WO1992022609A1 - Sealants and adhesives based on silane-modified prepolymers - Google Patents
Sealants and adhesives based on silane-modified prepolymers Download PDFInfo
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- WO1992022609A1 WO1992022609A1 PCT/EP1992/001194 EP9201194W WO9222609A1 WO 1992022609 A1 WO1992022609 A1 WO 1992022609A1 EP 9201194 W EP9201194 W EP 9201194W WO 9222609 A1 WO9222609 A1 WO 9222609A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- 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
- C08K5/02—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0239—Oxides, hydroxides, carbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0411—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/04—Non-macromolecular organic compounds
- C09K2200/0447—Fats, fatty oils, higher fatty acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0635—Halogen-containing polymers, e.g. PVC
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/068—Containing also other elements than carbon, oxygen or nitrogen in the polymer main chain
- C09K2200/0685—Containing silicon
Definitions
- the invention relates to compositions based on branched or unbranched prepolymers modified with silane at the chain ends, a process for their preparation and their use.
- Adhesives and sealants reacting when moisture enters into elastic masses are known. They usually consist of a moisture-reactive prepolymer, plasticizers, fillers and additives as well as a catalyst system.
- US Pat. No. 3,971,751 describes compounds which are moisture-reactive and which carry silicon atoms with at least one hydrolyzable radical at the chain ends, with the hydrolyzable group (s) being, for example, alkoxy, aminoxy, acid amide or ketoximato groups own.
- the dimethoxymethylsilyl group is mentioned as the preferred silyl end group.
- EP 0 326 862 A further method for reducing the surface tack is described in EP 0 326 862, in which fluorine compounds containing silicon groups are used to reduce the tack.
- fluorine compounds containing silicon groups are used to reduce the tack.
- these compounds have the disadvantage that they are sensitive to hydrolysis and, moreover, can intervene in the polymer system as chain terminators, the more the more additive is added, the more so.
- compositions of different wettable silicone prepolymers based on siloxanes which contain ethoxylated, nonionic surfactants or fluorosurfactants. These surfactants serve to make the silicone crosslinked later hydrophilic.
- a disadvantage of the compositions containing these fluorosurfactants 5 is, however, that the fluorosurfactants prevent or at least considerably complicate the overpainting of the crosslinked silicone.
- the object of the invention is to avoid the disadvantages mentioned and to provide compositions based on silane-modified prepolymers which lead to a crosslinked polymer, the surface tack of which is considerably reduced, but which is nevertheless overlaid with aqueous dispersions - can be. 15
- the invention is also based on the object of making it possible to reduce the surface tack while maintaining good paintability by means of an easy-to-handle and commercially available additive.
- compositions which contain branched or unbranched prepolymers and fluorosurfactants which are silane-modified at the chain ends.
- R and R ' are used, wherein R and R 'are alkyl, alkoxy, aminoxy, acid amide or ketoximato groups, n is a number from 1 to 35,500, in particular from 100 to 300 and a is a number from 0 to 2, where at least a hydrolyzable group is bonded directly to the Si atom.
- R is a branched or unbranched CC 10 alkyl group, particularly preferably a Cx-Cs-alkyl group and in particular a methyl group and R 'is an alkoxy group, a ketoximato group, an aminoxy group, particularly preferably an alkoxy group with the structure OR ", where R "is a C ! -C 10 - alkyl group, particularly preferably a Ci-Cs alkyl group and in particular a methyl group.
- inert, solid or liquid, saturated fluorine compounds which are also known as fluorosurfactants, are used as additives with respect to the silane-modified prepolymer.
- Aliphatic fluorosurfactants are preferably used. In their chemical structure they correspond to fluorinated alkyl (poly) alkoxylates, fluorinated alkyl (poly) sulfonamides or mixtures thereof. Compounds of this type are sold under the names Fluorad ® or Dynamar ® by 3M for example. If appropriate, these fluorosurfactants can be mixed with further fluorine compounds.
- the compositions according to the invention contain 0.01 to 10% by weight, in particular 0.05 to 5% by weight, of fluorine compounds, based on the weight of the compositions.
- compositions according to the invention can contain one or more unbranched or branched silane-modified prepolymer components and further optionally other polymers or prepolymers.
- other additives such as plasticizers, fillers, silanes, antioxidants, dyes or catalysts can be present in the compositions.
- compositions according to the invention are prepared by mixing the prepolymers with the fluorine compounds and, if appropriate, with the addition of further additives specified above.
- the fluorine compounds are preferably added at the beginning of the preparation of the mixture. If solid fluorine compounds are used, it may be advisable to pre-dissolve them in a plasticizer or a solvent. paste to ensure a quick and homogeneous distribution in the prepolymer.
- the fluorine compounds in the compositions according to the invention do not impair the ability to be painted over. Due to the lack of siloxane oligomers, the sealing compounds according to the invention are also absolutely "free from discoloration".
- Recipe A is a comparative example that contains no fluorosurfactant.
- formulation C contains, in addition to 30% of the silane-modified prepolymer, 5% of polyvinyl chloride. The figures are in% by weight.
- compositions A, B and C were applied to glass or polyethylene plates or lacquered wood in order to test adhesion, Shore A hardness, through-hardening speed and surface tack. The results are summarized in Table 2.
- the fluorosurfactants according to the invention can of course also be used in multi-component, preferably in two-component systems.
- the latter is understood to mean systems in which the hardening is accomplished not by diffusing air humidity but by mixing two or more components.
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
Dicht- und Klebstoffe auf Basis silanmodifizierter Präpolymere Sealants and adhesives based on silane-modified prepolymers
Die Erfindung betrifft Zusammensetzungen auf Basis verzweigter oder unverzweigter an den Kettenenden silanmodifizierter Präpo¬ lymere, ein Verfahren zu deren Herstellung und deren Verwendung.The invention relates to compositions based on branched or unbranched prepolymers modified with silane at the chain ends, a process for their preparation and their use.
Bei Zutritt von Feuchtigkeit zu elastischen Massen reagierende Kleb- und Dichtstoffe sind bekannt. Sie bestehen in der Regel aus einem feuchtigkeitsreaktiven Präpolymer, Weichmacher, Füll- und Zusatzstoffen sowie einem Katalysatorsystem. Als feuchtig¬ keitsreaktive Präpolymere wurden in der US-PS 3 971 751 Verbin¬ dungen beschrieben, die an den Kettenenden Siliciumatome mit mindestens einem hydrolysierbaren Rest tragen, wobei sich als hydrolisierbare Gruppe(n) z.B. Alkoxy-, Aminoxy-, Säureamid- oder Ketoximatogruppen eignen. Als bevorzugte Silylendgruppe wird die Dimethoxymethylsilylgruppe genannt. In Abhängigkeit von den bei der Synthese der silanmodifizierten Präpolymere verwen¬ deten Rohstoffe lassen sich auch höherwertige (z.B. dreiwertige) Präpolymere mit Silylendgruppen herstellen. Bei der Formulierung von Kleb-, insbesondere aber von weichen Dichtstoffen auf Basis der obengenannten silan odifizierten Präpolymere ergeben sich Produkte, die auch nach vollständiger Durchhärtung noch eine erhebliche Oberflächenklebrigkeit, auch "Tack" genannt, aufwei- sen. Dies ist für viele Anwendungen von so großem Nachteil, daß oftmals zu anderen Dichtstoffen gegriffen werden muß, die zwar weniger Tack aufweisen, aber anderweitige Nachteile zeigen. Beispielsweise ist bei der Einglasung von Fenstern eine Grund- Voraussetzung, daß der deutlich sichtbare Dichtstoff in der Fuge zwischen Fensterglas und -rahmen eine glatte und staubfreie Oberfläche aufweist, die gegebenenfalls mit üblichen Mitteln leicht zu reinigen sein muß. Weist ein Dichtstoff nach der Bil¬ dung einer Oberflächenhaut jedoch noch einen erheblichen Rest- Tack auf, d.h. deutlich spürbare Oberflächenklebrigkeit, kann sich beispielsweise Staub auf dem Dichtstoff absetzen. Der an dem Dichtstoff haftende Staub ist dann mit einfachen Mitteln nicht mehr entfernbar.Adhesives and sealants reacting when moisture enters into elastic masses are known. They usually consist of a moisture-reactive prepolymer, plasticizers, fillers and additives as well as a catalyst system. US Pat. No. 3,971,751 describes compounds which are moisture-reactive and which carry silicon atoms with at least one hydrolyzable radical at the chain ends, with the hydrolyzable group (s) being, for example, alkoxy, aminoxy, acid amide or ketoximato groups own. The dimethoxymethylsilyl group is mentioned as the preferred silyl end group. Depending on the raw materials used in the synthesis of the silane-modified prepolymers, higher-quality (eg trivalent) prepolymers with silyl end groups can also be produced. When formulating adhesives, but especially soft sealants, based on the above-mentioned silane-modified prepolymers, products are obtained which, even after they have completely hardened, still have considerable surface tack, also called "tack". sen. For many applications this is such a disadvantage that it is often necessary to resort to other sealants which have less tack but show other disadvantages. For example, when windows are glazed in, a basic prerequisite is that the clearly visible sealant in the joint between the window glass and frame has a smooth and dust-free surface, which may have to be easy to clean with conventional means. However, if a sealant has a considerable residual tack after the formation of a surface skin, ie clearly noticeable surface stickiness, dust can, for example, settle on the sealant. The dust adhering to the sealant can then no longer be removed with simple means.
In der Literatur wurde dieser Nachteil der unter Verwendung von silanmodifiziertenPräpolymeren (SMP-Präpolymeren) hergestellten Dichtstoffe bereits vor längerem beschrieben. Es sind daher Ver¬ suche unternommen worden, diesen Mangel zu beheben. In der EP 0 327 896 wird z.B. beschrieben, daß durch Zugabe von luftoxi- dierbaren Verbindungen wie Leinöl oder Polybutadienöl eine kleb¬ freie Haut erzielt werden kann. Nachteilig ist hierbei jedoch, daß der Vorgang der "Lufttrocknung", d.h. der oxidativen Ver¬ netzung des Additivs, einen langen Zeitraum in Anspruch nimmt, in der Regel mehrere Tage bis Wochen. Während dieser Zeit kann sich aber, bedingt durch den noch vorhandenen Tack, Staub auf dem Dichtstoff absetzen.This disadvantage of the sealants produced using silane-modified prepolymers (SMP prepolymers) has been described for some time in the literature. Attempts have therefore been made to remedy this deficiency. EP 0 327 896 e.g. described that a tack-free skin can be achieved by adding air-oxidizable compounds such as linseed oil or polybutadiene oil. The disadvantage here, however, is that the "air drying" process, i.e. the oxidative crosslinking of the additive takes a long time, usually several days to weeks. During this time, due to the tack still present, dust can settle on the sealant.
Ein weiteres Verfahren zur Verminderung der Oberflächenklebrig¬ keit wird in der EP 0 326 862 beschrieben, bei dem zur Tackver- minderung siliciumgruppenhaltige Fluorverbindungen eingesetzt werden. Diese Verbindungen weisen neben ihrer schweren Zugäng¬ lichkeit den Nachteil auf, daß sie hydrolyseempfindlich sind und zudem als Kettenabbrecher in das Polymersystem eingreifen kön¬ nen, dies um so stärker, je mehr Additiv zugesetzt wird.A further method for reducing the surface tack is described in EP 0 326 862, in which fluorine compounds containing silicon groups are used to reduce the tack. In addition to being difficult to access, these compounds have the disadvantage that they are sensitive to hydrolysis and, moreover, can intervene in the polymer system as chain terminators, the more the more additive is added, the more so.
Ferner sind in der US-PS 4 657 959 Zusammensetzungen aus ver- netzbaren Silikon-Präpolymeren auf Basis von Siloxanen beschrie¬ ben, die ethoxylierte, nichtionische Tenside oder Fluortenside enthalten. Diese Tenside dienen dazu, das später vernetzte Sili¬ kon hydrophil zu machen. Nachteilig an den diese Fluortenside 5 enthaltenden Zusammensetzungen ist jedoch, daß die Fluortenside das Überlackieren des vernetzten Silikons verhindern oder zu¬ mindest erheblich erschweren.In addition, US Pat. No. 4,657,959 describes compositions of different wettable silicone prepolymers based on siloxanes which contain ethoxylated, nonionic surfactants or fluorosurfactants. These surfactants serve to make the silicone crosslinked later hydrophilic. A disadvantage of the compositions containing these fluorosurfactants 5 is, however, that the fluorosurfactants prevent or at least considerably complicate the overpainting of the crosslinked silicone.
Aufgabe der Erfindung ist es, die genannten Nachteile zu ver- 10 meiden und Zusammensetzungen auf Basis silanmodifizierter Prä¬ polymere zur Verfügung zu stellen, die zu einem vernetzten Poly¬ mer führen, dessen Oberflächenklebrigkeit erheblich vermindert ist, daß aber trotzdem mit wäßrigen Dispersionen gut überlak- kierbar ist. 15The object of the invention is to avoid the disadvantages mentioned and to provide compositions based on silane-modified prepolymers which lead to a crosslinked polymer, the surface tack of which is considerably reduced, but which is nevertheless overlaid with aqueous dispersions - can be. 15
Ferner liegt der Erfindung die Aufgabe zugrunde, die Verminde¬ rung der Oberflächenklebrigkeit bei Erhaltung der guten Über- lackierbarkeit durch ein einfach handhabbares und kommerziell erhältliches Additiv zu ermöglichen. 20The invention is also based on the object of making it possible to reduce the surface tack while maintaining good paintability by means of an easy-to-handle and commercially available additive. 20th
Das Problem wird erfindungsgemäß durch Zusammensetzungen gelöst, die verzweigte oder unverzweigte, an den Kettenenden silanmodi¬ fizierte Präpolymere und Fluortenside enthalten.According to the invention, the problem is solved by compositions which contain branched or unbranched prepolymers and fluorosurfactants which are silane-modified at the chain ends.
25 Als silanmodifizierte Präpolymere können beispielsweise die in der US-PS 3 971 751 beschriebenen, unverzweigten Präpolymere mit der nachstehend aufgeführten allgemeinen Formel:25 For example, the unbranched prepolymers described in US Pat. No. 3,971,751 with the general formula listed below can be used as silane-modified prepolymers:
(R' )3_aRaSi-(CH2)3-O-(CH2-CH-0)n-(CH2)3)-SiRa(R' )3.a 30 I(R ') 3 _ a R a Si- (CH 2 ) 3 -O- (CH 2 -CH-0) n - (CH 2 ) 3 ) -SiR a (R') 3 . a 30 I
CH3 CH 3
verwendet werden, worin R und R' Alkyl-, Alkoxy-, Aminoxy-, Säureamid- oder Ketoximatogruppen sind, n eine Zahl von 1 bis 35 500, insbesondere von 100 bis 300 ist und a eine Zahl von 0 bis 2 ist, wobei mindestens eine hydrolisierbare Gruppe direkt an das Si-Atom gebunden ist. Bevorzugt ist, daß R eine verzweigte oder unverzweigte C-C10- Alkylgruppe, besonders bevorzugt eine Cx-Cs-Alkylgruppe und insbesondere eine Methylgruppe ist und R' eine Alkoxygruppe, eine Ketoximatogruppe, eine Aminoxygruppe, besonders bevorzugt eine Alkoxygruppe mit der Struktur OR" ist, wobei R" eine C!-C10- Alkylgruppe, besonders bevorzugt eine Ci-Cs-Alkylgruppe und insbesondere eine Methylgruppe ist.are used, wherein R and R 'are alkyl, alkoxy, aminoxy, acid amide or ketoximato groups, n is a number from 1 to 35,500, in particular from 100 to 300 and a is a number from 0 to 2, where at least a hydrolyzable group is bonded directly to the Si atom. It is preferred that R is a branched or unbranched CC 10 alkyl group, particularly preferably a Cx-Cs-alkyl group and in particular a methyl group and R 'is an alkoxy group, a ketoximato group, an aminoxy group, particularly preferably an alkoxy group with the structure OR ", where R "is a C ! -C 10 - alkyl group, particularly preferably a Ci-Cs alkyl group and in particular a methyl group.
Erfindungsgemäß werden als Additive gegenüber dem silanmodifi- zierten Präpolymeren inerte, feste oder flüssige, gesättigte Fluorverbindungen verwendet, die auch als Fluortenside bekannt sind. Vorzugsweise werden aliphatische Fluortenside eingesetzt. In ihrem chemischen Aufbau entsprechen sie fluorierten Alkyl(poly)alkoxylaten, fluoriertenAlkyl(poly)sulfonamiden oder Mischungen davon. Verbindungen dieser Art werden z.B. unter den Bezeichnungen Fluorad® bzw. Dynamar® von der Firma 3M vertrieben. Gegebenenfalls können diese Fluortenside mit weiteren Fluorver¬ bindungen gemischt werden. Die erfindungsgemäßen Zusammensetzun¬ gen enthalten 0,01 bis 10 Gew.%, insbesondere 0,05 bis 5 Gew.% Fluorverbindungen, bezogen auf das Gewicht der Zusammensetzun¬ gen.According to the invention, inert, solid or liquid, saturated fluorine compounds, which are also known as fluorosurfactants, are used as additives with respect to the silane-modified prepolymer. Aliphatic fluorosurfactants are preferably used. In their chemical structure they correspond to fluorinated alkyl (poly) alkoxylates, fluorinated alkyl (poly) sulfonamides or mixtures thereof. Compounds of this type are sold under the names Fluorad ® or Dynamar ® by 3M for example. If appropriate, these fluorosurfactants can be mixed with further fluorine compounds. The compositions according to the invention contain 0.01 to 10% by weight, in particular 0.05 to 5% by weight, of fluorine compounds, based on the weight of the compositions.
Die erfindungsgemäßen Zusammensetzungen können eine oder mehrere unverzweigte oder verzweigte silanmodifizierte Präpolymerkom- ponenten und ferner gegebenenfalls andere Polymere oder Präpoly¬ mere enthalten. Außerdem können weitere Additive wie Weichma¬ cher, Füllstoffe, Silane, Antioxidantien, Farbstoffe oder Kata¬ lysatoren in den Zusammensetzungen enthalten sein.The compositions according to the invention can contain one or more unbranched or branched silane-modified prepolymer components and further optionally other polymers or prepolymers. In addition, other additives such as plasticizers, fillers, silanes, antioxidants, dyes or catalysts can be present in the compositions.
Die erfindungsgemäßen Zusammensetzungen werden durch Vermischen der Präpolymeren mit den Fluorverbindungen und gegebenenfalls unter Zusatz weiterer, oben angegebener Additive hergestellt. Vorzugsweise erfolgt der Zusatz der Fluorverbindungen bereits am Anfang der Mischungsherstellung. Sollten feste Fluorverbindungen eingesetzt werden, ist es gegebenenfalls zweckmäßig, diese in einem Weichmacher oder einem Lösungsmittel vorzulösen bzw. anzu- pasten, um eine schnelle und homogene Verteilung im Präpolymer zu gewährleisten.The compositions according to the invention are prepared by mixing the prepolymers with the fluorine compounds and, if appropriate, with the addition of further additives specified above. The fluorine compounds are preferably added at the beginning of the preparation of the mixture. If solid fluorine compounds are used, it may be advisable to pre-dissolve them in a plasticizer or a solvent. paste to ensure a quick and homogeneous distribution in the prepolymer.
Obwohl durch Zugabe von Fluortensiden im allgemeinen, so z.B. auch bei Silikon-Dichtmassen, eine Uberlackierung mit wäßrigen Dispersionen erschwert oder ganz unmöglich gemacht wird, beein¬ trächtigen die Fluorverbindungen in den erfindungsgemäßen Zu¬ sammensetzungen die Überlackierbarkeit nicht. Durch das Fehlen von Siloxanoligomeren sind die erfindungsgemäßen Dichtmassen auch absolut "verfärbungsfrei" .Although by adding fluorosurfactants in general, e.g. Even in the case of silicone sealing compounds, overpainting with aqueous dispersions is made difficult or completely impossible, the fluorine compounds in the compositions according to the invention do not impair the ability to be painted over. Due to the lack of siloxane oligomers, the sealing compounds according to the invention are also absolutely "free from discoloration".
In der Tabelle sind zur näheren Erläuterung der Erfindung drei typische Rezepturen aufgeführt. Rezeptur A ist ein Vergleichs¬ beispiel, das kein Fluortensid enthält. Rezeptur C enthält im Unterschied zu Rezeptur B neben 30 % des silanmodifizierten Prä¬ polymeren auch 5 % Polyvinylchlorid. Die Angaben sind jeweils in Gew.%.In the table, three typical formulations are listed for a more detailed explanation of the invention. Recipe A is a comparative example that contains no fluorosurfactant. In contrast to formulation B, formulation C contains, in addition to 30% of the silane-modified prepolymer, 5% of polyvinyl chloride. The figures are in% by weight.
Tabelle 1Table 1
*Bis[3-(methyldimethoxysilyl)propyl]polyoxypropylen* Bis [3- (methyldimethoxysilyl) propyl] polyoxypropylene
**Paste aus 50 Teilen Dioctylphthalat und 50 Teilen Fluortensid. Nach der Mischungsherstellung wurden die Zusammensetzungen A, B und C auf Glas- bzw. Polyethylenplatten oder lackierte Hölzer aufgetragen, um Haftung, Shore-A-Härte, Durchhärtegeschwindig- keit und Oberflächenklebrigkeit zu prüfen. Die Ergebnisse sind in Tabelle 2 zusammengefaßt.** Paste of 50 parts dioctyl phthalate and 50 parts fluorosurfactant. After the mixture had been produced, compositions A, B and C were applied to glass or polyethylene plates or lacquered wood in order to test adhesion, Shore A hardness, through-hardening speed and surface tack. The results are summarized in Table 2.
Tabelle 2Table 2
BB
+ + + + 27 26+ + + + 27 26
3 33 3
+ ++ +
0,39 abesL0.39 abesL
Die Oberflächenklebrigkeit wird bestimmt, indem eine Stahlkugel mit einem Durchmesser von 3 mm auf das Ende eines ca. 2 mm star- ken Feldes der ausvulkanisierten Zusammensetzung gelegt wird, das auf einer beweglichen Platte (L = 40 cm) befestigt ist. An der Seite, an der sich die Kugel befindet, wird die Platte lang¬ sam hochgehoben. Es wird die Höhe H bestimmt, bei der die Kugel die entstandene schiefe Ebene hinabzurollen beginnt. Je kleb- riger die Oberfläche der zu testenden Zusammensetzung ist, desto höher muß das Ende der Platte gehoben werden, bevor die Kugel in Bewegung gerät. Die Kugel wird daher um so eher ins Rollen gera¬ ten, je weniger Tack die ausvulkanisierte Zusammensetzung auf¬ weist, d.h. desto niedriger sind die erhaltenen Werte für H. Aus Tabelle 2 erkennt man, daß durch den Zusatz des erfindungsgemä¬ ßen Fluortensids eine deutliche Reduzierung der Öberflächenkleb- rigkeit erzielt werden kann. Der Rollbeginn von ca. 5 cm liegt hierbei in der Größenordnung, wie er auch mit neutralvernetzen¬ den Silikonen erreicht wird.The surface stickiness is determined by placing a steel ball with a diameter of 3 mm on the end of an approximately 2 mm thick field of the vulcanized composition, which is attached to a movable plate (L = 40 cm). On the side on which the ball is located, the plate is slowly lifted up. The height H at which the ball begins to roll down the resulting inclined plane is determined. The more sticky the surface of the composition to be tested, the higher the end of the plate has to be lifted before the ball starts to move. The ball will therefore start rolling the sooner the less tack the vulcanized composition has, ie the lower the values obtained for H. From Table 2 it can be seen that the addition of the fluorosurfactant according to the invention results in a clear reduction Reduction of surface adhesive can be achieved. The start of rolling of about 5 cm is of the order of magnitude that is also achieved with neutral cross-linking silicones.
Die erfindungsgemäßen Fluortenside können selbstverständlich neben ihrem Einsatz in Einkomponenten-Systemen, wie in den Bei¬ spielen A bis C gezeigt ist, auch in Mehr-, vorzugsweise in Zweikomponenten-Systemen verwendeten werden. Unter letzteren versteht man Systeme, bei denen die Härtung nicht durch eindif- fundierende Luftfeuchtigkeit sondern durch Vermischen von zwei oder mehr Komponenten bewerkstelligt wird. In addition to their use in one-component systems, as shown in Examples A to C, the fluorosurfactants according to the invention can of course also be used in multi-component, preferably in two-component systems. The latter is understood to mean systems in which the hardening is accomplished not by diffusing air humidity but by mixing two or more components.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4119484.5 | 1991-06-13 | ||
| DE19914119484 DE4119484C2 (en) | 1991-06-13 | 1991-06-13 | Sealants and adhesives based on silane-modified prepolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992022609A1 true WO1992022609A1 (en) | 1992-12-23 |
Family
ID=6433847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1992/001194 Ceased WO1992022609A1 (en) | 1991-06-13 | 1992-05-31 | Sealants and adhesives based on silane-modified prepolymers |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE4119484C2 (en) |
| WO (1) | WO1992022609A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1179571A4 (en) * | 1999-03-23 | 2002-06-05 | Kaneka Corp | Curable resin compositions |
| JP2007070629A (en) * | 2005-09-02 | 2007-03-22 | Sika Technology Ag | Aqueous two-component organic alkoxysilane composition |
| JP2007530725A (en) * | 2004-03-23 | 2007-11-01 | シーカ・テクノロジー・アーゲー | Use of a two-component adhesion promoter composition and a package with two compartments |
| EP1650261A4 (en) * | 2003-07-18 | 2008-02-27 | Kaneka Corp | Curable composition |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4306997A1 (en) * | 1993-03-05 | 1994-09-08 | Thera Ges Fuer Patente | Hydrophilized polyethers |
| DE4412261C2 (en) * | 1994-04-09 | 1996-10-17 | Jonas Konrad H | Device for merging at least two flow media |
| US5476889A (en) * | 1995-01-05 | 1995-12-19 | Minnesota Mining And Manufacturing Company | Curable sealer and/or adhesive composition, and a method for coating same in a dry state with automotive paint, and coated substrates formed therewith |
| DE19517452A1 (en) * | 1995-05-12 | 1996-11-14 | Henkel Teroson Gmbh | Two-component adhesive / sealant with high initial adhesion |
| DE19730424A1 (en) * | 1997-07-16 | 1999-01-21 | Henkel Teroson Gmbh | Device for storing and squeezing flowable compositions |
| DE202004020308U1 (en) | 2004-12-20 | 2005-04-07 | Pichler Gabriel | Seal for a building gap comprises an insulating material in the form of a polymer foam, and a sealing material which prevents vapor diffusion and has an elasticity equal to or greater than that of the insulating material |
| EP1882469A1 (en) | 2006-07-28 | 2008-01-30 | 3M Innovative Properties Company | Polyether-based preparations and use thereof |
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|---|---|---|---|---|
| JPS59217757A (en) * | 1983-05-24 | 1984-12-07 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing composition |
| EP0326862A2 (en) * | 1988-01-21 | 1989-08-09 | Kanegafuchi Chemical Industry Co., Ltd. | Curable polymer composition |
| WO1991011467A1 (en) * | 1990-01-26 | 1991-08-08 | Isp Investments Inc. | Alkenyl ethers and radiation curable compositions |
| JPH1188556A (en) * | 1993-05-10 | 1999-03-30 | Roehm Properties Bv | Communicator and software distribution system using the communicator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3971751A (en) * | 1975-06-09 | 1976-07-27 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Vulcanizable silylether terminated polymer |
| US4657959A (en) * | 1985-11-15 | 1987-04-14 | Minnesota Mining And Manufacturing Company | Hydrophilic silicones |
| DE3816808C1 (en) * | 1988-05-14 | 1989-10-26 | Teroson Gmbh, 6900 Heidelberg, De |
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1991
- 1991-06-13 DE DE19914119484 patent/DE4119484C2/en not_active Expired - Fee Related
-
1992
- 1992-05-31 WO PCT/EP1992/001194 patent/WO1992022609A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59217757A (en) * | 1983-05-24 | 1984-12-07 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing composition |
| EP0326862A2 (en) * | 1988-01-21 | 1989-08-09 | Kanegafuchi Chemical Industry Co., Ltd. | Curable polymer composition |
| WO1991011467A1 (en) * | 1990-01-26 | 1991-08-08 | Isp Investments Inc. | Alkenyl ethers and radiation curable compositions |
| JPH1188556A (en) * | 1993-05-10 | 1999-03-30 | Roehm Properties Bv | Communicator and software distribution system using the communicator |
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| Title |
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| PATENT ABSTRACTS OF JAPAN vol. 13, no. 479 (C-648)(3827) 30. Oktober 1989 & JP,A,11 88 556 ( ASAHI GLASS CO LTD ) 27. Juli 1989 * |
| PATENT ABSTRACTS OF JAPAN vol. 9, no. 88 (C-276)(1811) 17. April 1985 & JP,A,59 217 757 ( KANEGAFUCHI ) 7. Dezember 1984 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1179571A4 (en) * | 1999-03-23 | 2002-06-05 | Kaneka Corp | Curable resin compositions |
| US6569980B1 (en) | 1999-03-23 | 2003-05-27 | Kaneka Corporation | Curable resin compositions |
| EP1650261A4 (en) * | 2003-07-18 | 2008-02-27 | Kaneka Corp | Curable composition |
| JP2007530725A (en) * | 2004-03-23 | 2007-11-01 | シーカ・テクノロジー・アーゲー | Use of a two-component adhesion promoter composition and a package with two compartments |
| JP2012188665A (en) * | 2004-03-23 | 2012-10-04 | Sika Technology Ag | Two-component adhesion promoter composition and use of package comprising two compartments |
| JP2007070629A (en) * | 2005-09-02 | 2007-03-22 | Sika Technology Ag | Aqueous two-component organic alkoxysilane composition |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4119484C2 (en) | 1993-12-23 |
| DE4119484A1 (en) | 1992-12-17 |
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