EP1406960A1 - Adhesion promoter for plastisols - Google Patents

Adhesion promoter for plastisols

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Publication number
EP1406960A1
EP1406960A1 EP02751035A EP02751035A EP1406960A1 EP 1406960 A1 EP1406960 A1 EP 1406960A1 EP 02751035 A EP02751035 A EP 02751035A EP 02751035 A EP02751035 A EP 02751035A EP 1406960 A1 EP1406960 A1 EP 1406960A1
Authority
EP
European Patent Office
Prior art keywords
plastisols
plastisol
meth
additives
copolymers
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.)
Withdrawn
Application number
EP02751035A
Other languages
German (de)
French (fr)
Inventor
Günter Butschbacher
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
Original Assignee
Henkel Teroson GmbH
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Filing date
Publication date
Application filed by Henkel Teroson GmbH filed Critical Henkel Teroson GmbH
Publication of EP1406960A1 publication Critical patent/EP1406960A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to plastisol compositions based on powdery organic polymers and plasticizers and adhesion-promoting additives.
  • Plastisols are generally understood to mean dispersions of organic plastics in plasticizers which gel when heated to a higher temperature and harden when cooled.
  • the plastisols commonly used in practice today mostly contain fine powder homo- or copolymers of vinyl chloride which are dispersed in a liquid plasticizer and form a paste.
  • Such polyvinyl chloride plastisols (PVC plastisols) are used for a wide variety of purposes. They are used, among other things, as sealing compounds, e.g. for seam seals in metal containers or as flanged seam adhesives in the metal industry, as corrosion protection coatings for metals (e.g. as underbody protection for motor vehicles), for impregnating and coating substrates made of textile materials (e.g.
  • Plastisols based on finely powdered methacrylate copolymers (PMMA) or styrene copolymers have also become known.
  • PMMA finely powdered methacrylate copolymers
  • styrene copolymers styrene copolymers
  • Such plastisols are also used extensively in body-in-white construction in the automotive industry.
  • stiffening structures such as bonnets, trunk lids, doors, roof structures, as well as for flanged seam bonding and for sealing seams from other joining processes.
  • Advantageous when using plastisols for these purposes are their favorable flow behavior, especially at room temperature.
  • these plastisol compositions are often gelled in a pre-gelling process to such an extent that their viscosity is high enough to ensure this laundry resistance and an initial strength of the components .
  • additional additives are added to the plastisols.
  • additives are, for example, rheology aids, stabilizers, adhesion promoters, fillers, pigments, blowing agents, reactive (crosslinkable) additives and water-absorbing substances.
  • Adhesion promoters are added to the plastisols in order to ensure long-term adhesion of the plastisols to steel, aluminum or galvanized and / or electrocoated or otherwise pretreated metal sheets.
  • basic compounds such as polyaminoamides (PAA) are used as adhesion promoters for PVC plastisols.
  • PAA polyaminoamides
  • polymethacrylate plastisols basic vinylimidazoles are usually used as adhesion promoters, which are copolymerized as comonomers.
  • polyaminoamides are added to these PMMA plastisols as an additional adhesion promoter component.
  • Other additives for plastisols are also known.
  • GB-A-1193896 describes a PVC plastisol which contains an epoxy resin and dicyandiamide and ⁇ -benzyldimethyldiamine as adhesion-promoting substances.
  • DE-A-2642514 proposes adding Schiff bases and / or enamines based on polyaminoamides and epoxy resins to the PVC pastisols in order to improve their adhesion to metallic substrates.
  • polyaminoamides and their derivatives and reaction products as adhesion promoters for plastisols, in particular PVC - plastisols is also the subject of a large number of patent applications, examples of which are DE-A-2906134, DE-A-3111815, DE-A-3201265, EP-A - 171850 or EP-A-263053.
  • US-A-5039768 proposes the use of organosilanes, acrylate monomers, and unsaturated carboxylic acid monomers and epoxy resins with hardeners as adhesion-promoting additives for PVC plastisols.
  • the EP A-343101 proposes the addition of anhydride compounds and epoxy resins to PVC plastisols in order to improve the adhesion.
  • EP-A-533026 proposes copolymers of methyl methacrylate with comonomers containing carboxyl or anhydride groups as adhesion promoters for acrylate plastisols, which may optionally contain polyaminoamide additives.
  • EP-A-209653 proposes reaction products of epoxy resins and low molecular weight aliphatic polyamines, in particular ethylenediamine, as adhesion-promoting additives to plastisols, in particular to plastisols based on methyl methacrylate copolymers.
  • Polyvinyl chloride (PVC), vinyl chloride copolymers with vinyl acetate, styrene and / or alkyl (meth) acrylates, copolymers of styrene with (meth) acrylic acid, (meth) acrylamide and / or alkyl (meth) acrylates or else copolymers can preferably be used as powdered organic polymers of methyl or ethyl methacrylate with C 3 to C 8 alkyl (meth) acrylates or Alkyl (meth) acrylate homopolymers or mixtures of the aforementioned polymers can be used.
  • the mono-, di- or oligosaccharides are preferably used as finely divided powders, the average particle size should be between 1 and 100 ⁇ m, preferably it should be between 1 and 20 ⁇ m. It may be expedient to grind the commercially available powdered saccharides more finely, for this purpose, in particular, they can be pasted with the plasticizer to be used in the plastisol, this paste then being rubbed off with conventional colloid mills or on a roller, so that the desired average particle size of the saccharide is achieved becomes.
  • plasticizers are generally suitable as plasticizers (see, for example, Paul E. Bruins, Plasticizer Technology [Reinhold Publ. Corp., New York], Vol. 1, pp. 228-232).
  • C 4 to C 16 alkyl phthalates such as dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, benzyl butyl phthalate, dibenzyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and diundecyl phthalate (DIUP) are preferred.
  • plasticizers from the group of organic phosphates, adipates and sebacates or also benzyl benzoate and other benzoate plasticizers, alkyl sulfonic acid esters of phenol or cresol, dibenzyl toluene or diphenyl ether are also suitable.
  • the selection criteria for the preferred plasticizers depend on the one hand on the polymer composition and on the other hand on viscosity, Gelling conditions of the plastisol and the desired acoustic properties of a plastisol-coated composite.
  • the plastisols according to the invention can contain further reactive additives, for example di- or polyisocyanates, these preferably being blocked or microencapsulated, and also di- or polyamines or polyaminoamides based on polyamines and dimerized or polymerized fatty acids and / or hydroxy-functional compounds, such as eg Polyester polyols or polyether polyols.
  • further examples of reactive additives are combinations of di- or polyepoxy compounds in combination with di- or polyamines or polyaminoamides.
  • Plastisol compositions belong to the fact that the addition of the monomeric (meth) acrylates in combination with peroxides often leads to storage stability problems. In addition, the low-temperature flexibility of such compositions is often unsatisfactory because of the high degree of crosslinking. Furthermore, carboxylic acid derivatives, in particular dicarboxylic acids, di- or tricarboxylic acid anhydrides, can be added to the plastisols according to the invention as reactive additives.
  • adipic acid pimelic acid anhydride, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, phthalic acid, maleic anhydride, succinic anhydride, 1, 2,3-Propantricarbon Textre-, phthalic anhydride, anhydrides of the isomeric Benzoltribarbon Acid, pyromellitic anhydride, methyl-hexahydrophthalic anhydride, and similar common carboxylic acids or their anhydrides.
  • ⁇ -dicarbonyl compounds such as, for example, acetylacetone, acetoacetic ester, dialkyl malonates, benzoyl acetate or corresponding metal chelates such as, for example, zinc acetylacetonate can also be added.
  • the reactive additives are usually used in amounts between 0.01 and 4% by weight, preferably between 0.1 and 20% by weight, based on the entire plastisol formulation.
  • the plastisols according to the invention can optionally contain further auxiliaries and additives, as are customary in plastisol technology.
  • auxiliaries and additives include e.g. Color pigments, anti-aging agents, rheology aids and blowing agents for the production of foamed plastisols.
  • common additives include, for example, epoxy plasticizers, preferably epoxidized natural oils such as epoxidized soybean oil, epoxidized linseed oil or epoxidized tall oils.
  • epoxy plasticizers are used in small quantities, in particular in PVC plastisols, as heat stabilizers.
  • the plastisols can also contain the usual anti-aging agents and stabilizers, rheology aids such as e.g. contain fumed silicas, bentones, castor oil derivatives.
  • fillers which are common and known per se in plastisol technology can be used as fillers.
  • suitable fillers are limestone powder, natural, ground chalk (calcium carbonate or calcium magnesium carbonate), precipitated chalk, heavy spar, talc, mica, clays, pigments such as e.g. Titanium dioxide, carbon black, iron oxides.
  • the powdery saccharides can be used in very high proportions in the plastisols according to the invention and thus replace some of the fillers. Therefore, the saccharides can make up up to 50% by weight of the total formulation. Many formulations contain between 3 and 10 or 20% by weight saccharide.
  • so-called “light fillers” of organic or inorganic composition can also be used, these include, for example, hollow glass spheres, fly ash (“fillite”) and organic hollow microspheres based on epoxy resins or phenolic resins.
  • conductivity-imparting pigments such as special carbon blacks, graphite or antimony-doped silicates can be added. This is particularly necessary if the plastisols are applied to the shell and then electrophoretically deposited lacquer layers are to be applied to these plastisol layers.
  • blowing agents are all blowing agents known per se, preferably organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonyl hydrazides or
  • Sulfonyl examples from the class of azo compounds are azobis-isobutyronitrile and in particular azodicarbonamide, from the class of nitroso compounds the di-nitrosopentamethylenetetramine should be mentioned, from the class of sulfohydrazides 4,4'-oxybis (benzenesulfonic acid hydrazide) and from the class of Semicarbazide called the p-toluenesulfonylsemicarbazid.
  • microspheres can either be added directly to the plastisol in the pre-expanded form as hollow microspheres or, in a particularly preferred manner, the "hollow microspheres" are added to the plastisol as finely divided powder in the unfoamed form. These unfoamed "hollow micro spheres" only expand when the plastisol is gelled and thus result in a very uniform and fine-pored foaming.
  • the hollow microspheres contain a liquid blowing agent based on aliphatic hydrocarbons or fluorocarbons as the core and a shell made of a copolymer of acrylonitrile with vinylidene chloride and / or methyl methacrylate and / or methacrylonitrile.
  • a liquid blowing agent based on aliphatic hydrocarbons or fluorocarbons as the core and a shell made of a copolymer of acrylonitrile with vinylidene chloride and / or methyl methacrylate and / or methacrylonitrile.
  • the plastic gel in particular the abrasion resistance
  • a compound which reacts at the gelation temperature with the carboxyl groups of the optionally present copolymers with crosslinking in an amount of up to 40% by weight
  • Long-chain epoxy compounds, epoxidized polybutadienes or also epoxidized natural oils such as epoxidized soybean oil or solid, powdered epoxy derivatives are particularly suitable for a reaction with the carboxyl groups present.
  • Liquid hydroxy-functional polybutadienes or mercaptan-terminated liquid polymers can also be used instead of or in combination with polypropylene glycols.
  • ester bonds between these compounds and the carboxyl groups of the copolymer generally takes place when the plastisol is heated to the setting temperature.
  • suitable catalysts can be added in an amount of about 0.01 to 2.0% by weight, for example imidazole or substituted imidazoles such as N-alkylimidazoles, for example N-methylimidazole, tertiary amines, tetramethylene diamine or urea derivatives, if appropriate precipitated on inert fillers.
  • Alkylbenzenesulfonic acids and titanates are also suitable as catalysts for the ester formation with glycols.
  • amino and / or amido-functional compounds and / or blocked polyurethanes can be added individually or in combination to the plastisols according to the invention, as are known from the PVC plastisol technology as adhesion promoters, they bring about a considerable improvement in the abrasion resistance.
  • examples of such compounds are the well known polyaminoamides based on dimerized fatty acids and low molecular weight di or polyamines, e.g. are known under the trade names Versamid 115, 125 or 140 and / or amino-functional condensation products from epoxides based on the bisglycidyl ether of bisphenol A with diamines or polyamines such as e.g. Ethylenediamine, propylenediamine, etc.
  • the isocyanate prepolymers preferably contain blocked isocyanate groups, for example isocyanate groups blocked by caprolactam, or they are in the form of solid, microencapsulated or surface-deactivated isocyanate compounds as a dispersion in the liquid phase.
  • isocyanate derivatives can be present in an amount of up to 30% by weight of the total formulation, the (cyclo) aliphatic diamines can be up to 5% by weight in the case of low molecular weight amines up to a molecular weight of about 500 and up to 30% by weight in the case of higher molecular weight diamines. make up the overall wording.
  • the plastisol polymer may form an IPN structure (Interpenetrating Polymer Network).
  • the plastisols according to the invention can contain further reactive additives to improve the mechanical properties. These depend on the crosslinking comonomer used.
  • di- or polyisocyanates can be added, the latter preferably being blocked or microencapsulated; in the case of epoxy-functional comonomers, di- or polyamines or polyaminoamides are preferably added; in the case of (blocked) isocyanate-functional comonomers, amino- and / or hydroxy-functional additives can be used. If appropriate, these crosslinking reactions can be accelerated by catalysts known per se.
  • the plastisol compositions contain:
  • saccharides as an adhesion-promoting additive has the following advantages over the known prior art: improved resistance to aging, especially after
  • the plastisol compositions according to the invention have good adhesion properties on a wide variety of substrates such as steel, electrolytically galvanized steel, hot-dip galvanized steel or organically coated steel ("Granocoat” or "Bonazink”). According to the current state of the art, aging-resistant adhesion and good corrosion protection were only possible by adding - often containing heavy metals - corrosion protection pigments and / or corrosion inhibitors.
  • the plastisols according to the invention are suitable as adhesives, in particular as so-called structural adhesives, but also for underbody protection, for seam sealing, for relining engine hoods, trunk lids, doors or, if pre-gelling is used, also as a roof bow.
  • the plastisols according to the invention are suitable for seam sealing, as a flanged seam adhesive, for flared seam sealing or as a spot welding paste. Because of the good adhesive properties on a large number of substrates, the plastisols according to the invention can therefore be used both in body-in-white, as well as in the lacquer area or in the trim area in the manufacture of automobiles. Underbody application on raw sheet metal is also possible.
  • Flare seam adhesive and flare seam sealing based on a PVC plastisol In the following case, a basic approach according to the state of the art used corrosion protection pigment or powdered sugar according to the invention:
  • Example 3 (According to the invention) commercially available underbody protection to which 10% cane sugar was added.
  • Example 4 (Comparison) standard underbody protection.
  • example 2 according to the invention shows good results in all layer thicknesses of the coating after short-term gelation at high temperatures, followed by moisture storage. In no case blistering is observed in the coating, whereas blistering is frequently observed with the adhesive according to the prior art.
  • the strontium-containing corrosion protection pigment can be dispensed with in the example according to the invention.
  • Example 3 shows an underbody protection which contains sucrose in large amounts, partly as a filler, so that the proportion of specifically heavy calcium carbonate could be drastically reduced. This enables a specifically light underbody protection which is absolutely equal in its adhesion behavior to a specifically heavier commercially available underbody protection with a high proportion of calcium carbonate (example 4).
  • the underbody protection according to the invention based on PMMA of Example 5 results in a specifically particularly light underbody protection, since it was also possible to dispense with the addition of calcium carbonate as a filler.
  • the abrasion resistance of the underbody protection according to the invention according to Example 5 is even better than that of Comparative Example 6 according to the prior art.
  • sucrose in plastisol adhesives or sealants and underbody protection compositions enables the formulation of plastisols with very good properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to plastisols that have good adhesive properties with a large number of substrates used in the automotive industry. The inventive plastisols are obtained by adding pulverulent monosaccharides, disaccharides or oligosaccharides to plastisols on the basis of pulverulent organic polymers and plasticizers. The inventive plastisols are characterized by a good adhesive behavior and excellent aging stability and can be used in the automotive industry both in the body construction as well as in the enameling line and in the trim shop as adhesive, sealing or coating agents.

Description

"Haftvermittler für Plastisole" "Adhesion promoter for plastisols"
Die Erfindung betrifft Plastisol - Zusammensetzungen auf der Basis von pulverförmigen organischen Polymeren und Weichmachern und haftvermittelnden Zusätzen.The invention relates to plastisol compositions based on powdery organic polymers and plasticizers and adhesion-promoting additives.
Unter Plastisolen werden allgemein Dispersionen von organischen Kunststoffen in Weichmachern verstanden, welche beim Erwärmen auf höhere Temperatur gelieren und beim Abkühlen aushärten. Die in der Praxis heute gebräuchlichen Plastisole enthalten ganz überwiegend feinpulvrige Homo- oder Copolymere des Vinylchlorids, die in einem flüssigen Weichmacher dispergiert sind und eine Paste bilden. Derartige Polyvinylchloridplastisole (PVC-Plastisole) finden für die verschiedensten Zwecke Anwendung. Sie werden u.a. als Dichtungsmassen, z.B. für Nahtabdichtungen bei Metallbehältern oder als Bördelnahtkleber in der Metallindustrie, als Korrosionsschutzüberzüge für Metalle (beispielsweise als Unterbodenschutz für Kraftfahrzeuge), zum Imprägnieren und Beschichten von Substraten aus textilen Materialien (z.B. als Teppichrückseitenbeschichtung), als Kabelisolierungen usw. eingesetzt). Es sind auch Plastisole auf der Basis von feinpulvrigen Methacrylatcopolymeren (PMMA) oder Styrolcopolymeren bekannt geworden. Derartige Plastisole, insbesondere auf Basis von PVC oder PMMA werden auch im Rohbau im Automobilbau in umfangreichem Masse eingesetzt. Zur Unterfütterung von versteifenden Strukturen wie Motorhauben, Kofferraumdeckeln, Türen, Dachkonstruktionen sowie zur Bördelnahtverklebung und zur Versiegelung von Nähten aus anderweitigen Fügungsverfahren. Vorteilhaft bei der Verwendung von Plastisolen für diese Anwendungszwecke sind deren günstiges Fließverhalten, insbesondere bei Raumtemperatur. Um die Wäscherbeständigkeit in den diversen Reinigungs-, Phosphatier- und Tauchgrundierungsstufen bei der Fertigung der Automobilkarossen zu gewährleisten, werden diese Plastisol - Zusammensetzungen häufig in einem Vorgelierungsprozess soweit angeliert, daß ihre Viskosität hoch genug ist, um diese Wäscherbeständigkeit und eine Anfangsfestigkeit der Bauteile zu gewährleisten. Den Plastisolen werden je nach Anwendungszweck weitere Zuschlagstoffe zugesetzt. Derartige Zuschlagstoffe sind beispielsweise Rheologiehilfsmittel, Stabilisatoren, Haftvermittler, Füllstoffe, Pigmente, Treibmittel, reaktive (vernetzungsfähige) Zusätze und wasserabsorbierende Substanzen. Haftvermittler werden den Plastisolen zugesetzt, um eine Langzeithaftung der Plastisole auf Stahl, Aluminium oder verzinkten und /oder elektrotauchlackierten oder anderweitig vorbehandelten Blechen zu bewirken. Als Haftvermittler für PVC- Plastisole werden beispielsweise basische Verbindungen wie Polyaminoamide (PAA) verwendet. Für Polymethacrylat-Plastisole werden als Haftvermittler üblicherweise basische Vinylimidazole verwendet, die als Comonomer einpolymerisiert sind. Diesen PMMA-Plastisolen sind gegebenenfalls Polyaminoamide als zusätzliche Haftvermittlerkomponente zugesetzt. Andere Haftvermittler-Zusätze für Plastisole sind ebenfalls bekannt.Plastisols are generally understood to mean dispersions of organic plastics in plasticizers which gel when heated to a higher temperature and harden when cooled. The plastisols commonly used in practice today mostly contain fine powder homo- or copolymers of vinyl chloride which are dispersed in a liquid plasticizer and form a paste. Such polyvinyl chloride plastisols (PVC plastisols) are used for a wide variety of purposes. They are used, among other things, as sealing compounds, e.g. for seam seals in metal containers or as flanged seam adhesives in the metal industry, as corrosion protection coatings for metals (e.g. as underbody protection for motor vehicles), for impregnating and coating substrates made of textile materials (e.g. as carpet backing), as cable insulation, etc. ). Plastisols based on finely powdered methacrylate copolymers (PMMA) or styrene copolymers have also become known. Such plastisols, in particular those based on PVC or PMMA, are also used extensively in body-in-white construction in the automotive industry. For relining stiffening structures such as bonnets, trunk lids, doors, roof structures, as well as for flanged seam bonding and for sealing seams from other joining processes. Advantageous when using plastisols for these purposes are their favorable flow behavior, especially at room temperature. In order to ensure the laundry resistance in the various cleaning, phosphating and immersion priming stages in the manufacture of the automobile bodies, these plastisol compositions are often gelled in a pre-gelling process to such an extent that their viscosity is high enough to ensure this laundry resistance and an initial strength of the components , Depending on the application, additional additives are added to the plastisols. Such additives are, for example, rheology aids, stabilizers, adhesion promoters, fillers, pigments, blowing agents, reactive (crosslinkable) additives and water-absorbing substances. Adhesion promoters are added to the plastisols in order to ensure long-term adhesion of the plastisols to steel, aluminum or galvanized and / or electrocoated or otherwise pretreated metal sheets. For example, basic compounds such as polyaminoamides (PAA) are used as adhesion promoters for PVC plastisols. For polymethacrylate plastisols, basic vinylimidazoles are usually used as adhesion promoters, which are copolymerized as comonomers. If appropriate, polyaminoamides are added to these PMMA plastisols as an additional adhesion promoter component. Other additives for plastisols are also known.
So beschreibt die GB - A - 1193896 ein PVC - Plastisol, das ein Epoxyharz und Dicyandiamid sowie α- Benzyldimethyldiamin als haftvermittelnde Substanzen enthält. In der DE - A - 2642514 wird vorgeschlagen, Schiff- Basen und / oder Enamine auf der Basis von Polyaminoamiden und Epoxyharze den PVC- Pastisolen zuzufügen um deren Haftung auf metallischen Substraten zu verbessern. Die Verwendung von Polyaminoamiden sowie deren Derivate und Umsetzungsprodukte als Haftvermittler für Plastisole, insbesondere PVC - Plastisole ist weiterhin Gegenstand einer Vielzahl von Patentanmeldungen, beispielhaft genannt seien DE-A-2906134, DE-A-3111815, DE-A-3201265, EP-A- 171850 oder EP-A-263053.GB-A-1193896 describes a PVC plastisol which contains an epoxy resin and dicyandiamide and α-benzyldimethyldiamine as adhesion-promoting substances. DE-A-2642514 proposes adding Schiff bases and / or enamines based on polyaminoamides and epoxy resins to the PVC pastisols in order to improve their adhesion to metallic substrates. The use of polyaminoamides and their derivatives and reaction products as adhesion promoters for plastisols, in particular PVC - plastisols is also the subject of a large number of patent applications, examples of which are DE-A-2906134, DE-A-3111815, DE-A-3201265, EP-A - 171850 or EP-A-263053.
Weiterhin wird die Verwendung von blockierten Diisocyanatpolymeren entweder alleine oder in Kombination mit Amin-Derivaten oder Polyaminoamidderivaten als haftvermittelnde Substanzen für Plastisole vorgeschlagen, beispielhaft erwähnt seien die EP-A-214495 oder US-A-5130402.Furthermore, the use of blocked diisocyanate polymers either alone or in combination with amine derivatives or polyaminoamide derivatives is proposed as adhesion-promoting substances for plastisols. Examples include EP-A-214495 or US-A-5130402.
In der US-A-5039768 wird die Verwendung von Organosilanen, Acrylat- Monomeren, sowie ungesättigten Carbonsäuremonomeren und Epoxyharzen mit Härtern als haftvermittelnde Zusätze zu PVC-Plastisolen vorgeschlagen. Die EP- A-343101 schlägt den Zusatz von Anhydridverbindungen und Epoxyharzen zu PVC-Plastisolen vor, um dadurch die Haftung zu verbessern. In ähnlicher Weise schlägt die EP-A-533026 Copolymere von Methyl methacrylat mit Carboxyl- oder Anhydridgruppen -haltigen Comonomeren als Haftvermittler für Acrylatplastisole vor, die ggf. Polyaminoamidzusätze enthalten können. Die EP-A-209653 schlägt Umsetzungsprodukte aus Epoxyharzen und niedermolekularen aliphatischen Polyaminen, insbesondere Ethylendiamin als haftvermittlnde Zusätze zu Plastisolen vor, insbesondere zu Plastisolen auf der Basis von Methylmethacrylat- Copolymeren.US-A-5039768 proposes the use of organosilanes, acrylate monomers, and unsaturated carboxylic acid monomers and epoxy resins with hardeners as adhesion-promoting additives for PVC plastisols. The EP A-343101 proposes the addition of anhydride compounds and epoxy resins to PVC plastisols in order to improve the adhesion. Similarly, EP-A-533026 proposes copolymers of methyl methacrylate with comonomers containing carboxyl or anhydride groups as adhesion promoters for acrylate plastisols, which may optionally contain polyaminoamide additives. EP-A-209653 proposes reaction products of epoxy resins and low molecular weight aliphatic polyamines, in particular ethylenediamine, as adhesion-promoting additives to plastisols, in particular to plastisols based on methyl methacrylate copolymers.
Trotz einer Vielzahl von Lösungsvorschlägen zur Erzielung von guter Haftung von Plastisol - Zusammensetzungen auf den verschiedensten Substraten, insbesondere metallischen Substraten, ist es wünschenswert, möglichst kostengünstig eine dauerhafte und alterungsbeständige Haftung von Plastisolen zu erzielen, die verlässlich als Bördelnahtklebstoff, Unterfütterungsklebstoff, Nahtabdichtung, als Punktschweißpaste oder auch als Beschichtungsmasse, ggf. mit akustischen Eigenschaften, einsetzbar sind. Die so eingesetzten Produkte sollen hohe Anforderungen an den Korrosionsschutz erfüllen. Der Erfindung liegt daher die Aufgabe zugrunde, kostengünstige, leicht verfügbare haftvermittelnde Zusätze für Plastisole zur Verfügung zu stellen, die den heutigen Anforderungen an Korrosionsschutz im Automobilbau genügen.Despite a large number of proposed solutions for achieving good adhesion of plastisol compositions on a wide variety of substrates, in particular metallic substrates, it is desirable to achieve permanent and aging-resistant adhesion of plastisols as cost-effectively as possible, which can be used reliably as a crimp seam adhesive, relining adhesive, seam sealant, as spot welding paste or can also be used as a coating compound, possibly with acoustic properties. The products used in this way should meet high requirements for corrosion protection. The invention is therefore based on the object of providing inexpensive, readily available adhesion-promoting additives for plastisols which meet today's requirements for corrosion protection in automobile construction.
Die erfindungsgemäße Lösung der Aufgabe ist den Patentansprüchen zu entnehmen, sie besteht im wesentlichen darin, Plastisol - Zusammensetzungen auf der Basis von pulverförmigen organischen Polymeren und Weichmachern bereitzustellen, die pulverförmige Monosaccharide, Disaccharide oder Oligosaccharide enthalten.The solution to the problem according to the invention can be gathered from the patent claims; it essentially consists in providing plastisol compositions based on powdered organic polymers and plasticizers which contain powdered monosaccharides, disaccharides or oligosaccharides.
Als pulverförmige organische Polymere können dabei bevorzugterweise Polyvinylchlorid (PVC), Vinylchloridcopolymere mit Vinylacetat, Styrol und / oder Alkyl(meth)acrylaten, Copolymere des Styrols mit (Meth)acrylsäure, (Meth)acrylamid und / oder Alkyl(meth)acrylaten oder auch Copolymere des Methyl- oder Ethylmethacrylates mit C3-bis C8- Alkyl(meth)acrylaten oder Alkyl(meth)acrylathomopoIymere oder Mischungen der vorgenannten Polymere eingesetzt werden.Polyvinyl chloride (PVC), vinyl chloride copolymers with vinyl acetate, styrene and / or alkyl (meth) acrylates, copolymers of styrene with (meth) acrylic acid, (meth) acrylamide and / or alkyl (meth) acrylates or else copolymers can preferably be used as powdered organic polymers of methyl or ethyl methacrylate with C 3 to C 8 alkyl (meth) acrylates or Alkyl (meth) acrylate homopolymers or mixtures of the aforementioned polymers can be used.
Als Monosaccharide, Disaccharide oder Oligosaccharide können Glucose, Galactose, Mannose, Fructose, Arabinose, Xylose, Ribose, 2-Desoxy-ribose, Cellobiose, Maltose (Malzzucker), Lactose (Milchzucker), Saccharose (Rohrzucker) - letzterer ist wegen seiner besonders guten Verfügbarkeit und seines niedrigen Preises besonders bevorzugt, Gentiobiose, Melibiose, Trehalose, Turanose, Gentianose, Kestose, Maltotriose, Melecitose, Raffinose, Stachyose, Lychnose, Secalose, oder deren Mischungen eingesetzt werden.As monosaccharides, disaccharides or oligosaccharides, glucose, galactose, mannose, fructose, arabinose, xylose, ribose, 2-deoxy-ribose, cellobiose, maltose (malt sugar), lactose (milk sugar), sucrose (cane sugar) - the latter is particularly good Availability and its low price particularly preferred, Gentiobiose, Melibiose, Trehalose, Turanose, Gentianose, Kestose, Maltotriose, Melecitose, Raffinose, Stachyose, Lychnose, Secalose, or mixtures thereof are used.
Vorzugsweise werden die Mono-, Di- oder Oligosaccaride als feinteilige Pulver eingesetzt, die mittlere Teilchengröße sollte zwischen 1 und 100 μm liegen, vorzugsweise sollte sie zwischen 1 und 20 μm betragen. Es kann zweckmäßig sein, die handelsüblichen pulverförmigen Saccaride feiner zu mahlen, hierzu bietet sich insbesondere deren Anpastung mit dem im Plastsisol einzusetzenden Weichmacher an, wobei diese Paste anschließend mit herkömmlichen Kolloidmühlen oder auf einer Walze abgerieben werden, so daß die gewünschte mittlere Teilchengröße des Saccarides erreicht wird.The mono-, di- or oligosaccharides are preferably used as finely divided powders, the average particle size should be between 1 and 100 μm, preferably it should be between 1 and 20 μm. It may be expedient to grind the commercially available powdered saccharides more finely, for this purpose, in particular, they can be pasted with the plasticizer to be used in the plastisol, this paste then being rubbed off with conventional colloid mills or on a roller, so that the desired average particle size of the saccharide is achieved becomes.
Als Weichmacher sind in der Regel alle herkömmlichen Weichmacher geeignet (vergleiche hierzu z.B. Paul E. Bruins, Plasticizer Technology [Reinhold Publ. Corp., New York], Bd. 1 , S. 228-232). Bevorzugt werden C4- bis C16-Alkylphthalate wie Dibutylphthalat, Dioctylphthalat, Diheptylphthalat, Benzylbutylphthalat, Dibenzylphthalat, Diisononylphthalat (DINP), Diisodecylphthalat (DIDP) sowie Diundecylphthalat (DIUP). Geeignet sind jedoch auch die bekannten Weichmacher aus der Gruppe der organischen Phosphate, Adipate und Sebacate oder auch Benzylbenzoat und andere Benzoatweichmacher, Alkylsulfonsäureester des Phenols bzw. Kresols, Dibenzyltoluol oder Di-phenylether. Die Auswahlkriterien für die bevorzugt verwendeten Weichmacher richten sich zum einen nach der Polymerzusammensetzung sowie zum anderen nach Viskosität, Gelierbedingungen des Plastisols sowie den gewünschten akustischen Eigenschaften eines plastisolbeschichteten Verbundes.All conventional plasticizers are generally suitable as plasticizers (see, for example, Paul E. Bruins, Plasticizer Technology [Reinhold Publ. Corp., New York], Vol. 1, pp. 228-232). C 4 to C 16 alkyl phthalates such as dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, benzyl butyl phthalate, dibenzyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and diundecyl phthalate (DIUP) are preferred. However, the known plasticizers from the group of organic phosphates, adipates and sebacates or also benzyl benzoate and other benzoate plasticizers, alkyl sulfonic acid esters of phenol or cresol, dibenzyl toluene or diphenyl ether are also suitable. The selection criteria for the preferred plasticizers depend on the one hand on the polymer composition and on the other hand on viscosity, Gelling conditions of the plastisol and the desired acoustic properties of a plastisol-coated composite.
Die erfindungsgemäßen Plastisole können weitere reaktive Zusätze enthalten, wie zum Beispiel Di- oder Polyisocyanate, wobei diese vorzugsweise blockiert oder mikroverkapselt sind, sowie Di- oder Polyamine oder Polyaminoamide auf der Basis von Polyaminen und dimerisierten bzw. polymerisierten Fettsäuren und/oder hydroxyfunktionelle Verbindungen, wie z.B. Polyesterpolyole oder Polyetherpolyole. Weitere Beispiele für reaktive Zusätze sind Kombinationen von Di- oder Polyepoxyverbindungen in Kombination mit Di- oder Polyaminen oder Polyaminoamiden. Auch der Zusatz von monomeren Mono-, Di- und/oder Trimethacrylaten bzw. -acrylaten oder Polyesterharzen, die ggf. olefinisch ungesättigte Doppelbindungen enthalten, in Kombination mit Peroxiden ist möglich, obwohl die Verwendung von (Meth)acrylatmonomeren nicht zu den bevorzugten Ausführungsformen der erfindungsgemäßenThe plastisols according to the invention can contain further reactive additives, for example di- or polyisocyanates, these preferably being blocked or microencapsulated, and also di- or polyamines or polyaminoamides based on polyamines and dimerized or polymerized fatty acids and / or hydroxy-functional compounds, such as eg Polyester polyols or polyether polyols. Further examples of reactive additives are combinations of di- or polyepoxy compounds in combination with di- or polyamines or polyaminoamides. It is also possible to add monomeric mono-, di- and / or trimethacrylates or -acrylates or polyester resins, which may contain olefinically unsaturated double bonds, in combination with peroxides, although the use of (meth) acrylate monomers is not one of the preferred embodiments of the invention
Plastisolzusammensetzungen gehört, da der Zusatz der monomeren (Meth)acrylate in Kombination mit Peroxiden häufig zu Lagerstabilitätsproblemen führt, außerdem ist die Kälteflexibilität derartiger Zusammensetzungen wegen des hohen Vernetzungsgrades vielfach unbefriedigend. Weiterhin können den erfindungsgemäßen Plastisolen als reaktive Zusätze Carbonsäurederivate insbesondere Dicarbonsäuren, Di- oder Tricarbonsäureanhydride zugesetzt werden. Konkrete Beispiele sind Adipinsäure, Pimelinsäure, Korksäure, Acelainsäure, Sebazinsäure, Undecandisäure, Dodecandisäure, Phthalsäure, Maleinsäureanhydrid, Bernsteinsäureanhydrid, 1 ,2,3-Propantricarbonsäure- anhydrid, Phthalsäureanhydrid, Anhydride der isomeren Benzoltribarbonsäuren, Pyromellitsäureanhydrid, Methyl-hexahydrophthalsäureanhydrid und ähnliche gängige Carbonsäuren bzw. deren Anhydride. Weiterhin können ß-Dicarbonyl- verbindungen wie z.B. Acetylaceton, Acetessigester, Dialkylmalonate, Benzoylessigester oder entsprechende Metallchelate wie z.B. Zinkacetylacetonat zugesetzt werden. Die reaktiven Zusätze werden üblicherweise in Mengen zwischen 0,01 und 4 Gew.%, vorzugsweise zwischen 0,1 und 20 Gew. %, bezogen auf die gesamte Plastisolformulierung, verwendet.Plastisol compositions belong to the fact that the addition of the monomeric (meth) acrylates in combination with peroxides often leads to storage stability problems. In addition, the low-temperature flexibility of such compositions is often unsatisfactory because of the high degree of crosslinking. Furthermore, carboxylic acid derivatives, in particular dicarboxylic acids, di- or tricarboxylic acid anhydrides, can be added to the plastisols according to the invention as reactive additives. Concrete examples are adipic acid, pimelic acid anhydride, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, phthalic acid, maleic anhydride, succinic anhydride, 1, 2,3-Propantricarbonsäure-, phthalic anhydride, anhydrides of the isomeric Benzoltribarbonsäuren, pyromellitic anhydride, methyl-hexahydrophthalic anhydride, and similar common carboxylic acids or their anhydrides. Β-dicarbonyl compounds such as, for example, acetylacetone, acetoacetic ester, dialkyl malonates, benzoyl acetate or corresponding metal chelates such as, for example, zinc acetylacetonate can also be added. The reactive additives are usually used in amounts between 0.01 and 4% by weight, preferably between 0.1 and 20% by weight, based on the entire plastisol formulation.
Außerdem können die erfindungsgemäßen Plastisole gegebenenfalls weitere Hilfs- und Zusatzstoffe, wie sie in der Plastisol-Technologie üblich sind, enthalten. Hierzu zählen z.B. Farbpigmente, Alterungsschutzmittel, Rheologie-Hilfsmittel sowie Treibmittel zur Herstellung von geschäumten Plastisolen. Zu diesen üblichen Zusatzstoffen zählen beispielsweise die Epoxidweichmacher, vorzugsweise epoxidierte natürliche öle wie das epoxidierte Sojabohnenöl, epoxidierte Leinöl oder epoxidierte Tallöle. Diese Epoxidweichmacher werden bekanntermaßen in geringen Mengen insbesondere in PVC-Plastisolen als Hitzestabilisatoren verwendet. Die Plastisole können weiterhin die üblichen Alterungsschutzmittel und Stabilisatoren, Rheologie-Hilfsmittel wie z.B. pyrogene Kieselsäuren, Bentone, Rizinusöl-Derivate enthalten.In addition, the plastisols according to the invention can optionally contain further auxiliaries and additives, as are customary in plastisol technology. These include e.g. Color pigments, anti-aging agents, rheology aids and blowing agents for the production of foamed plastisols. These common additives include, for example, epoxy plasticizers, preferably epoxidized natural oils such as epoxidized soybean oil, epoxidized linseed oil or epoxidized tall oils. As is known, these epoxy plasticizers are used in small quantities, in particular in PVC plastisols, as heat stabilizers. The plastisols can also contain the usual anti-aging agents and stabilizers, rheology aids such as e.g. contain fumed silicas, bentones, castor oil derivatives.
Als Füllstoff können alle in der Plastisol-Technologie gängigen und an sich bekannten Füllstoffe verwendet werden. Beispiele für geeignete Füllstoffe sind Kalksteinmehl, natürliche, gemahlene Kreiden (Calciumcarbonate oder Calcium- Magnesium-Carbonate), gefällte Kreiden, Schwerspat, Talk, Glimmer, Tone, Pigmente wie z.B. Titandioxid, Ruß, Eisenoxide.All fillers which are common and known per se in plastisol technology can be used as fillers. Examples of suitable fillers are limestone powder, natural, ground chalk (calcium carbonate or calcium magnesium carbonate), precipitated chalk, heavy spar, talc, mica, clays, pigments such as e.g. Titanium dioxide, carbon black, iron oxides.
Wegen der positiven Eigenschaften und des niedrigen Preises können die pulverförmigen Saccharide in sehr hohen Anteilen in den erfindungsgemäßen Plastisolen eingesetzt werden und so einen Teil der Füllstoffe ersetzen. Daher können die Saccharide bis zu 50 Gew. % der Gesamtformulierung ausmachen. In vielen Formulierungen sind zwischen 3 und 10 oder 20 Gew. % Saccharid enthalten. Weiterhin können auch sogenannte „Leichtfüllstoffe" organischer oder anorganischer Zusammensetzung eingesetzt werden, hierzu zählen beispielsweise Glashohlkugeln, Flugasche („fillite") sowie organische Mikrohohlkugeln auf der Basis von Epoxydharzen oder Phenolharzen. Weiterhin können leitfähigkeitsvermittelnde Pigmente wie spezielle Leitfähigkeitsruße, Graphit oder Antimon-dotierte Silikate zugesetzt werden. Dies ist insbesondere erforderlich, wenn die Plastisole im Rohbau appliziert werden und anschließend auf diesen Plastisolschichten elektrophoretisch abgeschiedene Lackschichten aufgebracht werden sollen.Because of the positive properties and the low price, the powdery saccharides can be used in very high proportions in the plastisols according to the invention and thus replace some of the fillers. Therefore, the saccharides can make up up to 50% by weight of the total formulation. Many formulations contain between 3 and 10 or 20% by weight saccharide. Furthermore, so-called “light fillers” of organic or inorganic composition can also be used, these include, for example, hollow glass spheres, fly ash (“fillite”) and organic hollow microspheres based on epoxy resins or phenolic resins. Furthermore, conductivity-imparting pigments such as special carbon blacks, graphite or antimony-doped silicates can be added. This is particularly necessary if the plastisols are applied to the shell and then electrophoretically deposited lacquer layers are to be applied to these plastisol layers.
Zur Herstellung von spezifisch leichten Plastisolen können außerdem sogenannte Mikrohohlkugeln oder in expandierter und nicht expandierter Form Treibmittel zugesetzt werden, wenn die Plastisole während des Gelierprozesses aufgeschäumt werden sollen. Als Treibmittel geeignet sind alle an sich bekannten Treibmittel, vorzugsweise organische Treibmittel aus der Klasse der Azoverbindungen, N-Nitrosoverbindungen, Sulfonylhydrazide oderFor the production of specifically light plastisols, so-called hollow microspheres or blowing agents in expanded and unexpanded form can also be added if the plastisols are to be foamed during the gelling process. Suitable blowing agents are all blowing agents known per se, preferably organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonyl hydrazides or
Sulfonylsemicarbazide. Aus der Klasse der Azoverbindungen seien beispielhaft das Azobis-isobutyronitril und insbesondere das Azodicarbonamid genannt, aus der Klasse der Nitrosoverbindungen sei beispielhaft das Di- Nitrosopentamethylentetramin genannt, aus der Klasse der Sulfohydrazide das 4,4'-Oxybis(benzolsulfonsäurehydrazid) und aus der Klasse der Semicarbazide das p-Toluolsulfonylsemicarbazid genannt.Sulfonyl. Examples from the class of azo compounds are azobis-isobutyronitrile and in particular azodicarbonamide, from the class of nitroso compounds the di-nitrosopentamethylenetetramine should be mentioned, from the class of sulfohydrazides 4,4'-oxybis (benzenesulfonic acid hydrazide) and from the class of Semicarbazide called the p-toluenesulfonylsemicarbazid.
Eine weitere Möglichkeit, die erfindungsgemäßen Plastisole aufzuschäumen, besteht darin, sogenannte Mikrohohlkugeln ("Microspheres") den Plastisolen zuzusetzen. Derartige Mikrohohlkugeln können entweder in der vorgeschäumten Form als Mikrohohlkugeln direkt dem Plastisol zugesetzt werden oder in einer besonders bevorzugten Art werden die "Mikrohohlkugeln" als feinteiliges Pulver in der ungeschäumten Form dem Plastisol zugesetzt. Diese ungeschäumten "Mikrohohlkugeln" expandieren erst bei der Gelierung des Plastisols und ergeben so eine sehr gleichmäßige und feinporige Schäumung. Die Mikrohohlkugeln enthalten ein flüssiges Treibmittel auf der Basis von aliphatischen Kohlenwasserstoffen oder Fluorkohlenwasserstoffen als Kern und eine Schale aus einem Copolymer aus Acrylnitril mit Vinylidenchlorid und/oder Methylmethacrylat und/oder Methacrylnitril. Beim Einsatz derartiger Microspheres erfolgt die Expansion der Microspheres und damit das Schäumen erst während des Gelierprozesses des Plastisols. Die Verwendung derartiger Microspheres ist beispielsweise in der EP-A-559254 beschrieben. Derartige "Mikrohohlkugeln" sind z.B. unter dem Handelsnamen „Expancel" der Fa. Nobel Industries oder als „Dualite" von der Firma Pierce & Stevens im Handel erhältlich. Erfindungsgemäß ist es darüber hinaus möglich, Eigenschaften des Plastigels, insbesondere die Abriebfestigkeit, dadurch weiter zu verbessern, daß man dem Plastisol eine bei der Geliertemperatur mit den Carboxylgruppen des ggf. vorhandenen Copolymeren unter Vernetzung reagierende Verbindung in einer Menge bis zu 40 Gew. % zusetzt. Für eine Reaktion mit den vorhandenen Carboxylgruppen kommen insbesondere langkettige Epoxyverbindungen, epoxidierte Polybutadiene oder auch epoxidierte natürliche Öle wie epoxidiertes Sojabohnenöl oder feste, pulverförmige Epoxiderivate in Betracht. Weiterhin können flüssige hydroxyfunktionelle Polybutadiene oder mercaptan-terminierte Flüssigpolymere anstelle von oder in Kombination mit Polypropylenglykolen verwendet werden. Die Bildung von Esterbindungen zwischen diesen Verbindungen und den Carboxylgruppen des Co-polymeren findet im allgemeinen bereits beim Erwärmen des Plastisols auf die Geliertemperatur statt. Gegebenenfalls können jedoch geeignete Katalysatoren in einer Menge von etwa 0.01 bis 2.0 Gew.%, z.B. Imidazol oder substituierte Imidazole wie N- Alkylimidazole, z.B. N-Methylimidazol, tertiäre Amine, Tetramethylendiamin oder Harnstoffderivate, ggf. auf inerten Füllstoffen niedergeschlagen, zugesetzt werden. Für die Esterbildung mit Glykolen sind auch Alkylbenzolsulfonsäuren und Titanate als Katalysatoren geeignet.Another possibility of foaming up the plastisols according to the invention is to add so-called microspheres to the plastisols. Such hollow microspheres can either be added directly to the plastisol in the pre-expanded form as hollow microspheres or, in a particularly preferred manner, the "hollow microspheres" are added to the plastisol as finely divided powder in the unfoamed form. These unfoamed "hollow micro spheres" only expand when the plastisol is gelled and thus result in a very uniform and fine-pored foaming. The hollow microspheres contain a liquid blowing agent based on aliphatic hydrocarbons or fluorocarbons as the core and a shell made of a copolymer of acrylonitrile with vinylidene chloride and / or methyl methacrylate and / or methacrylonitrile. When using such microspheres, the expansion of the microspheres and thus the foaming takes place only during the gelling process of the plastisol. The use of such microspheres is described for example in EP-A-559254. Such "hollow microspheres" are commercially available, for example, under the trade name "Expancel" from Nobel Industries or as "Dualite" from Pierce & Stevens. According to the invention, it is also possible to further improve properties of the plastic gel, in particular the abrasion resistance, by adding to the plastisol a compound which reacts at the gelation temperature with the carboxyl groups of the optionally present copolymers with crosslinking in an amount of up to 40% by weight , Long-chain epoxy compounds, epoxidized polybutadienes or also epoxidized natural oils such as epoxidized soybean oil or solid, powdered epoxy derivatives are particularly suitable for a reaction with the carboxyl groups present. Liquid hydroxy-functional polybutadienes or mercaptan-terminated liquid polymers can also be used instead of or in combination with polypropylene glycols. The formation of ester bonds between these compounds and the carboxyl groups of the copolymer generally takes place when the plastisol is heated to the setting temperature. If necessary, however, suitable catalysts can be added in an amount of about 0.01 to 2.0% by weight, for example imidazole or substituted imidazoles such as N-alkylimidazoles, for example N-methylimidazole, tertiary amines, tetramethylene diamine or urea derivatives, if appropriate precipitated on inert fillers. Alkylbenzenesulfonic acids and titanates are also suitable as catalysts for the ester formation with glycols.
Weiterhin können den erfindungsgemäßen Plastisolen amino- und/oder amidofunktionelle Verbindungen und/oder blockierte Polyurethane einzeln oder in Kombination zugesetzt werden, wie sie aus der PVC - Plastisoltechnologie als Haftvermittler bekannt sind, sie bewirken eine erhebliche Verbesserung der Abriebfestigkeit. Beispiele für derartige Verbindungen sind die wohlbekannten Polyaminoamide auf Basis dimerisierter Fettsäuren und niedermolekularen Dioder Polyaminen, wie sie z.B. unter den Handelsnamen Versamid 115, 125 oder 140 bekannt sind und/oder aminofunktionelle Kondensationsprodukte aus Epoxiden auf Basis des Bisglycidylethers des Bisphenols A mit Diaminen oder Polyaminen wie z.B. Ethylendiamin, Propylendiamin usw.Furthermore, amino and / or amido-functional compounds and / or blocked polyurethanes can be added individually or in combination to the plastisols according to the invention, as are known from the PVC plastisol technology as adhesion promoters, they bring about a considerable improvement in the abrasion resistance. Examples of such compounds are the well known polyaminoamides based on dimerized fatty acids and low molecular weight di or polyamines, e.g. are known under the trade names Versamid 115, 125 or 140 and / or amino-functional condensation products from epoxides based on the bisglycidyl ether of bisphenol A with diamines or polyamines such as e.g. Ethylenediamine, propylenediamine, etc.
Eine weitere Möglichkeit zur Verbesserung der mechanischen Eigenschaften der Plastigele besteht darin, daß man in dem Weichmacher Polyurethanbildner in Form von Isocyanatprepolymeren und niedermolekularen aliphatischen oder cycloaliphatischen Diaminen löst. Die Isocyanatprepolymeren enthalten dabei vorzugsweise blockierte Isocyanatgruppen, z.B. durch Caprolactam blockierte Isocyanatgruppen, oder sie liegen in Form von festen, mikroverkapselten oder oberflächendesaktivierten Isocyanatverbindungen als Dispersion in der flüssigen Phase vor. Diese Isocyanatderivate können in einer Menge bis zu 30 Gew. % der Gesamtformulierung vorliegen, die (cyclo)aliphatischen Diamine können bei niedrigmolekularen Aminen bis zu einem Molekulargewicht von etwa 500) bis zu 5 Gew.%, bei höhermolekularen Diaminen bis zu 30 Gew.% der Gesamtformulierung ausmachen. Beim Erhitzen auf die Geliertemperatur tritt eine Polyurethanbildung ein, wobei mit dem Plastisolpolymeren möglicherweise eine IPN-Struktur (Interpenetrating Polymer Network) gebildet wird.Another way to improve the mechanical properties of the plastic gels is that in the plasticizer in polyurethane Form of isocyanate prepolymers and low molecular weight aliphatic or cycloaliphatic diamines dissolves. The isocyanate prepolymers preferably contain blocked isocyanate groups, for example isocyanate groups blocked by caprolactam, or they are in the form of solid, microencapsulated or surface-deactivated isocyanate compounds as a dispersion in the liquid phase. These isocyanate derivatives can be present in an amount of up to 30% by weight of the total formulation, the (cyclo) aliphatic diamines can be up to 5% by weight in the case of low molecular weight amines up to a molecular weight of about 500 and up to 30% by weight in the case of higher molecular weight diamines. make up the overall wording. When heated to the setting temperature, polyurethane formation occurs, whereby the plastisol polymer may form an IPN structure (Interpenetrating Polymer Network).
Wenn in das Copolymere ein anderes vernetzend wirkendes Comonomeres einpolymerisiert wurde, können die erfindungsgemäßen Plastisole zur Verbesserung der mechanischen Eigenschaften noch weitere reaktive Zusätze enthalten. Diese richten sich nach dem eingesetzten vernetzend wirkenden Comonomer. Bei hydroxyfunktionellen Comonomeren können Di- oder Polyisocyanate zugesetzt werden, wobei letztere vorzugsweise blockiert oder mikroverkapselt sind, bei epoxyfunktionellen Comonomeren werden vorzugsweise Di- oder Polyamine oder Polyaminoamide zugesetzt, bei (blockierten) isocyanatfunktionellen Comonomeren können amino- und/oder hydroxyfunktionelle Zusätze verwendet werden. Gegebenenfalls können diese Vernetzungsreaktionen durch an sich bekannte Katalysatoren beschleunigt werden.If another crosslinking comonomer has been polymerized into the copolymer, the plastisols according to the invention can contain further reactive additives to improve the mechanical properties. These depend on the crosslinking comonomer used. In the case of hydroxy-functional comonomers, di- or polyisocyanates can be added, the latter preferably being blocked or microencapsulated; in the case of epoxy-functional comonomers, di- or polyamines or polyaminoamides are preferably added; in the case of (blocked) isocyanate-functional comonomers, amino- and / or hydroxy-functional additives can be used. If appropriate, these crosslinking reactions can be accelerated by catalysts known per se.
Die Plastisolzusammensetzungen enthalten :The plastisol compositions contain:
a) 5 bis 60 Gew.% mindestens eines pulverförmigen Polymers, b) 5 bis 65 Gew.% Weichmacher, c) 0 bis 40 Gew.% Füllstoffe, d) 1 bis 30 Gew.% mindestens eines Mono-, Di- oder Oligosaccharids e) 2 bis 40 Gew.% reaktive Zusätze, ausgewählt aus der Gruppe der ggf. blockierten oder mikroverkapselten Di- oder Polyisocyanate; amino- und/oder hydroxyfunktionelle Zusätze, insbesondere Di- oder Polyamine oder Polyaminoamide, Imidazolderivate, Epoxidharze, Kondensationsprodukte aus Epoxidharzen und Polyaminoamiden und/oder Di- oder Polyaminen, Dicarbonsäuren Di- oder Tricarbonsäureanhydriden, Acetylacetonaten, Peroxiden oder Mischungen der vorgenannten reaktiven Zusätze f) ggf. weitere Hilfs- und Zusatzstoffe, wobei die Summe der Einzelkomponenten 100 Gew.% beträgt.a) 5 to 60% by weight of at least one powdered polymer, b) 5 to 65% by weight of plasticizer, c) 0 to 40% by weight of fillers, d) 1 to 30% by weight of at least one mono-, di- or oligosaccharide e) 2 to 40% by weight of reactive additives, selected from the group of optionally blocked or microencapsulated di- or polyisocyanates; amino- and / or hydroxy-functional additives, especially di- or polyamines or polyaminoamides, imidazole derivatives, epoxy resins, condensation products from epoxy resins and polyaminoamides and / or di- or polyamines, dicarboxylic acids, di- or tricarboxylic acid anhydrides, acetylacetonates, peroxides or mixtures of the aforementioned reactive additives f) If necessary, further auxiliaries and additives, the sum of the individual components being 100% by weight.
Bei dem Einsatz von Sacchariden als haftvermittelnden Zusatz ergeben sich gegenüber dem bekannten Stand der Technik die folgenden Vorteile: verbesserte Alterungsbeständigkeit, insbesondere nach demThe use of saccharides as an adhesion-promoting additive has the following advantages over the known prior art: improved resistance to aging, especially after
Salzsprühtest gemäß DIN 50021 , dem VDA-Test (VDA 621-415), demSalt spray test according to DIN 50021, the VDA test (VDA 621-415), the
Spritzwassertest oder Kombinationen dieser Tests, verringerte Neigung zur Blasenbildung nach Feuchtigkeitsaufnahme,Splash water test or combinations of these tests, reduced tendency to bubble after moisture absorption,
Einsatz nachwachsender Rohstoffe, geringe Materialkosten frei von toxischen Schwermetallen, daher toxikologisch unbedenklich und umweltfreundlich.Use of renewable raw materials, low material costs free of toxic heavy metals, therefore toxicologically harmless and environmentally friendly.
Insbesondere bei den Methacrylat-Plastisolen kann, wenn erwünscht, auf den Zusatz von Graphit verzichtet werden und trotzdem werden alterungsbeständige Formulierungen erzielt, dies war bisher immer nur mit Graphit-Zusatz möglich.In the case of methacrylate plastisols in particular, the addition of graphite can be dispensed with, if desired, and nonetheless aging-resistant formulations are achieved, which has previously only been possible with the addition of graphite.
Die erfindungsgemäßen Plastisol - Zusammensetzungen haben gute Haftungseigenschaften auf den unterschiedlichsten Substraten wie Stahl, elektrolytisch verzinkter Stahl, feuerverzinkter Stahl oder organisch beschichteter Stahl („Granocoat" oder „Bonazink"). Nach dem bisherigen Stand der Technik war eine alterungsbeständige Haftung und guter Korrosionsschutz nur durch Zusatz von - häufig schwermetallhaltigen - Korrosionsschutzpigmenten und/oder Korriosionsinhibitoren möglich. Die erfindungsgemäßen Plastisole eignen sich als Klebstoffe, insbesondere als sogenannte Rohbauklebstoffe, aber auch für den Unterbodenschutz, für die Nahtabdichtung, für die Unterfütterung von Motorhauben, Kofferraumdeckeln, Türen oder bei Einsatz von Vorgelierung auch als Dachspriegel. Weiterhin eignen sich die erfindungsgemäßen Plastisole zur Nahtabdichtung, als Bördelnahtklebstoff, zur Bördelnahtversiegelung oder als Punkschweißpaste. Wegen der guten Hafteigenschaften auf einer Vielzahl von Substraten können die erfindungsgemäßen Plastisole also sowohl im Rohbau, als auch im Lackbereich oder im Trimmbereich bei der Fertigung von Automobilen eingesetzt werden. Auch eine Unterbodenapplikation auf Rohblech ist möglich.The plastisol compositions according to the invention have good adhesion properties on a wide variety of substrates such as steel, electrolytically galvanized steel, hot-dip galvanized steel or organically coated steel ("Granocoat" or "Bonazink"). According to the current state of the art, aging-resistant adhesion and good corrosion protection were only possible by adding - often containing heavy metals - corrosion protection pigments and / or corrosion inhibitors. The plastisols according to the invention are suitable as adhesives, in particular as so-called structural adhesives, but also for underbody protection, for seam sealing, for relining engine hoods, trunk lids, doors or, if pre-gelling is used, also as a roof bow. Furthermore, the plastisols according to the invention are suitable for seam sealing, as a flanged seam adhesive, for flared seam sealing or as a spot welding paste. Because of the good adhesive properties on a large number of substrates, the plastisols according to the invention can therefore be used both in body-in-white, as well as in the lacquer area or in the trim area in the manufacture of automobiles. Underbody application on raw sheet metal is also possible.
Zur näheren Erläuterung der Erfindung sollen die nachfolgenden Beispiele dienen, sie haben nur exemplarischen Charakter und decken nicht die gesamte Breite der erfindungsgemäßen Plastisole ab. Aus den o.g. Angaben kann der Fachmann die gesamte Anwendungsbreite jedoch leicht herleiten.The following examples are intended to explain the invention in more detail; they are only exemplary in nature and do not cover the entire breadth of the plastisols according to the invention. From the above However, the person skilled in the art can easily derive information from the entire range of applications.
BeispieleExamples
Beispiel 1 : (Vergleich)Example 1: (comparison)
Bördelnaht Klebstoff und Bördelnahtversiegelung auf Basis eines PVC-Plastisols: Im nachfolgenden Fall wurde in einem Grundsatzansatz gemäß Stand der Technik Korrosionsschutzpigment bzw. erfindungsgemäß Puderzucker eingesetzt:Flare seam adhesive and flare seam sealing based on a PVC plastisol: In the following case, a basic approach according to the state of the art used corrosion protection pigment or powdered sugar according to the invention:
Beispiel 2: (erfindungsgemäß)Example 2: (according to the invention)
Beispiel 3: (erfindungsgemäß) handelsüblicher Unterbodenschutz, dem 10 % Rohrzucker zugemischt wurden.Example 3: (According to the invention) commercially available underbody protection to which 10% cane sugar was added.
Beispiel 4: (Vergleich) handelsüblicher Unterbodenschutz. Example 4: (Comparison) standard underbody protection.
Beispiel 5: (erfindungsgemäß)Example 5
Unterbodenschutz auf PMMA-BasisUnderbody protection based on PMMA
Beispiel 6:Example 6:
Unterbodenschutz auf PMMA-Basis ohne DextroseUnderbody protection based on PMMA without dextrose
Das erfindungsgemäße Beispiel 2 zeigt gegenüber dem Vergleichsbeispiel 1 in allen Schichtstärken der Beschichtung gute Ergebnisse nach kurzfristiger Gelierung bei hohen Temperaturen gefolgt von Feuchtigkeitslagerung. Es werden in keinem Fall Blasenbildungen in der Beschichtung beobachtet wohingegen beim Klebstoff gemäß Stand der Technik vielfach Blasenbildung beobachtet wird. Außerdem kann im erfindungsgemäßen Beispiel auf das strontiumhaltige Korrosionsschutzpigment verzichtet werden. Compared to comparative example 1, example 2 according to the invention shows good results in all layer thicknesses of the coating after short-term gelation at high temperatures, followed by moisture storage. In no case blistering is observed in the coating, whereas blistering is frequently observed with the adhesive according to the prior art. In addition, the strontium-containing corrosion protection pigment can be dispensed with in the example according to the invention.
Das erfindungsgemäße Beispiel 3 zeigt einen Unterbodenschutz, der Saccharose in hohen Mengen, zum Teil als Füllstoff, enthält, so daß der Anteil an spezifisch schwerem Calciumcarbonat drastisch reduziert werden konnte. Dadurch wird ein spezifisch leichter Unterbodenschutz möglich, der in seinem Haftungsverhalten einem spezifisch schwererem handelsüblichen Unterbodenschutz mit einem hohen Anteil an Calciumcarbonat (Beispiel 4) absolut ebenbürtig ist.Example 3 according to the invention shows an underbody protection which contains sucrose in large amounts, partly as a filler, so that the proportion of specifically heavy calcium carbonate could be drastically reduced. This enables a specifically light underbody protection which is absolutely equal in its adhesion behavior to a specifically heavier commercially available underbody protection with a high proportion of calcium carbonate (example 4).
In gleicher Weise ergibt der erfindungsgemäße Unterbodenschutz auf PMMA - Basis des Beispiels 5 einen spezifisch besonders leichten Unterbodenschutz, da ebenfalls auf den Zusatz von Calciumcarbonat als Füllstoff verzichtet werden konnte. Die Abriebfestigkeit des erfindungsgemäßen Unterbodenschutzes gemäß Beispiel 5 ist sogar besser als die des Vergleichsbeispiels 6 gemäß Stand der Technik.In the same way, the underbody protection according to the invention based on PMMA of Example 5 results in a specifically particularly light underbody protection, since it was also possible to dispense with the addition of calcium carbonate as a filler. The abrasion resistance of the underbody protection according to the invention according to Example 5 is even better than that of Comparative Example 6 according to the prior art.
Aus den vorstehenden Beispielen geht besonders deutlich hervor, daß die Verwendung von Saccharose in Plastisol-Kleb- oder Dichtstoffen sowie Unterbodenschutz - Zusammensetzungen die Formulierung von Plastisolen mit sehr guten Gebrauchseigenschaften ermöglicht. It is particularly clear from the above examples that the use of sucrose in plastisol adhesives or sealants and underbody protection compositions enables the formulation of plastisols with very good properties.

Claims

Patentansprüche claims
1. Plastisolzusammensetzung auf der Basis von pulverförmigen organischen Polymeren und Weichmachern, dadurch gekennzeichnet, daß sie pulverförmige Monosaccharide, Disaccharide oder Oligosaccharide enthält.1. plastisol composition based on powdered organic polymers and plasticizers, characterized in that it contains powdered monosaccharides, disaccharides or oligosaccharides.
2. Plastisolzusammensetzung nach Anspruch 1 dadurch gekennzeichnet, daß die pulverförmigen organischen Polymeren ausgewählt werden aus der Gruppe gebildet durch Polyvinylchlorid, Vinylchloridcopolymere mit Vinylacetat, Styrol und / oder Alkyl(meth)arylaten, Copolymeren des Styrols mit (Meth)acrylsäure, (Meth)acrylamid und / oder Alkyl(meth)acrylaten, Copolymeren des Methyloder Ethylmethacrylatens mit C3-bis C8-Acryl(meth)acrylaten, Alkylmethacrylat- homopolymeren oder Mischungen der vorgenannten Polymeren.2. plastisol composition according to claim 1, characterized in that the powdery organic polymers are selected from the group formed by polyvinyl chloride, vinyl chloride copolymers with vinyl acetate, styrene and / or alkyl (meth) arylates, copolymers of styrene with (meth) acrylic acid, (meth) acrylamide and / or alkyl (meth) acrylates, copolymers of methyl or ethyl methacrylate with C 3 to C 8 acrylic (meth) acrylates, alkyl methacrylate homopolymers or mixtures of the aforementioned polymers.
3. Plastisolzusammensetzungen nach Anspruch 1 oder 2 dadurch gekennzeichnet, daß die pulverförmigen Monosaccharide, Disaccharide oder Oligosaccharide ausgewählt werden aus Glucose, Galactose, Mannose, Fructose, Arabinose, Xylose, Ribose, 2-Desoxy-ribose, Cellobiose, Maltose (Malzzucker), Lactose (Milchzucker), Saccharose (Rohrzucker), Gentiobiose, Melibiose, Trehalose, Turanose, Gentianose, Kestose, Maltotriose, Melecitose, Raffinose, Stachyose, Lychnose, Secalose oder deren Mischungen.3. plastisol compositions according to claim 1 or 2, characterized in that the powdered monosaccharides, disaccharides or oligosaccharides are selected from glucose, galactose, mannose, fructose, arabinose, xylose, ribose, 2-deoxy-ribose, cellobiose, maltose (malt sugar), lactose (Milk sugar), sucrose (cane sugar), gentiobiose, melibiose, trehalose, turanose, gentianose, kestose, maltotriose, melecitose, raffinose, stachyose, lychnose, secalose or mixtures thereof.
4. Plastisolzusammensetzungen nach Anspruch 3, dadurch gekennzeichnet, daß das oder die Mono-, Di- oder Oligosaccharid(e) eine mittlere Teilchengröße von 1 bis 100 μm, vorzugsweise zwischen von 1 bis 20 μm haben.4. plastisol compositions according to claim 3, characterized in that the mono-, di- or oligosaccharide (s) have an average particle size of 1 to 100 microns, preferably between 1 to 20 microns.
5. Plastisolzusammensetzungen nach mindestens einem der vorhergehenden Ansprüche, enthaltend g) 5 bis 60 Gew.% mindestens eines pulverförmigen Polymers, h) 5 bis 65 Gew.% Weichmacher, i) 0 bis 40 Gew.% Füllstoffe, j) 1 bis 30 Gew.% mindestens eines Mono-, Di- oder Oligosaccharids k) 2 bis 40 Gew.% reaktive Zusätze, ausgewählt aus der Gruppe der ggf. blockierten oder mikroverkapselten Di- oder Polyisocyanate; amino- und/oder hydroxyfunktionelle Zusätze, insbesondere Di- oder Polyamine oder Polyaminoamide, Imidazolderivate, Epoxidharze, Kondensationsprodukte aus Epoxidharzen und Polyaminoamiden und/oder Di- oder Polyaminen, Dicarbonsäuren Di- oder Tricarbonsäureanhydriden, Acetylacetonaten, Peroxiden oder Mischungen der vorgenannten reaktiven Zusätze5. plastisol compositions according to at least one of the preceding claims, containing g) 5 to 60 wt.% Of at least one powdery polymer, h) 5 to 65 wt.% Plasticizer, i) 0 to 40 wt.% Fillers, j) 1 to 30 wt % of at least one mono-, di- or oligosaccharide k) 2 to 40% by weight of reactive additives, selected from the group of optionally blocked or microencapsulated di- or polyisocyanates; Amino- and / or hydroxy-functional additives, especially di- or polyamines or polyaminoamides, imidazole derivatives, epoxy resins, condensation products from epoxy resins and polyaminoamides and / or di- or polyamines, dicarboxylic acids di- or tricarboxylic acid anhydrides, acetylacetonates, peroxides or mixtures of the aforementioned reactive additives
I) ggf. weitere Hilfs- und Zusatzstoffe, wobei die Summe der Einzelkomponenten 100 Gew.% beträgt.I) if necessary, further auxiliaries and additives, the sum of the individual components being 100% by weight.
6. Verwendung einer Plastisolzusammensetzung nach mindesten einem der Ansprüche 1 bis 5 im Kraftfahrzeugbau als Unterbodenschutzmittel, als Klebstoff für die Haubenunterfütterung, als Masse zum Schwellerschutz, als Metall klebstoff, insbesondere als Bördelnahtklebstoff, zur6. Use of a plastisol composition according to at least one of claims 1 to 5 in motor vehicle construction as an underbody protection agent, as an adhesive for the hood relining, as a mass for sill protection, as a metal adhesive, in particular as a seam seam adhesive
Bördelnahtversiegelung oder als Punktschweißpaste. Flared seam sealing or as spot welding paste.
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