, zirconium and / or aluminum salt.
  • aphiphilic agents have been described and recommended for the wet-end finishing of, in particular, mineral-tanned leathers and fur files, which represent specifically selected co-oligomers of, on the one hand, hydrophobic or oleophilic monomers and, on the other hand, hydrophilic monomer components.
  • Amphiphilic agents of this type can be worked into the leather or skins to be finished in the form of aqueous dispersions, emulsions and / or solutions after completion of the main tanning, for example by being rolled in.
  • these amphiphilic finishing agents can simultaneously take on the function of retanning.
  • amphiphilic agents can be finally fixed with, in particular, mineral tanning agents.
  • the more recent patent literature describes auxiliaries of the type concerned here.
  • EP 372746 describes corresponding agents and their use, the amphiphilic copolymers being formed from a predominant portion of at least one hydrophobic monomer and a minor portion of at least one copolymerizable hydrophilic monomer .
  • hydrophobic monomers long-chain alkyl (meth) acrylates, long-chain alkoxy- or alkylphenoxy (polyethylene oxide) - (meth) acrylates, primary alkenes, vinyl esters of long-chain alkylcarboxylic acids and their mixtures.
  • the minor proportion of hydrophilic comonomers are ethylenically unsaturated water-soluble acids or hydrophilic basic comonomers.
  • the molecular weight (weight average) of the copolymers is in the range from 2,000 to 100,000.
  • EP 412389 describes the use of copolymers as agents for the hydrophobization of leather and fur, which are obtained by radical copolymerization of (a) C8-40 monoolefins with (b) ethylenically unsaturated C4_8 dicarboxylic acid anhydrides in the manner of a bulk polymerization at temperatures from 80 to 300 ⁇ C to copolymers with molar masses of 500 to 20,000 g / mol, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed during the solvolysis have been prepared in an aqueous medium with bases and in the form of aqueous dispersions or solutions in front- lie.
  • EP 418661 describes for the same purpose the use of copolymers which (a) contain 50 to 90% by weight of C8-40-A1-alkyl (meth) acrylates, vinyl testers of C8-40-carboxylic acids or mixtures thereof ⁇ genes and (b) 10 to 50% by weight of monoethylenically unsaturated C3_i2-carboxylic acids r monoethylenically unsaturated dicarboxylic acid anhydrides, half-esters or half-amides of monoethylenically unsaturated C_ ⁇ i2-dicarboxylic acids, A ide of C3_i2-monocarboxylic acids or mixtures thereof in copolymerized form and containing 500 mol own up to 30,000 g / mol.
  • the copolymers are present in at least partially neutralized form in aqueous solution or in aqueous dispersion for the stated purpose.
  • the invention is based on the object of providing a new class of amphiphilic co-oligomers which can be used in an improved manner in the finishing steps of pretanned leather and fur skins, which are particularly suitable for penetrating the skin substance impregnate and, on the one hand, set the desired greasing and possibly also certain hydrophobic effects, but on the other hand can also replace the usual retanning at the same time.
  • the invention seeks to create the possibility of at least largely cleaning-resistant greasing, so that appropriately equipped leathers and skins become accessible for water-surfactant washing and / or chemical cleaning without suffering substantial losses in value.
  • the invention provides for the use of the co-olomer class described below, if desired also in a mixture with other greasing and / or hydrophobicizing, in particular known mixtures.
  • Components before, in one embodiment, both the class of amphiphilic co-oligomers selected according to the invention and the auxiliary substances of the type specified above, which may also be used, can be fixed in the skin material by post-treatment with, in particular, mineral tanning agents.
  • (c) may contain minor amounts of further hydrophilic and / or oleophilic comonomers in the oligomer molecule,
  • the invention relates to the use of the aqueous dispersions of these amphiphilic agents, in particular for finishing mineral-tanned leather and / or fur skins, the amphiphilic agents of the invention described above also taking on or re-tanning as part of this treatment can exercise.
  • the invention relates to aqueous dispersions of the amphiphilic co-oligomers from the previously defined components (a) and (b) and optionally (c), the molar ratios of (a) in these co-oligomers: (b) are in the range from about 1: 1 to 2: 1.
  • the component (s) (c) which may be present are present in smaller amounts by weight, based on the sum of (a) + (b) - contained.
  • the aqueous dispersions are adjusted to pH values in the range from neutral to slightly basic and are in particular in the form of a water-dilutable aqueous-pasous mass with valuable content of the co-oligomer in the range of about 30 to 50% by weight. % in front.
  • the basic element of the invention is the use of the co-oligomers from half-esters of maleic acid with selected oleophilic alcohols - component (a) - and acrylic acid and / or methacrylic acid - component (b), hereinafter also for the sake of simplicity as (meth) acrylic acid referred to as main components.
  • these co-oligomers can have minor amounts either of comonomers with a hydrophilic character and / or of comonomers with an oleophilic character.
  • These additional components of the co-oligomer molecule, if any, are collectively referred to as components of the type (c).
  • co-oligomers For the function of co-oligomers' purposes of the invention is ent distinctive, that is a lipophilic moiety of the co-oligomer molecule - the Halbester function of maleic acid with oleophilic alcohols - is connected with the carboxyl groups, both from the monomer components to (a ) as well as to (b).
  • Preferred embodiments for co-oligomers of the definition according to the invention provide that at least approximately equal amounts of (a) to (b) are used to build up the co-oligomer molecule, but it is preferred to use component ( a) to be used in molar excess over component (b). This ensures that a possible There is a large proportion of fatty and / or hydrophobizing lipophilic molecule components in the wet-end leather to be finished, but on the other hand there is a sufficiently large number of free carboxyl groups in the co-oligomer molecule, both of which consist of the components (a) as resulting from the components of (b).
  • this creates the possibility of specifically setting greasing effects in the fiber structure of the leather or fur, but at the same time there is a large number of reactive free carboxyl groups for interaction with the skin substance and / or auxiliaries which are already present or to be added subsequently - in particular mineral tanning ⁇ fabrics - available.
  • the desired combination of the majority of equipment effects is thus made controllably accessible.
  • the auxiliary substance can be fixed in the skin structure in such a way that cleaning by washing and / or chemical cleaning agents becomes accessible while maintaining the greased soft leather structure.
  • This component is formed by half-esters of maleic acid with lipophilic or oleophilic alcohols, in addition to or instead of the alcohols, their alkylene oxide adducts with a restricted and in addition known number of alkylene oxide residues adapted to the chain length of the alcohols can be used. Details of this can be found, for example, in EP 193832 cited at the outset.
  • oleophilic maleic acid half-esters as component (a) are used which are free from such an alkylene oxide derivatization.
  • Particularly suitable here are half esters of maleic acid with straight-chain and / or branched alcohols of an oleophilic character which contain at least predominantly 8 to 10 or more carbon atoms in the molecule.
  • the use of corresponding maleic acid half-esters may preferably be used, the alcohol residues of which have 12 to 24 carbon atoms, which are generally saturated, but if desired, at least partially but also may be olefinically 1- and / or polyunsaturated.
  • ester-forming fatty alcohols are corresponding components of natural origin, such as are obtained, for example, by reduction from fatty acids of natural origin in a manner known per se.
  • Saturated fatty alcohols in the range from C 12 to 18 can be of particular importance for the formation of the monomeric components to (a). By using or using these components, optimized greasy and water-repellent effects are obtained.
  • branched chain alcohols can also contain fewer than 12 carbon atoms in the molecule, corresponding components with at least 6 carbon atoms, preferably with at least 8 carbon atoms, being suitable.
  • An important branched chain alcohol in connection with the production the maleic acid half ester according to (a) can be used is 2-ethylhexanol.
  • the amount of branched-chain, in particular shorter, alcohols used will always be comparatively limited.
  • no more than 20% by weight, preferably no more than 15 or even 10% by weight, of the alcohol residues present in (a) is formed by such branched-chain lower alcohols.
  • Quantity ratios of about 95% by weight of pronounced oleophilic long-chain fatty alcohols, in particular in the range C 12 to 18 with about 5% by weight of a branched-chain alcohol of the 2-ethylhexanol type have proven to be sufficient for practical work.
  • the components of (a) are obtained in a manner known per se from maleic anhydride by alcoholysis with the respectively chosen hydrophobic fatty alcohol or alcohol mixture.
  • the preferred monomer component for (b) is acrylic acid, but also mixtures of acrylic acid and methacrylic acid with, in particular, predominant amounts of acrylic acid can be particularly considered here.
  • co-oligomerization is expediently carried out in such a way that the co-oligomers formed are obtained with average molecular weights (weight average) in the range from about 500 to 20,000.
  • Particularly suitable co-oligomers of the type described have corresponding average molecular weights in the range from about 1,000 to 10,000.
  • additional oleophilic monomer components according to (c) and / or additional hydrophilizing monomer components according to (c) can also be used.
  • copolymerizable oleophilic monomer compounds - for example the (meth) acrylates of long-chain alcohols known from the prior art - can also be used.
  • further acid groups for example vinyl sulfonic acid and the like, the character of the fixability or the ability for retanning are strengthened.
  • the amphiphilic agents according to the invention contain the component (s) (c) which may also be used in comparatively smaller amounts by weight, based on the sum of (a) + (b).
  • component (s) (c) which may also be used in comparatively smaller amounts by weight, based on the sum of (a) + (b).
  • co-oligomers of the type described which additionally contain oleophilic components (c).
  • their content is not more than 45% by weight and in particular less than 30% by weight of the co-oligomer.
  • co-oligomers are used which have been produced without adding such oleophilic components to (c). If additional greasing and / or hydrophobizing additional effects are desired here, then in the sense of the teaching according to the invention, mixture components are also used, which will be discussed separately below.
  • the co-oligomers from (a) and (b) and, if appropriate, (c) are prepared according to the invention by aqueous emulsion copolymerization.
  • the individual procedure is expediently carried out as follows: the separately prepared maleic acid half-ester is finely emulsified in slightly preheated water, if necessary, after melting.
  • Alkalisie- tion with in particular NaOH wfrd a best weakly acidic to neu ⁇ tral pH ensured '.
  • Preferred pH values are in the range from about 4.5 to 7, in particular 6 to 7.
  • an aqueous solution of component (s) becomes (b) - in particular Acrylic acid - metered in and simultaneous pH regulation ensures compliance with the specified weakly acidic pH value at best.
  • an initiator for the radical reaction in particular hydrogen peroxide, is metered in.
  • a neutral to weakly alkaline pH is set in the aqueous reaction medium.
  • pasty masses can be produced whose co-oligomer value Substance content is, for example, in the range from about 30 to 45% by weight and the unreacted constituents only contain amounts significantly below 1% by weight, preferably below 0.5% by weight.
  • Preferred pH values for the storage-stable product are in the range around pH 7 to 8.
  • the pasty masses are to be mixed with water and / or aqueous active ingredient mixtures of the type described below at any time and put to practical use.
  • amphiphilic agents of the described type are used, in the production of which in the stage of the aqueous co-oligomerization emulsifiers have been used which, when added to mineral-tanned leather and / or furs in particular, provide additional greasing effect or hydrophobization and can preferably be fixed simultaneously via acidic groups in the tanned leather or fur.
  • An important example of compounds of this type are the water-emulsifiable sulfosuccinic acid half-esters, which are derived from long-chain fatty alcohols and / or their alkylene oxide adducts. The statements made above in connection with the half-esters of the maleic acid component for (a) apply to the specific nature of the alcohols.
  • emulsifier class of the type concerned here are C 18 sulfosuccinate half esters which can be used in the course of the co-oligomerization, for example in amounts of 5 to 10% by weight (anhydrous basis). It has been shown that by using such emulsifier-like auxiliary components - which are known per se as finishing agents for leather greasing - advantageous effects can be achieved in the co-oligomerization according to the invention. For example, particularly finely divided aqueous-pasty reaction products with high recyclable content of co-oligomers are obtained.
  • auxiliaries of this type do not have to have been used as mixture components in the course of the co-oligomerization; they can also be used as the aqueous mixture of valuable substances used according to the invention Mix components are added afterwards.
  • connection types of this type are examples of connection types of this type:
  • the co-oligomers of (a) and (b) and optionally (c) defined according to the invention are combined with impregnating and / or hydrophobizing fatliquoring agents, the sulfosuccinic acid monoester salts with Ci2-24 " Fe ' fc'fcres'ten TM combination with other impregnating fatliquoring agents, selected in particular from the group of oxidized or oxidized and partially sulfated i8-26" ⁇ ° h1enementStof e or C3 -40 ⁇ waxes.
  • additional imgarg ⁇ alternating fatliquoring agents are phosphoric acid mono-Ci2-24 ⁇ a l ⁇ yl eS ⁇ er "P ar ⁇ tialester of polycarboxylic acids such CitronenTalkremono Ci6_24-alkyl esters, partial esters of polyalcohols, such as sorbitan, glycerol or pentaerythritol thrit -Ci6_24- esters of acid.
  • the amount of the co-oligomers of (a) and (b) and, if appropriate, defined according to the invention is (c) preferably at least about 35% by weight of the material mixture and in particular at least about 50% by weight - based on the same basis. It may be expedient to provide at least about 70 to 80% by weight of the mixture of valuable substances to be incorporated into the wet-end leather to be finished, based on the co-oligomers according to the invention.
  • the co-oligomer dispersions according to the invention are suitable for the treatment of all customary tanned skins, in particular corresponding material which has been tanned with mineral tanning agents.
  • the tanned skins are usually deacidified before the treatment. They may have been stained before treatment. Coloring can also only be carried out after the treatment according to the invention.
  • the leather to be impregnated in the wet state is advantageously mixed with the dispersions in an aqueous liquor at pH values of about 4 to 10, preferably at pH 5 to 8, and at temperatures of about 20 to 60 ° C., preferably 30 to 50 ° C. treated in several stages if necessary for a period of up to a few hours.
  • the treatment takes place, for example, by drumming in a barrel.
  • the amount of co-oligomer dispersion required is usually 0.1 to 30% by weight, in particular 1 to 20% by weight, based on the shaved weight of the leather or the wet weight of the fur skins.
  • the liquor length is usually 10 to 1,000%, preferably 30 to 150%, for fur files 50 to 500%.
  • the pH of the treatment liquor is shifted into the slightly acidic range by adding acids.
  • the addition of organic acids is particularly suitable, preferably formic acid.
  • Preferred pH values are in the range from 3 to 5, preferably in the range from about 3.5 to 4.
  • a fixation with, in particular, mineral tanning agents can be added, in which case the use of aluminum salts can be particularly preferred.
  • reaction vessel with stirrer, heating, cooling, reflux condenser, temperature measurement and 3 feed vessels, a mixture of maleic acid half ester and optionally maleic anhydride and enough water is given that an approximately 44% by weight reaction mixture is present.
  • the procedure is as follows:
  • the water is placed in a well-stirred reaction vessel and heated to approx. 35 ° C.
  • maleic anhydride (Examples 1 and 2) is also used, this component is first added in portions at such a rate that the internal temperature of the reaction mixture remains below approx. 55 ° C. (time required approx. 20 minutes; possibly weak external cooling). After the maleic anhydride has completely dissolved, the maleic half-ester, if necessary melted, is added.
  • the template is then neutralized by adding NaOH cookies in portions to a pH of approximately 7.0. The internal temperature rises to a maximum of 80 ° C.
  • the reactor contents are then heated to 90 ° C.
  • feed solutions were previously prepared separately from this reaction template: feed solution 1: acrylic acid / water (demineralized); Inlet solution 2: onium peroxidisulfate / water (demineralized); Feed solution 3: 35% by weight hydrogen peroxide After the temperature inside the reactor has reached 90 ° C., the addition of the feed solutions and the starter is started.
  • feed solution 1 acrylic acid / water (demineralized);
  • Inlet solution 2 onium peroxidisulfate / water (demineralized);
  • Feed solution 3 35% by weight hydrogen peroxide
  • Allowance 1 is added evenly over a period of 5 hours.
  • feed solutions 2 and 3 are added evenly over a period of 6 hours at an internal temperature of 100 ° C - this can cause slight reflux.
  • reaction mixture is then reheated at 100 ° C. for 1 hour.
  • Example 1 A mixture based on maleic anhydride (MA) and maleic anhydride half-ester (MA half ester) is used as the reaction component based on maleic acid.
  • the half ester was prepared by reacting the appropriate amount of MSA with C ⁇ 2 fatty alcohol.
  • Example 2 A mixture of MSA / MSA half esters is also used here.
  • the half ester is the reaction product of the MSA with Ci ⁇ fatty alcohol.
  • the oligomer obtained is initially lumpy, and only after standing overnight and warming is there a homogeneous reaction mass.
  • Example 3 The MA half ester is a mixed product based on the alcohol components Ci5 / i8 _ fatty alcohol mixture and 2-ethylhexanol (2-EHOH), for the quantitative ratio see the table below.
  • the reaction mixture is very lumpy during the reaction and is subsequently diluted with water because of its high viscosity.
  • Example 4 The quality of the aqueous maleic acid half ester approach corresponds to the approach of Example 3, but in addition to this reaction approach Ci8 sulfosucsinate half ester is added as an emulsifier. A highly viscous but homogeneous reaction product is obtained.
  • Example 5 The half-ester with C 2 ⁇ fatty alcohol - without the addition of MA - is used as the reaction component based on maleic acid.
  • Example 6 The reaction component based on MAA half esters is the mixture of the half esters based on Ci6 / i8 fatty alcohols and 2-ethylhexanol (2-EHOH) identified in the table below; in deviation from Example 3, however, from the start, twice the amount of water is used in the template. This produces a reaction product that separates into two phases after 24 hours at room temperature. Table 1
  • chrome leather samples are treated with the oligomers according to the invention under the working conditions of Examples 7 to 11 below.
  • Examples 7 to 11 which are summarized in tabular form, the products of the definition according to the invention from Examples 1, 4 and 5 are used as oligomers of the invention. In all cases, soft, supple and well-filled leathers are obtained, which have a pleasant grip and are characterized by high grain resistance.
  • the samples can be subjected to both aqueous-surfactant washing (30 ° C) and chemical cleaning without causing lasting damage to the product properties. Even after repeated repetitive cleaning steps of the specified type, no lasting stiffening of the leather material can be determined.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Detergent Compositions (AREA)

Abstract

On décrit l'utilisation de dispersions aqueuses de co-oligomères obtenus par copolymérisation par émulsion aqueuse amorcée par des radicaux, dans une plage de pH réglée de faiblement acide à neutre, des composés suivants: a) des semi-esters de l'acide maléique avec des alcools oléophiles et/ou leurs produits d'addition avec des oxydes d'alkylène inférieurs, et b) de l'acide acrylique et/ou méthacrylique, comme principaux constituants, lesquels peuvent contenir en outre: c) des quantités accessoires d'autres co-monomères hydrophiles et/ou oléophiles dans la molécule d'oligomère, comme agents amphiphiles pour l'apprêt graisseux et résistant au lavage des cuirs et des peaux. L'invention a également pour objet des dispersions aqueuses de ces co-oligomères amphiphiles contenant des composés a) et b) dans un rapport molaire de a) à b) compris entre 1:1 et 2:1 et, le cas échéant, des composants c) en plus faibles quantités pondérales, ces dispersions étant réglées à des pH neutres à faiblement basiques et étant constituées de manière à former notamment une masse pâteuse aqueuse diluable dans l'eau. Lorsqu'elles sont mélangées aux co-oligomères, ces dispersions aqueuses peuvent contenir d'autres agents connus de graissage ou rendant hydrophobe pour les cuirs et les peaux.
EP92917518A 1991-09-03 1992-08-24 Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation Expired - Lifetime EP0602071B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4129244A DE4129244A1 (de) 1991-09-03 1991-09-03 Waessrige dispersionen von neuen amphiphilen co-oligomeren fuer die wasch- und reinigungsbestaendige fettende ausruestung von leder und pelzfellen sowie ihre verwendung
DE4129244 1991-09-03
PCT/EP1992/001938 WO1993005188A1 (fr) 1991-09-03 1992-08-24 Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation

Publications (2)

Publication Number Publication Date
EP0602071A1 true EP0602071A1 (fr) 1994-06-22
EP0602071B1 EP0602071B1 (fr) 1995-03-01

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EP92917518A Expired - Lifetime EP0602071B1 (fr) 1991-09-03 1992-08-24 Dispersions aqueuses de nouveaux co-oligomeres amphiphiles pour l'appret graisseux resistant au lavage et au nettoyage des cuirs et des peaux, et leur utilisation

Country Status (8)

Country Link
US (1) US5501707A (fr)
EP (1) EP0602071B1 (fr)
JP (1) JP3295080B2 (fr)
AT (1) ATE119208T1 (fr)
DE (2) DE4129244A1 (fr)
ES (1) ES2070009T3 (fr)
MX (1) MX9205019A (fr)
WO (1) WO1993005188A1 (fr)

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US8816029B2 (en) 2009-08-28 2014-08-26 3M Innovative Properties Company Compositions and articles comprising polymerizable ionic liquid mixture, and methods of curing
WO2011031442A2 (fr) 2009-08-28 2011-03-17 3M Innovative Properties Company Liquide ionique polymérisable comprenant un cation multifonctionnel et revêtements antistatiques
US8853338B2 (en) 2009-12-22 2014-10-07 3M Innovative Properties Company Curable dental compositions and articles comprising polymerizable ionic liquids
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Publication number Publication date
MX9205019A (es) 1993-04-01
DE4129244A1 (de) 1993-03-04
JP3295080B2 (ja) 2002-06-24
JPH06510083A (ja) 1994-11-10
ATE119208T1 (de) 1995-03-15
US5501707A (en) 1996-03-26
DE59201561D1 (de) 1995-04-06
ES2070009T3 (es) 1995-05-16
WO1993005188A1 (fr) 1993-03-18
EP0602071B1 (fr) 1995-03-01

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