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EP1343841A1 - Masses de caoutchouc reticulees par le soufre a nuisance olfactive reduite - Google Patents

Masses de caoutchouc reticulees par le soufre a nuisance olfactive reduite

Info

Publication number
EP1343841A1
EP1343841A1 EP01989588A EP01989588A EP1343841A1 EP 1343841 A1 EP1343841 A1 EP 1343841A1 EP 01989588 A EP01989588 A EP 01989588A EP 01989588 A EP01989588 A EP 01989588A EP 1343841 A1 EP1343841 A1 EP 1343841A1
Authority
EP
European Patent Office
Prior art keywords
rubber
composition according
groups
composition
compositions
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Withdrawn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
EP01989588A
Other languages
German (de)
English (en)
Inventor
Peter Born
Ralf Sauer
Thomas Zahn
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 Teroson GmbH
Original Assignee
Henkel Teroson GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Teroson GmbH filed Critical Henkel Teroson GmbH
Publication of EP1343841A1 publication Critical patent/EP1343841A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J121/00—Adhesives based on unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof

Definitions

  • the present invention relates to heat-curing, reactive compositions based on natural and / or synthetic rubbers and sulfur-containing vulcanizing agents which cause little to no odor nuisance during curing. Furthermore, this invention relates to the use of such compositions, their production and a method for connecting metal parts and / or sealing joints between metal parts.
  • these adhesives must be resistant to the various washer baths and systems, preferably without pre-gelling, and must be able to withstand the high temperatures of up to approximately 240 ° C of the stoving ovens for electrocoating without damage and harden in this temperature range.
  • these adhesives / sealants must have good aging-resistant adhesion on the various galvanized steels such as, for example, electrolytically galvanized, hot-dip galvanized as well as the corresponding thermally post-treated galvanizations or galvanized and subsequently phosphated steel sheets as well as non-galvanized steels and aluminum.
  • Structural adhesives for this Applications must still have a minimum strength of around 15 MPa. Sealing and sealing materials as well as relining adhesives have strengths between 0.2 and 3 MPa. For reasons of the simple workflow, only one-component materials that can be conveyed by pumps and that can be applied by machine are suitable.
  • epoxy adhesives Because of the high strength requirements, one-component heat-curing epoxy adhesives were predominantly used for these applications in the past. In addition to the advantages of high tensile strength, epoxy adhesives have a number of decisive disadvantages.
  • the pasty, heat-curing one-component epoxy adhesives do not have sufficient wash-out resistance in the scrubbing and phosphating baths, so that these bonds usually have to be pre-gelled by induction heating or special ovens. However, this means an additional step. Attempts have been made to circumvent this by developing one-component, thermosetting, epoxy adhesives with a hotmelt character, but these require special application systems, since these adhesives have to be applied hot.
  • Epoxy adhesives are characterized by a high tensile strength, but their elongation at break is generally very low, even the epoxy adhesives made flexible by the addition of rubber only have an elongation at break of less than 5%.
  • the use of epoxy adhesives based on low molecular weight epoxy compounds is undesirable for reasons of occupational hygiene, since these low molecular weight epoxy compounds can trigger allergic or sensitizing reactions in contact with skin.
  • EP-B-97394 describes an adhesive mixture based on a liquid polybutadiene rubber, powdered sulfur, organic accelerators and, if appropriate, solid rubber.
  • BD Ludbrook, Int. J. Adhesion and Adhesives Vol. 4, No.4, S. 148-150 states that such adhesives based on liquid polybutadienes can achieve strength values which are equivalent to those of flexible epoxy adhesives by appropriate selection of the amount of sulfur and accelerators.
  • DE-C-3834818 proposes to use OH-terminated polybutadienes for the liquid rubber.
  • As functional rubber polymer in addition to hydroxy-functional homopolymers or copolymers, those having thiol, amino, amido, carboxyl, epoxy, isocyanate, anhydride or acetoxy groups can also be used, but the cured one Adhesive mixture has an elongation at break that does not exceed 15%.
  • polyfunctional epoxy compounds can be added to the adhesive mixtures based on liquid rubbers in order to improve the adhesion or to improve the tensile shear strength.
  • epoxy resin-containing adhesive compositions Apart from the fact that it is undesirable to use epoxy resin-containing adhesive compositions for the reasons mentioned above, the adhesive compositions described in the latter two publications are not suitable as structural adhesives since they only achieve a very low strength level of at most 3 MPa.
  • WO 96/23040 describes high-strength structural raw rubber-based adhesives which are equivalent in strength to epoxy resin adhesives. With these compositions, tensile shear strengths of over 15 MPa can be achieved, the elongation at break being clearly above 15%, very often above 20%.
  • the abovementioned rubber compositions are preferably used in automobile construction; overall, they have an excellent one
  • the range of properties, disadvantageous and very disruptive is that of
  • vulcanizing agents that are free of elemental sulfur. So do vulcanization systems based on peroxides, quinones or
  • the object of the present invention was to further develop heat-curing, reactive compositions based on natural and / or synthetic rubbers and the technically evaluated sulfur-containing vulcanizing agents in such a way that the formation of odors during curing is eliminated or at least drastically is reduced.
  • Another object of the present invention is the use of heterocyclic compounds with at least two nitrogen atoms in the ring to eliminate or reduce the formation of odors during the vulcanization of the thermosetting rubber compositions with sulfur-containing vulcanizing agents, and a method for producing these rubber compositions.
  • Another object of the present invention is a method for connecting metal parts and / or sealing joints between metal parts, in which
  • the adhesive / sealant compositions according to the invention contain at least one of the following substances:
  • liquid rubbers and / or solid rubbers or elastomers one or more liquid rubbers and / or solid rubbers or elastomers
  • Liquid rubbers or elastomers can be selected from the following group of homo- and / or copolymers:
  • Polybutadienes in particular the 1, 4- and 1, 2-polybutadienes, polybutenes, polyisobutylenes, 1,4- and 3,4-polyisoprenes, styrene-butadiene copolymers, butadiene-acrylonitrile copolymers, these polymers being terminal and / or (statistically distributed ) may have lateral functional groups. Examples of such functional groups are hydroxyl, amino, carboxyl, carboxylic anhydride or epoxy groups.
  • the molecular weight of these liquid rubbers is typically below 20,000, preferably between 900 and 10,000.
  • the proportion of liquid rubber in the overall composition depends on the desired rheology of the uncured composition and the desired mechanical properties of the cured composition.
  • the proportion of liquid rubber or elastomer normally varies between 5 and 50% by weight of the total formulation. It has proven expedient to use mixtures of liquid rubbers of different molecular weights and different configurations with respect to the remaining double bonds. In order to achieve optimal adhesion to the various substrates, a proportion is used in the particularly preferred formulations
  • Liquid rubber component with hydroxyl groups or acid anhydride groups used. At least one of the liquid rubbers should contain a high proportion of cis-1,4 double bonds, another one a high proportion of vinyl double bonds.
  • suitable rubbers are polybutadiene, preferably with a very high proportion of cis-1,4-double bonds (typically over 95%), styrene-butadiene rubber, Butadiene acrylonitrile rubber, synthetic or natural isoprene rubber, butyl rubber or polyurethane rubber.
  • the addition of finely divided thermoplastic polymer powders brings a significant improvement in tensile shear strength while maintaining a very high elongation at break, which was previously unusual for structural adhesives.
  • thermoplastic polymer powders are suitable as an additive, for example vinyl acetate, either as a homopolymer or as a copolymer with ethylene, such as other olefins and acrylic acid derivatives, polyvinyl chloride, vinyl chloride ⁇ / inyl acetate copolymers, styrene copolymers, as described, for example, in DE A-4034725 are described, polymethyl methacrylate and its copolymers with other (meth) acrylic acid esters and functional comonomers, as described for example in DE-C-2454235, or polyvinyl acetals such as polyvinyl butyral.
  • vinyl acetate either as a homopolymer or as a copolymer with ethylene, such as other olefins and acrylic acid derivatives
  • polyvinyl chloride vinyl chloride ⁇ / inyl acetate copolymers
  • styrene copolymers as described, for example, in DE A-40
  • the average particle size should be less than 1 mm, preferably less than 350 ⁇ m, very particularly preferably between 100 ⁇ m and 20 ⁇ m.
  • Polyvinyl acetate or copolymers based on ethylene vinyl acetate (EVA) are very particularly preferred.
  • the amount of thermoplastic polymer powder added depends on the desired strength range, it is between 2 and 20% by weight, based on the total composition, a particularly preferred range is 10 to 15%. Since the crosslinking or curing reaction of the rubber composition has a decisive influence on the tensile shear strength and on the elongation at break of the cured adhesive composition, the vulcanization system must be selected and coordinated with particular care.
  • a large number of vulcanization systems based on elemental sulfur as well as vulcanization systems without elemental sulfur are suitable, the latter being the vulcanization systems based on thiuram disulfides.
  • Vulcanization systems based on elemental sulfur and organic vulcanization accelerators and zinc compounds are particularly preferred.
  • the powdered sulfur is used in amounts of 1 to 15% by weight, based on the total composition, and amounts of between 4 and 8% are particularly preferably used.
  • Suitable organic accelerators are the dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde / amine accelerators (for example hexamethylene tetramine) and guanidine accelerators; dibenzothiazyl disulfide (MB) is very particularly preferred ).
  • These organic accelerators are used in amounts of between 2 and 8% by weight, based on the overall formulation, preferably between 3 and 6%.
  • a choice can be made between the zinc salts of fatty acids, zinc dithiocarbamates, basic zinc carbonates and, in particular, finely divided zinc oxide.
  • the content of zinc compounds is in the range between 1 and 10% by weight, preferably between 3 and 7% by weight.
  • other typical rubber vulcanization aids such as, for example, fatty acids (for example stearic acid) can be present in the formulation.
  • compositions according to the invention generally already have very good adhesion to the substrates to be bonded due to the content of liquid rubber with functional groups, if necessary, tackifiers and / or adhesion promoters can be added.
  • Suitable for this purpose are, for example, hydrocarbon resins, phenolic resins, terpene-phenolic resins, resorcinol resins or their derivatives, modified or unmodified resin acids or esters (abietic acid derivatives), polyamines, polyamino amides, anhydrides and copolymers containing anhydrides.
  • the addition of polyepoxide resins in small amounts ( ⁇ 1% by weight) can also improve the adhesion on some substrates.
  • the solid epoxy resins with a molecular weight of significantly more than 700 are preferably used in finely ground form, so that the formulations are nevertheless essentially free of epoxy resins, in particular those with a molecular weight of less than 700. If tackifiers or adhesion promoters are used, their nature depends and amount of the Polymer composition of the adhesive / sealant, on the desired strength of the cured composition and on the substrate to which the composition is applied.
  • Typical tackifying resins such as the terpene phenol resins or resin acid derivatives are normally used in concentrations between 5 and 20% by weight, typical adhesion promoters such as polyamines, polyaminoamides or resorcinol derivatives are used in the range between 0.1 and 10% by weight.
  • blowing agents can be used to achieve foaming during the curing process, but organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonylhydrazides or sulfonylsemicarbazides are preferred.
  • azo compounds to be used according to the invention include azobisisobutyronitrile and in particular azodicarbonamide, from the class of nitroso compounds the di-nitroso-pentamethylenetetramine is mentioned, from the class of sulfohydrazides 4,4'-oxybis (benzenesulfonic acid hydrazide), diphenyl sulfone 3,3'-disulfohydrazide or the benzene-1,3-disulfohydrazide and from the class of the semicarbazides the p-toluenesulfonylsemicarbazide.
  • the so-called expandable microspheres i.e. Unexpanded thermoplastic polymer powders occur that are soaked or filled with low-boiling organic liquids.
  • Such "microspheres” are described, for example, in EP-A-559254, EP-A-586541 or EP-A-594598.
  • hollow microspheres which have already been expanded can also be used or also used. If necessary, these expandable / expanded hollow microspheres can be combined in any quantity ratio with the above-mentioned "chemical" blowing agents.
  • the chemical blowing agents are used in foamable compositions in amounts between 0.1 and 3% by weight, preferably between 0.2 and 2% by weight, the hollow microspheres between 0.1 and 4% by weight, preferably between 0.2 and 2% by weight .% used.
  • compositions according to the invention are preferably free from plasticizers for the thermoplastic polymer.
  • plasticizers for the thermoplastic polymer are free from phthalic acid esters.
  • extender oils ie aliphatic, aromatic or naphthenic oils.
  • the fillers can be selected from a large number of materials, in particular chalks, naturally ground or precipitated calcium carbonates, calcium magnesium carbonates, silicates, heavy spar, graphite and carbon black.
  • flaky fillers e.g. Vermiculite, mica, talc or similar layered silicates are suitable as fillers. It may be expedient that at least some of the fillers have been surface-pretreated, in particular a coating with stearic acid has proven to be expedient for the various calcium carbonates or chalks in order to reduce the moisture introduced and to reduce the sensitivity to moisture of the cured composition.
  • the compositions according to the invention generally contain between 1 and 20% by weight, preferably between 8 and 15% by weight. Calcium oxide.
  • the total proportion of fillers in the formulation can vary between 10 and 70% by weight, the preferred range is between 25 and 60% by weight.
  • compositions according to the invention Against the thermal, thermooxidative or ozone depletion of the compositions according to the invention, conventional stabilizers such as sterically hindered phenols or amine derivatives are used, typical quantity ranges for these stabilizers are 0.1 to 5% by weight.
  • the rheology of the compositions according to the invention can normally be brought into the desired range by the selection of the fillers and the quantitative ratio of the low-molecular liquid rubbers
  • conventional rheological aids such as, for example, pyrogenic silicas, bentones or fibrillated or pulp short fibers can be used in the range between 0.1 and 7% are added.
  • other conventional auxiliaries and additives can be used in the compositions according to the invention.
  • heterocyclic compounds examples include imidazole compounds, pyrazole compounds, thiadiazole compounds,
  • Pyrimidine compounds pyriddizine compounds, pyrazine compounds and tiadiazine compounds and mixtures thereof. Specific examples are imidazole and its N-alkyl derivatives or C-alkyl derivatives and alkyl dimercapto-1, 3,4-thiadiazoles.
  • Alkylated 2,5-dimercapto-1,4-thiadiazoles are known from WO 94/17164 for use as sulfur scavengers in hydraulic oil compositions. This document does not, however, indicate that these compounds are also suitable as sulfur scavengers in sulfur-containing vulcanization systems for heat-curing rubber compositions.
  • a preferred field of application for the 1-component heat-curing adhesive / sealant compositions according to the invention is the body-in-white in the automotive industry, so that the curing of the compositions in a temperature range between 80 and 240 ° C. in about 10 to 35 minutes. to be held. Temperatures between 160 and 200 ° C are preferably used in the shell.
  • a decisive advantage of the compositions according to the invention is that they have all the advantages of the rubber-based adhesives / sealants known per se, ie they have a so-called "laundry resistance" immediately after the adhesives have been applied. This means that they do not require any pre-gelling, such as epoxy adhesives, to be stable in the various washing and phosphating baths in the body shop.
  • compositions have the advantage that no or a drastically reduced odor nuisance occurs during curing.
  • compositions according to the invention can be used both for a large number of structural adhesive applications and for adhesive / sealing functions in the automotive sector. Examples include seam sealing of spot welds, (high-strength) structural adhesives, flat coatings for stiffening and / or acoustic damping, pumpable or profiled (highly) expandable rubber foams in contact with the air space of the vehicle interior, e.g. (Pumpable) "pillar filler”. According to the invention, these materials compositions have the following preferred compositions:
  • compositions according to the invention can be prepared in a manner known per se in high-shear mixing units, these include, for example Kneaders, planetary mixers, internal mixers, so-called “Banbury mixers” and similar mixing units known to those skilled in the art.
  • Polybutadiene with active carboxyl groups MW 1700 10.00 low molecular weight, sterospec. PB- ⁇ I.MW 1800, vinyl 50% 19.00
  • Alkyl-dimercapto-1, 3,4-thiadiazole or imidazole added.
  • Adhesives under standard curing conditions (30 min 160 ° C to 15 min
  • Example 1 Example 2 3.5
  • compositions according to the invention cause a desired, significantly reduced odor nuisance than the comparative example of the prior art.

Landscapes

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

Abstract

L'invention concerne des compositions réactives durcissant à chaud qui comprennent des élastomères naturels et/ou synthétiques contenant des doubles liaisons oléfiniques, à base de polyènes liquides et éventuellement de caoutchoucs solides, des systèmes de vulcanisation comprenant du soufre et un ou plusieurs accélérateurs organiques et/ou oxydes de métaux, ainsi qu'un ou plusieurs composés hétérocycliques comprenant au moins deux atomes d'azote dans le cycle. Ces compositions sont vulcanisées par le soufre et par des composés soufrés sans nuisance olfactive ou avec une nuisance olfactive sensiblement réduite. Elles peuvent être utilisées en tant qu'adhésifs, produits d'étanchéité ou masses de revêtement, en particulier dans la construction automobile.
EP01989588A 2000-12-16 2001-12-07 Masses de caoutchouc reticulees par le soufre a nuisance olfactive reduite Withdrawn EP1343841A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10062861A DE10062861A1 (de) 2000-12-16 2000-12-16 Geruchsreduzierte schwefel-vernetzende Kautschukmassen
DE10062861 2000-12-16
PCT/EP2001/014397 WO2002048252A1 (fr) 2000-12-16 2001-12-07 Masses de caoutchouc reticulees par le soufre a nuisance olfactive reduite

Publications (1)

Publication Number Publication Date
EP1343841A1 true EP1343841A1 (fr) 2003-09-17

Family

ID=7667496

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01989588A Withdrawn EP1343841A1 (fr) 2000-12-16 2001-12-07 Masses de caoutchouc reticulees par le soufre a nuisance olfactive reduite

Country Status (4)

Country Link
EP (1) EP1343841A1 (fr)
AU (1) AU2002227999A1 (fr)
DE (1) DE10062861A1 (fr)
WO (1) WO2002048252A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10234369A1 (de) * 2002-07-27 2004-02-12 Henkel Kgaa Strahlungsvernetzbare Schmelzhaftklebstoffe
DE102006014190A1 (de) 2006-03-24 2007-09-27 Henkel Kgaa Hochfeste schlagschälfeste Klebstoffe
DE102006016577A1 (de) 2006-04-06 2007-10-11 Henkel Kgaa Kleb-/Dichtstoffe auf Basis von Flüssigkautschuken
DE102007029644A1 (de) 2007-06-26 2009-01-08 Henkel Ag & Co. Kgaa Einkomponentige, heißhärtende reaktive Zusammensetzung
EP3725827A1 (fr) * 2019-04-16 2020-10-21 Henkel AG & Co. KGaA Préparation thermiquement expansible pouvant être pompée
EP3789446A1 (fr) 2019-09-04 2021-03-10 Henkel AG & Co. KGaA Moyen de réticulation pour le durcissement à basse température
DE102019213413A1 (de) * 2019-09-04 2021-03-04 Henkel Ag & Co. Kgaa Vulkanisierungsmittel

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US3393173A (en) * 1964-07-15 1968-07-16 Interchem Corp Method of calking with a plasticized polychloroprene composition
US4919976A (en) * 1985-08-23 1990-04-24 Uniroyal Chemical Company, Inc. Insulating adhesive tape composition and composites thereof
US4822845A (en) * 1987-04-13 1989-04-18 The Firestone Tire & Rubber & Company Rubber compositions modified with heterocyclic di-N-oxides
DE3741165A1 (de) * 1987-12-04 1989-06-15 Henkel Kgaa Heisshaertende klebstoffe auf basis von hydroxylgruppen enthaltendem polybutadien
JPH01207337A (ja) * 1988-02-16 1989-08-21 Bridgestone Corp 低発熱性ゴム組成物
FR2635110B1 (fr) * 1988-08-05 1990-11-09 Saim Adhesifs Insonorisants Mo Adhesif pregelifiable
DE19502381A1 (de) * 1995-01-26 1996-08-01 Teroson Gmbh Strukturelle Rohbauklebstoffe auf Kautschukbasis
DE19518673A1 (de) * 1995-05-20 1996-11-21 Henkel Teroson Gmbh Heißhärtende geschäumte Kautschukmassen mit hoher Strukturfestigkeit
DE19644855A1 (de) * 1996-10-29 1998-04-30 Henkel Teroson Gmbh Schwefelfreie expandierende, heißhärtende Kautschuk-Formteile
US5739211A (en) * 1997-02-25 1998-04-14 The Goodyear Tire & Rubber Company Rubber compositions containing a pyrazine amide

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Also Published As

Publication number Publication date
AU2002227999A1 (en) 2002-06-24
DE10062861A1 (de) 2002-06-27
WO2002048252A1 (fr) 2002-06-20

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