EP1812525A1 - Feuchtigkeitshärtendes bindemittel - Google Patents

Feuchtigkeitshärtendes bindemittel

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Publication number
EP1812525A1
EP1812525A1 EP05803039A EP05803039A EP1812525A1 EP 1812525 A1 EP1812525 A1 EP 1812525A1 EP 05803039 A EP05803039 A EP 05803039A EP 05803039 A EP05803039 A EP 05803039A EP 1812525 A1 EP1812525 A1 EP 1812525A1
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EP
European Patent Office
Prior art keywords
group
substituted
silane
unsubstituted
moisture
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.)
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EP05803039A
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German (de)
English (en)
French (fr)
Inventor
Helmut Mack
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.)
Construction Research and Technology GmbH
Evonik Operations GmbH
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Construction Research and Technology GmbH
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Application filed by Construction Research and Technology GmbH filed Critical Construction Research and Technology GmbH
Publication of EP1812525A1 publication Critical patent/EP1812525A1/de
Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J133/00—Adhesives based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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

Definitions

  • This invention relates to a moisture-curing polyurethane-based binder, in particular for industrial and structural applications.
  • the invention further relates to a kit comprising two components for producing the moisture-curing binder, a method for producing the moisture-curing binder, and a moisture-cured binder prepared from the moisture-curing binder.
  • crosslinkable silane-terminated polyurethanes having at least one reactive silane group (these silane groups may contain either a hydroxyl group or a hydrolyzable group such as alkoxy, acetoxy, oxime, benzamide or a chlorine atom bonded to silicon), preferably with two or three reactive silane groups , have long been for the production of adhesives and sealants and other industrial and construction products such.
  • adhesives and sealants As leveling compounds, floor coverings, paints and varnishes, potting compounds, foam, etc. used. Products with a good property profile while maintaining a reasonable commercial framework can thus be formulated.
  • joints serve to compensate for movements between individual components, the z. B. caused by thermal expansion or setting operations.
  • sealants for example according to DIN EN ISO 11600, are used to seal the joints.
  • Silane-modified polyether urethanes with reactive silane groups and their use in adhesives and sealants are known and described, inter alia, in US 5,554,709, US 4,857,623, US 5,227,434, US 6,197,912, US 6,498,210 and US 4,364,955.
  • Polyether urethanes with reactive silane groups can be prepared by various methods.
  • One possibility is the reaction of aliphatic or aromatic diisocyanates in stoichiometric excess with polyether polyols, which are preferably composed of ethylene oxide and / or propylene oxide, to isocyanate-containing polyurethane prepolymers, which are then reacted with aminosilanes, preferably secondary aminosilanes, to silane-modified (silane-terminated) polyurethanes ,
  • polyether polyols which are preferably composed of ethylene oxide and / or propylene oxide
  • aminosilanes preferably secondary aminosilanes
  • silane-modified (silane-terminated) polyurethanes silane-modified (silane-terminated) polyurethanes
  • polyether polyols which are preferably composed of ethylene oxide and / or propylene oxide, to hydroxyl-terminated polyurethane prepolymers, which can then be reacted with an isocyanatosilane to silane-terminated polyurethanes.
  • silane groups can then be introduced via a hydrosilylation reaction with hydrogen silanes such as HSiMe (OMe) 2 or HSi (OMe) 3 , under noble metal catalysis, preferably platinum catalysis. This silane-terminated polyurethanes are obtained.
  • polyether diols or polyether blends can be reacted with isocyanatosilanes such as gamma- and alpha-isocyanatosilanes, more preferably di- and trialkxoxy-functional gamma and alpha-isocyanatosilanes.
  • EP 596360 and US 6599354 describe the Preparation of a non-cyclic urea derivative from maleic and / or fumaric acid esters and amino silanes with primary amino groups by Michael addition.
  • the noncyclic urea derivatives thus prepared are reacted with isocyanate-containing polyurethane prepolymers to give silane-terminated polyurethanes.
  • WO 2004/060953 and US 2004/0122200 state that cyclic silane-containing urea derivatives at the ends are necessary for good thermal stability of the silane-terminated polyurethanes thus prepared. These are obtained by treating the non-cyclic urea derivatives with heat and acidic catalysts.
  • US 2004/0087752 and WO 1996/34030 describe polydiorganosiloxane urethanes reacted from ⁇ , ⁇ -hydroxydiorganosiloxanes, diisocyanates and polyether polyols to hydroxyl-containing polydiorganosiloxane urethane prepolymers.
  • US 2004/0087752 describes the subsequent reaction with isocyanatosilanes to silane-modified polydiorganosiloxane urethanes.
  • the described silane-modified polyurethanes and polyurethane copolymers are capable, even at room temperature, of being activated by hydrolysis with elimination of the corresponding leaving group (eg alcohol, ketoxime, acetic acid, etc.). Then there is a condensation reaction, forming a Si-O-Si network. It is advantageous that in the silane crosslinking no gaseous by-product as in the classic urethane crosslinking is free. Thus, isocyanate-free products can be formulated largely safely. It is known that volatile isocyanate monomers are suspected to be harmful to health.
  • the corresponding leaving group eg alcohol, ketoxime, acetic acid, etc.
  • silane-terminated polyurethanes Depending on the content of the reactive silane groups and depending on the structure of the binder, long-chain polymers, relatively wide-meshed three-dimensional networks or highly crosslinked systems are formed. According to the countless possibilities for the design of such silane - terminated binders, the properties of the unvemetzten polymers (viscosity, solubilities, etc.) as well as the properties of the formulated and crosslinked compositions (mechanical properties such as modulus, tensile strength, elongation, etc. and hardness, through hardening, UV stability, heat resistance, adhesion, etc.) over a wide range , Accordingly diverse are the possible uses of such silane-terminated polyurethanes.
  • the described silane-modified polyurethanes are also distinguished by the fact that an extremely broad raw material base is available.
  • Adhesives can be formulated. Accordingly, the scope of application of classical sealing tasks in construction, in
  • the described silane-modified polyurethanes and diorganosiloxane urethane polymers have the disadvantage of having an organic polymer backbone, which is resistant to ultraviolet light and weathering influences such.
  • B. Heat must be stabilized by additives such as light stabilizers (eg HALS hindered amine light stabilizer) and antioxidants (eg on a phenolic basis). These stabilizers can adversely affect the properties of the polymers; In addition, their content in the polymer decreases over time due to decomposition and exudation.
  • the polyurethanes are characterized among others by their -NH-CO-O- grouping in the backbone.
  • ester groups When the ester bridges in the chain are broken, new alcohol and carboxyl groups are formed. The latter act catalytically on further hydrolysis reactions.
  • Polyether-based polyurethanes are hydrolyzed by acids. Thermal decomposition reactions are enhanced by oxygen and moisture. Basically, polyester polyurethanes are more stable than polyether polyurethanes. Light-induced aging is still promoted by high humidity. Polyurethanes are particularly vulnerable in this regard as compared to other plastics because the amino groups contained in them are photosensitive. Often there are additional tertiary amines in the polymer structure due to the manufacturing processes.
  • polyurethanes Under the influence of oxygen, hydroperoxides are formed during photochemical degradation and absorb in both UV and shorter-wave VIS.
  • the photostability of the polyurethane depends on its components of production: For example, polyurethanes from aromatic isocyanates are considered to be particularly unstable. Polyurethanes are also an exception among plastics for microbial infestation. Due to their high nitrogen content, they are considered to be attractive for microorganisms.
  • a moisture-curing binder which comprises:
  • This binder can cure in the presence of moisture by forming a siloxane network.
  • the invention further provides a kit for producing the moisture-curing binder according to the invention, wherein the kit contains the above components (i) and (ii) separately from each other, preferably airtight in each case.
  • the invention further provides the use of the above component (i) and the above component (ii) for the preparation of one-component or two-component elastomers, sealants, adhesives, elastic adhesives, hard and soft foams, coating systems such as paints or varnishes, molding compounds, casting compounds and leveling compounds. Flooring, etc ready.
  • the invention provides a moisture-cured binder obtainable by curing the moisture-curing composition of the invention Binder in a moisture-containing atmosphere.
  • the heat stability and the light stability and thus the weathering behavior of moisture-cured binders based on silane-modified polyurethanes can be improved if the moisture-curing binders are admixed with a silane-modified acrylate polymer.
  • the silane-modified acrylate polymer can crosslink under the influence of moisture both with the silane-modified polyurethane and with itself.
  • the binder according to the invention after curing has comparable good or improved physical properties in comparison to conventional binders based on silane-modified polyurethanes alone.
  • Another advantage of the invention is that the components (i) and (ii) are perfectly compatible with one another and form stable compositions in a wide mixing range.
  • the sealants and adhesives formulated with the binder thus produced are well suited for gluing and sealing glass. Without fillers and discoloring materials can be crystal clear Make formulations. These are suitable for applications in which the adhesive, sealing or casting point at the boundary of two substrates optically
  • the moisture-curing binder of the invention is easy to prepare, crosslinked quickly, is very stable in storage, is resistant to ultraviolet light and weathering, adheres very well to a variety of substrates, leads to a low odor during curing, can be formulated with little crosslinking catalyst and thus has Excellent development potential for industrial and structural applications.
  • silane-modified acrylate polymer it is possible to use silane-modified acrylate copolymers such as block copolymers, graft copolymers, alternating copolymers or random copolymers in which moisture-reactive silanes such as alkoxysilanes are incorporated by polymerization.
  • silane-modified acrylate copolymers such as block copolymers, graft copolymers, alternating copolymers or random copolymers in which moisture-reactive silanes such as alkoxysilanes are incorporated by polymerization.
  • the preparation of acrylate polymers as well as the preparation of silane-modified acrylate polymers is well known.
  • the monomers used for the polymerization are usually alkyl acrylates, ie alkyl acrylates or alkyl methacrylates, such as.
  • MMA methyl methacrylate
  • the crosslinkers are highly reactive, less volatile and have at least two polymerizable functions in one molecule.
  • the preparation of polymeric binders based on acrylate copolymers, generally known by the term of synthetic resin products, is an essential one Application for alkylacrylates.
  • a special position takes acrylic glass, which is made almost exclusively from methacrylic acid methyl ester.
  • the polymer softening temperature in copolymers with the usual monomers can be covered in a range of -70 0 C to +110 0 C.
  • Long-chain esters such. B. in SMA lead to waxy polymer properties.
  • Branched alcohol esters provide polymers of reduced solution viscosity.
  • Silane-modified acrylate polymers can not be alone in z. For example, use sealant formulations because the resulting products would be too brittle.
  • acrylate and methacrylate polymers are prepared so as to obtain desired structure-property relationships.
  • Such polymerization processes are e.g. ionic and living polymerization. These allow a specific structure of the polymer structures. With them, it is possible to obtain narrow molecular weight distributions, to determine the type and number of end groups and to adjust the number of blocks, the block length and the block length distribution in the preparation of block copolymers.
  • the polymerization with metallocene catalysts allows the preparation of polymers with narrow molecular weight distribution, uniform comonomer distribution, the control of tacticity and the use of new comonomers.
  • the preparation of block copolymers of nonpolar and polar monomers is also possible.
  • An example of metal catalyst polymerization is the use of Ziegler-Natta catalysts.
  • Free radical polymerization is the most widely used process for preparing synthetic polymers. In particular, bulk plastics such as LDPE, PVC and PMMA are produced almost exclusively by free radical polymerization. Free radical polymerization is a chain reaction. Chain start, chain growth and chain termination take place parallel to each other.
  • initiators compounds which form free radicals by supplying energy, such as. B. azo or peroxy compounds. These radicals react with the monomers and start the chains. During chain growth, the radicals formed at the start of the chain accumulate additional monomers in a multiple addition, thus forming the polymer chains.
  • the free radicals are highly reactive and react with one another in a diffusion-controlled manner under combination or disproportionation. Another possible reaction is the transfer of the active center to z.
  • Example, another chain, a monomer, a solvent molecule or a targeted chain transfer agent, for. Mercapto compounds such as DS MTMO, DS MTEO, etc. Ideally, a Schulz-Flory distribution with 1.5 ⁇ PMI Polymerization Index ⁇ 2 is obtained.
  • Living polymerization is defined as a chain reaction without irreversible transfer and termination reactions leading to defined polymers.
  • concentration of the active species and the number of polymer chains remain constant during the course of the polymerization.
  • the molecular weight distribution ideally corresponds to a Poisson distribution.
  • a living polymerization that meets these requirements can be anionically and with restrictions carried out cationically or by group transfer.
  • the living polymerization requires an increased preparative effort. Since the chain ends remain active in the living polymerization even after complete conversion, end-functionalized polymers are accessible by sequential addition of various monomers block copolymers and by selective addition of termination reagents. The combination of these methods allows the construction of a variety of complicated polymer architectures, eg. B. star, crest and Graft copolymers and di-, tri- or multiblock copolymers.
  • Controlled radical polymerization was developed in the mid-1990's and combines the advantages of free radical polymerization, such as a wide range of monomers and ease of use (e.g., insensitivity to water and impurities), with the benefits of living ionic polymerization, e.g. As narrow molecular weight distributions, construction of complex polymer architectures and introduction of defined end groups.
  • the concept of controlled radical polymerization is based on an active and a dormant species. Only the active species is polymerizable, but both species are in an equilibrium that is far on the side of the dormant, inactive species. The exchange between the species is fast and reversible. The consequence is a very low steady state concentration of free radicals. The termination reactions are pushed back against the growth reactions.
  • This controlled (or even "living") radical polymerization allows a control of the polymerisation process and thus of the polymer architecture.
  • the molecular weight distribution ideally corresponds to a Poisson distribution.
  • ATRP can be applied to a variety of monomers, e.g. B. also on acrylates and methacrylates.
  • the wide range of initiator / catalyst systems makes ATRP very flexible in the choice of reaction conditions such. B. temperature and solvent.
  • the removal of copper salts is a cost problem.
  • redox processes can occur between the copper salts and the iron. This is countered with immobilization of the catalyst (eg on silica gel, polystyrene, etc.).
  • solvents such as supercritical carbon dioxide or ionic liquids are further suggestions.
  • Telecheles are low molecular weight oligomers and / or polymers (M n about 1,000 to 12,000) that have two defined reactive end groups. With their help, it is possible to produce defined structures such as block copolymers or networks for applications in the coatings, adhesives and sealants industry. Telecheles can be prepared by using suitable initiators, termination or transfer agents, or by chain analogue conversion. The best known reactions for the preparation of telechelics which have an exact functionality of two are polyaddition (eg polyurethanes, polyureas), polycondensation (eg polyamide, polycarbonate, polyester) and ring-opening polymerization of heterocyclic monomers (e.g. cyclic esters, carbonates, ethers), optionally with termination reagents containing the desired groups.
  • polyaddition eg polyurethanes, polyureas
  • polycondensation eg polyamide, polycarbonate, polyester
  • ring-opening polymerization of heterocyclic monomers e
  • Free radical polymerization uses dead-end polymerisation to produce telelates by using a large excess of an initiator bearing the desired functional group (eg, carboxylic acid and hydroxy telechels)
  • an initiator bearing the desired functional group eg, carboxylic acid and hydroxy telechels
  • this method is unsuitable, but alternatively, this method is unsuitable if a combination of growing chains is the only termination reaction (eg for styrene, methyl acrylate, etc.)
  • the polymerization may be carried out in the presence of a suitable chain transfer agent (e.g., CCI 4 , CBr 4 , CHCl 3 , CHBr 3 , disulfides, sulfur silanes (e.g., (RO) 3 Si (CH 2 ) 3 -S 2 - (e.g.
  • Telecheles can also be prepared by living ionic polymerization or by ATRP.
  • the ATRP applicable to the manufacture of telechelium is based on the reversible exchange of a halogen atom between initiator or growing polymer chain and a transition metal-containing catalyst system (eg, Cu, Fe, Co, Ru, etc.), which can be used to suppress radical concentrations and thus suppress the typical radical polymerization termination reactions.
  • ATRP can be used to produce acrylate- and methacrylate-based telechelics with a narrower molecular weight distribution than is possible with classical polymerization techniques If the initiator carries two halogen groups (eg dichlorotoluene), a halo-telechelic agent is formed by mono- or di-directional growth ler groups, eg. B. Alkoxysilanend phenomenon produce.
  • Silane-modified acrylate polymers which can be used for this invention are e.g. in US 4,333,867 and in US 1, 096,898.
  • silane group-containing (preferably alkoxysilane group-containing) monomers such as vinyl, acrylic or
  • Methacrylsilane be copolymerized with the acrylate monomers according to one of the above-mentioned methods.
  • Acrylate polymer for use in the binders of the invention is obtainable by copolymerization of a silane of the formula (I):
  • R is a substituted or unsubstituted, linear or cyclic
  • Alkyl group a substituted or unsubstituted aryl or
  • Aralklytik a substituted or unsubstituted alkoxy group; an oxime group, an acyloxy group, or a
  • R 1 is - (CH 2 -CH 2 -O) 111 -R 2 or - (CH 2 -CHR'-O) m -R 2 ;
  • R 2 is H, a substituted or unsubstituted, linear or cyclic
  • Alkyl group or a substituted or unsubstituted aryl or aralkyl group
  • R 3 is a substituted or unsubstituted, linear or cyclic
  • R 4 is hydrogen, halogen, a substituted or unsubstituted, linear or cyclic alkyl group, a substituted or unsubstituted
  • Aryl or aralkyl group an alkenyl group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, a nitrile group,
  • R 5 is hydrogen, halogen, a substituted or unsubstituted, linear or cyclic alkyl group, or a substituted or unsubstituted aryl or aralkyl group.
  • R 6 is hydrogen, halogen, a substituted or unsubstituted, linear or cyclic alkyl group, or a substituted or unsubstituted aryl or aralkyl group
  • R 7 is hydrogen, halogen, a substituted or unsubstituted, linear or cyclic alkyl group, a substituted or unsubstituted aryl or aralkly group, an alkenyl group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, a nitrile group, a pyridyl group, an amide group, or a glycidoxy group is.
  • the resulting silane-modified acrylate polymer then preferably contains silane groups according to one of the following formulas:
  • R 1 , R 2 , R 3 , n, m, p and q are as defined above.
  • the substituted or unsubstituted, linear or cyclic alkyl group of the radical R may contain 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • Linear and cyclic alkyl groups are preferred for R, which may be substituted.
  • substituents of the linear or cyclic alkyl group are alkyl and alkoxy groups having 1 to 6 carbon atoms. Multiple substitutions are possible.
  • the linear or cyclic alkyl groups are unsubstituted or mono-substituted.
  • Examples of the linear alkyl groups are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl.
  • cyclic alkyl groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the aryl group of the radical R may be, for example, phenyl or naphthyl.
  • the aralkyl group is preferably an Ar-Ci -6- alkyl group. Possible Substituents of the aryl or aralkyl group correspond to those of the linear or cyclic alkyl groups, which substituents may also substitute the aryl group.
  • the alkoxy group and the acyloxy group may contain 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Possible substituents of the alkoxy group and the acyloxy group correspond to those of the linear or cyclic alkyl groups.
  • the substituted or unsubstituted, linear or cyclic alkyl group, as well as the substituted or unsubstituted aryl or aralkyl group of R 2 and R 3 generally correspond to those given for R, except that the number of carbon atoms of the substituted or unsubstituted , linear or cyclic alkyl group may be 1 to 20.
  • Particularly preferred for R 2 are methyl and n-butyl.
  • Particularly preferred for R 3 is methyl.
  • silanes of formula (I) can be incorporated into a silane-modified acrylate polymer.
  • Preferred examples of the silanes of the formula (I) are MEMO (3-methacryloxypropyltrimethoxysilane), methyl-MEMO (methacryloxypropylmethyldimethoxysilane), ACMO (acryloxypropyltrimethoxysilane), VTEO (vinyltriethoxysilane), VTMOEO (vinyltris (2-methoxyethoxy) silane).
  • VTEO vinyltriethoxysilane
  • VTMOEO vinyltris (2-methoxyethoxy) silane.
  • the substituted or unsubstituted, linear or cyclic alkyl group corresponds to the substituted or unsubstituted aryl or aralkyl group of R 4 , R 5 , R 6 and
  • R 7 independently of one another those given above for R 2 and R 3 .
  • Alkoxycarbonyl group of R 4 , R 5 ; R 6 and R 7 are independent of each other and may have 1 to 10, preferably 1 to 6, carbon atoms.
  • Halogen of R 4 , R 5 , R 6 and R 7 can, in each case independently of one another, fluorine,
  • R 4 is hydrogen and methyl, ie the compound of formula (II) is preferably a (meth) acrylate.
  • R 5 is methyl, ethyl, propyl, n-butyl, i-butyl, decyl, dodecyl, cyclohexyl, stearyl, benzyl, 2-hydroxyethyl and 2-ethylhexyl.
  • Examples of the acrylate of the formula (II) are acrylic acid, methacrylic acid, acrylonitrile, methyl acrylate, ethyl acrylate, n / iso-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, glycidyl acrylate, stearyl acrylate, methyl methacrylate, n / iso-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, stearyl methacrylate,
  • Glycidyl methacrylate acrylamide. These and other acrylates can be selected and combined depending on the desired properties of the silane-modified acrylate polymer to be obtained.
  • olefin of the formula (III) examples include ethylene, propylene, isoprene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, chlorostyrene, pyridine, 2-methylstyrene, divinylbenzene. These and other olefins can be selected and combined depending on the desired properties of the silane-modified acrylate polymer to be obtained.
  • 0.1 to 40 wt .-%, preferably 0.2 to 20 wt .-%, particularly preferably 0.2 to 10 wt .-% and most preferably 0.5 to 2 wt .-% of Silanes of the formula (I) are used in the monomer mixture and subjected to the copolymerization.
  • the acrylate of the formula (II) and the olefin of the formula (III) together preferably constitute at least 60% by weight, more preferably at least 80% by weight, and most preferably at least 90% by weight, of the copolymerization mixture.
  • TMPTMA trimethylolpropane trimethacrylate.
  • copolymers for the copolymerization such as amines (for example triethylamine, tripropylamine or tributylamine), halogen compounds (for example chloroform, carbon tetrachloride or carbon tetrabromide), mercaptans (such as 1-butanethiol, 1-hexanethiol, 1-dodecanethiol, ethyldisulphide, phenyldisulphide or Butyl disulfide), alcohols (such as ethanol, n- / iso-propanol or n- / iso- / tert-butanol), mercaptosilanes or sulfur silanes (such as Si 69, preferably MTMO, MTEO (3-
  • Mercaptopropyltriethoxysilane or methyl-MTMO
  • These may be used in an amount of 0.1 to 40 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% in the monomer mixture.
  • peroxo compounds for example benzoyl peroxide, benzoyl hydroperoxide, di-tert-butyl peroxide, di-tert-butyl hydroperoxide, acetyl peroxide, lauryl peroxide, hydrogen peroxide, persulfuric acid or diisopropyl peroxydicarbonate
  • azo compounds for example AIBN or substituted AIBN
  • the polymerization can be carried out in inert solvents such as diethyl ether, methyl ethyl ether, methyl cellosolve, pentane, hexane, heptane, xylene, benzene, toluene, methyl acetate, ethyl acetate, butyl acetate, etc. take place.
  • the polymerization temperature depends on the initiator used and is preferably between 45 ° C and 180 0 C.
  • the monomer mixture may be added portionwise or continuously. This allows a control of the heat of reaction.
  • Silanes such as ⁇ -and ⁇ -MEMO, methyl-MEMO, etc. are incorporated into the acrylate / methacrylate copolymer backbone and act Admission of moisture as crosslinking points.
  • the mechanical properties can be controlled, for example, via the monomer mixture, the amount of silane and the other reaction parameters (eg regulator amount).
  • Silane-modified polyurethanes suitable for use in this invention and methods for their preparation are known in the art (see Introduction).
  • Preferred polyurethanes are those based on polyalkylene glycol ethers (polyoxyalkylenes) or diorganosiloxanes (preferably dimethylsiloxane) as the diol component.
  • Such polyurethanes can be prepared as prepolymers and then silane-modified.
  • the silane modification usually occurs at the ends of the linear polyurethanes, so that the silane-modified polyurethanes for use in this invention are preferably silane-terminated polyurethanes.
  • silane-modified polyurethanes and their preparation are described.
  • NCO-terminated polyurethane prepolymers are prepared by excessively sessing the isocyanate.
  • the polyurethane prepolymer can be prepared from OH-terminated linear or branched diols or triols (preferably linear diols) with aliphatic or aromatic polyisocyanates (preferably diisocyanates).
  • the polyurethane prepolymer can also be prepared from aliphatic alcohols or OH-terminated linear and / or branched diols or triols with a mixture of aliphatic and / or aromatic mono- or diisocyanates.
  • This reaction is carried out preferably from 40 0 C to 100 ° C, particularly preferably from 40 0 C to 8O 0 C in the temperature range from 30 0 C to 12O 0 C,.
  • amine or organometallic catalysts known from polyurethane chemistry can be used in the preparation (for example described in US Pat. Nos. 5,554,709, 4,857,223 and 4,698,210).
  • the silane-modified polyurethane is obtainable by reaction with a silane of the formula (IV):
  • A is a linear alkylene group having 1 to 10 carbon atoms which may be substituted with one or more R 1 groups;
  • R ' is a substituted or unsubstituted, linear or cyclic
  • Alkyl group a substituted or unsubstituted aryl or aralkyl group, a substituted or unsubstituted alkoxy group; an oxime group, an acyloxy group or a benzamido group;
  • R 11 is - (CH 2 -CH 2 -O) m -R 12 or - (CH 2 -CHR'-O) m -R 12 ;
  • R 12 is hydrogen, a substituted or unsubstituted, linear or cyclic alkyl group or a substituted or unsubstituted aryl or aralkyl group;
  • R 13 is a substituted or unsubstituted, linear or cyclic
  • R 14 is hydrogen, a substituted or unsubstituted, linear or cyclic alkyl group, a substituted or unsubstituted aryl or aralkyl group or -A-SiR '(OR 11 ) p
  • the group Y can react with a terminal -NCO group, e.g. Polyurethanes can be obtained which contain end groups of one of the following formulas:
  • R 12 is particularly preferably methyl.
  • R 13 is particularly preferably methyl, ethyl, n-propyl, i-propyl or n-butyl.
  • R 14 is most preferably methyl or n-butyl.
  • R 14 is then preferably a substituted or unsubstituted, linear or cyclic alkyl group having 1 to 20 (preferably 1 to 10, more preferably 1 to 6) carbon atoms, a substituted or unsubstituted phenyl or phenylalkyl group or -A-SiR '(OR 11 ) p (OR 13 ) q .
  • the phenylalkyl group may enie phenyl-Ci- 6 alkyl group, preferably a phenyl-Ci- 3 alkyl group be such as benzyl.
  • Y is preferably -NHR 14 .
  • the radicals defined therein may be the same or different. 005/012258
  • R 14 -A- SiR '(OR 11 ) p (OR 13 ) q are those in which A is a linear alkylene group having 1 to 6, more preferably 1 to 3 Carbon atoms, such as the classes of the formulas HN [-CH 2 -CH 2 -CH 2 -SiR '(OR 11 ) p (OR 13 ) q )] 2 and HN [-CH 2 -SiR' (OR 11 ) p (OR 13 ) q)] 2 .
  • Examples of such compounds are ⁇ - and ⁇ -bis-AMMO (AMMO is 3-aminopropyltrimethoxysilane) and bis-AMEO (AMEO is 3-aminopropyltriethoxysilane).
  • the silane-modified polyurethane is preferably a metal-free silane-modified polyurethane, i. the above-described silane modification is preferably carried out in the absence of a metal catalyst to avoid traces of metal in the product.
  • metal-free silane-modified polyurethanes are described in detail in EP 1 245 602. The content of EP 1 245 602 is intended to be incorporated herein by reference.
  • the silane-modified polyurethane should have a molecular weight of 250 to 60,000, preferably 300 to 40,000, more preferably 1000 to 30,000.
  • polyether diols prepared for example in the KOH process, with a molecular weight of 1500 to 2000 for the Preparation of the NCO-terminated polyurethane prepolymers can be used.
  • such prepolymers are characterized by relatively high viscosities.
  • the formulation is associated with handling difficulties and should, for. B. be compensated by plasticizer additive and lower filler content.
  • a second example is the use of high molecular weight polyether (Acclaim ®) with low degree of unsaturation, by the metal cyanide (see US 5,227,434, WO 2004/060953 and DE 19849817).
  • Preference is given to polyols based on propylene oxide having molecular weights of 100 to 20,000, preferably 500 and 15,000, more preferably 1000 to 12000 used.
  • Suitable polyols are, for. Polyoxyalkylene diols (especially polyoxyethylene, polyoxypropylene and polyoxybutylene), polyoxyalkylene triols, polyteramethylene glycols,
  • Polycaprolactone diols and triols and similar compounds are, for.
  • Other usable polyols are, for.
  • one polyurethane molecule may contain more than two or more different diol components.
  • blends of different types of polyurethanes may be used, with the different types of polyurethane based on different diol components.
  • isocyanate usable for the preparation of the polyurethane prepolymers
  • aliphatic, cycloaliphatic and / or aromatic diisocyanates of the prior art having preferably an isocyanate content of 20 to 60% by weight may be used.
  • mixtures of said isocyanates can be used. It is also possible to use the numerous liquid diphenylmethane diiso
  • Desmodur ® N Desmodur ® N
  • a mixture of 2,4- and 4,4'-diphenylmethane diisocyanate (MDI) can be used, for.
  • OH-terminated polyurethane prepolymers are prepared by using the isocyanate in deficit.
  • the polyurethane prepolymers can be prepared from OH-terminated linear and / or branched diols and / or triols (preferably linear diols) with aliphatic and / or aromatic diisocyanates.
  • the polyurethane prepolymers can also be prepared from aliphatic alcohols such as OH-terminated linear and / or branched diols and / or triols with a mixture of aliphatic and / or aromatic mono- and diisocyanates.
  • the Reaction can be carried out in the temperature range from 30 0 C to 120 0 C, preferably 40 ° C to 100 0 C 1, more preferably 50 ° C to 80 ° C.
  • an OH / NCO equivalent ratio of 1.1: 1 to 3: 1, preferably 1.2: 1 to 1.7: 1 and particularly preferably 1.3: 1 to 1.6: 1 should be maintained.
  • the aminic or organometallic catalysts known per se from polyurethane chemistry can be used in the preparation (for example described in US 4345054, WO 2002/068501, WO 2004/060953 and US 2004/0181025).
  • the OH-terminated polyurethane prepolymer obtained is then silane-modified with an isocyanatosilane of the following formula (V):
  • A is a linear alkylene group having 1 to 10 carbon atoms which may be substituted with one or more R groups;
  • R ' is a substituted or unsubstituted linear or cyclic alkyl group, a substituted or unsubstituted aryl or aralkyl group, a substituted or unsubstituted alkoxy group; a
  • R 11 is - (CH 2 -CH 2 -O) 111 -R 12 or - (CH 2 -CH R'-O) m -R 12 ;
  • R 12 is hydrogen, a substituted or unsubstituted linear or cyclic alkyl group, or a substituted or unsubstituted aryl or aralkyl group;
  • R 13 is a substituted or unsubstituted linear or cyclic alkyl group, or a substituted or unsubstituted aryl or aralkyl group;
  • silane-modified polyurethanes which have end groups of the following formula:
  • the silane-terminated polyurethane should have a molecular weight of 250 to 60,000, preferably 300 to 40,000, more preferably 1000 to 30000th
  • This polyether diols prepared for example in the KOH process, with a molecular weight of 1500 to 2000 for the Production of the NCO terminated polyurethane prepolymers can be used.
  • such prepolymers are characterized by relatively high viscosities.
  • the formulation is associated with handling difficulties and should, for. B. be compensated by plasticizer additive and lower filler content.
  • a second example is the use of high molecular weight polyether (Acclaim ®) with low degree of unsaturation, by the metal cyanide (see US 5,227,434, WO 2004/060953 and DE 19849817).
  • Preference is given to using polyols based on propylene oxide having molecular weights of 100 to 20,000, preferably 500 and 15,000, particularly preferably 1,000 to 12,000.
  • Suitable polyols are, for.
  • Polyoxyalkylene diols especially polyoxyethylene, polyoxypropylene and polyoxybutylene
  • polyoxyalkylene triols especially polyteramethylene glycols,
  • Polycaprolactone diols and triols and similar compounds are, for. As tetraols, pentaols, hexaols, alkoxylated bisphenols or polyphenols, Zücker and sugar derivatives (eg., Sorbitol,
  • isocyanate usable for the production of the polyurethane prepolymers there can be used those mentioned above in process a).
  • ⁇ -silanes eg, OCN-CH 2 -Si (OR) 3
  • ⁇ -silanes eg, OCN-CH 2 -CH 2 -CH 2 -Si (OR) 3
  • the increased reactivity of the alpha-silanes also causes a reduced storage stability (dimer or trimer formation) of the silane or of the silane-modified or silane-terminated polyurethane produced in this way.
  • the preparation of the polyurethane prepolymer with terminal isocyanate groups can be carried out as in process a).
  • the "BAYER variant” is described, inter alia, in EP596360 and US Pat. No.
  • silane-modified polyurethanes are z. B. as Desmoseal ® LS 2237 (Bayer AG), polymer
  • Silicones and polyurethanes are in many ways complementary. Polyurethanes generally have a very good mechanics, silicones retain their elasticity, especially at low temperatures. In addition, silicones are water-repellent. The report describes the reaction of an NCO-terminated polyurethane silicone prepolymer with aminosilanes.
  • Polyurethane prepolymers with terminal isocyanate groups can by 005/012258
  • Polydiorganosiloxanes can be obtained.
  • the organo groups in the ⁇ , ⁇ -OH polydiorganosiloxanes are preferably linear alkyl groups of 1 to 6, preferably 1 to 3, carbon atoms. Particularly preferred are ⁇ , ⁇ -bishydroxypolydimethylsiloxanes.
  • polyols can be used. These polyurethane prepolymers can be reacted with an amino or
  • Mercaptosilane preferably silane-modified with a secondary ⁇ - or ⁇ -aminosilane or a ⁇ - or ⁇ -mercaptosilane.
  • Polyurethane prepolymers having terminal hydroxy groups can be obtained by reacting a deficit of an isocyanate with ⁇ , ⁇ ⁇ OH polydiorganosiloxanes.
  • polyols can be used.
  • These polyurethane prepolymers can be silane-modified with an isocyanatosilane, preferably with a ⁇ - or ⁇ -isocyanatosilane.
  • the moisture-curing binders according to the invention can be prepared by simple physical mixing of a silane-modified polyurethane (i) and a silane-modified acrylate polymer (ii), eg. B. based on a solids content of 50 wt .-% of a silane-modified polyurethane (i) to 50 wt .-% of a silane-modified acrylate polymer (ii).
  • Possible mixing ratios of the silane-modified polyurethane (i) to a silane-modified acrylate polymer (ii) of 99: 1% by weight to 1: 99% by weight.
  • z Example based on Mesamoll ®, aliphatic and / or aromatic hydrocarbons, phthalates (eg. B. DIUP, DIDP, DIOP, etc.), polyoxyalkylenes, Carbonklad (z. B. adipic acid esters, Sebazinklaster, etc.), etc. are added become.
  • plasticizer particularly preferably from 5 to 20% by weight of plasticizer, based on the total mixture.
  • water scavengers can also be added, for. Silane-based (such as VTMO (vinyltrimethoxysilane), VTEO (vinyl triethoxysilane), 6490, Si (OEt) 4 , HMDS, etc.), oxide base (e.g., CaO), isocyanate base, etc.
  • Preferred is Addition of 0.1 wt .-% to 10 wt .-% water scavenger, particularly preferably the addition of 0.2 wt .-% to 1.5 wt .-% water scavenger based on the total mixture of the moisture-curing binder.
  • the new binders can be used for one-component and two-component elastomers, sealants, adhesives, elastic adhesives, hard and soft foams, a wide variety of coating systems (paints and varnishes), impression compounds (eg for dental applications), casting compounds (eg in the automotive sector ) and leveling compounds (eg for structural applications), floor coverings, etc. These products can be applied in a variety of ways, such. As painting, spraying, pouring, pressing, etc. Preferably can be produced with the new binders adhesives and sealants and elastic adhesives.
  • Typical further constituents of a formulation of the binder according to the invention are solvents, fillers, pigments, plasticizers, stabilizing additives, water scavengers, adhesion promoters, thixotropic agents, crosslinking catalysts, tackifiers, etc.
  • Aromatic hydrocarbons e.g., toluene, xylene, etc.
  • esters e.g. Ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, etc.
  • ketones e.g., methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.
  • the solvent may be added already in the course of the radical polymerization.
  • the binders of the invention may be filled or unfilled.
  • fillers both extender fillers and reinforcing fillers can be used.
  • Extender fillers can make up more than 50% by weight of the total formulation. Preferably, 350 parts by weight of filler per 100 parts by weight of binder, more preferably 50 to 150 parts by weight of filler per 100 parts by weight of binder.
  • Extender and reinforcing fillers, surface-treated and / or not surface-treated, are e.g. B. natural and precipitated
  • Chalks such. As Imerseal ®, Carbital ®, Omyabond ®, Omya BLR3, Reverte ®, Winnofil ®, Socal ®, Hubercarb ®, Ultra Pflex ®, Hi Pflex ®, etc.), carbon black (such. B.
  • Corax® Black Pearls® , etc.
  • silicas used and / or precipitated and / or flame
  • silicas e.g. B. Cab-O-Sil ®, Aerosil ®, etc.
  • aluminum oxide also flame-alumina
  • Flammischoxide eg., SiO 2 O 3 ZAI 2 ZZFe 2 O 3
  • glass fibers aluminum silicates (such as.
  • kaolin calcined kaolin, clay, talc, wollastonite, etc.
  • aluminum hydroxide magnesium hydroxide
  • quartz cristobalite
  • barium sulfate glass beads
  • zeolites zinc oxide
  • nepheline syenite phyllosilicates
  • feldspar dolomite
  • magnesium carbonate Metal powder (eg zinc, iron, aluminum, etc.) and comparable fillers.
  • Metal powder eg zinc, iron, aluminum, etc.
  • Formulation with flame oxides eg Aerosil 0
  • the pigments may be of organic or inorganic origin (for example titanium dioxide, also flame titanium dioxide, aluminum-based effect pigments, for example from Eckart or Silberline, azo dyes, etc.).
  • the proportion of pigments in the formulation is preferably 0 to 80 parts based on 100 parts by weight of binder, more preferably 0 to 20 parts by weight.
  • z. To the final properties of the product to influence as positive or the compatibility of the filler to improve with the binder (to z. B. realize higher fill levels), can be common phthalates (z. B. Jayflex ®, Palatinol ®, etc. , Dibutyl phthalate,
  • Dicarboxylic acid esters e.g., dioctyl adipate, dioctyl sebacate, etc.
  • Polyalkylene glycol esters eg. B. Bezoflex ® 50 and 400, etc., diethylene glycol dibenzoate, triethylene glycol dibenzoate, etc.
  • chlorinated e.g. B. Bezoflex ® 50 and 400, etc., diethylene glycol dibenzoate, triethylene glycol dibenzoate, etc.
  • Hydrocarbons eg. As alkyldiphenyl, partially hydrogenated terphenyl, etc.
  • Mesamoll ® e.g. As alkyldiphenyl, partially hydrogenated terphenyl, etc.
  • Mesamoll ® e.g. As alkyldiphenyl, partially hydrogenated terphenyl, etc.
  • Mesamoll ® e.g. As alkyldiphenyl, partially hydrogenated terphenyl, etc.
  • Mesamoll ® epoxidized soybean oil
  • the plasticizer can already be added in the course of radical polymerization. In order to improve the compatibility of filler / plasticizer and to achieve handleable viscosities can in the course of formulation dispersing aids are used (eg. B. Dispex ®, low-viscosity polyacrylates, etc.).
  • the plasticizer content in the formulation is preferably 5 to 150 parts by weight based on 100 parts by weight of binder, more preferably 30 to 100 parts by weight.
  • Stabilizing additives such as ultraviolet light stabilizers and / or antioxidants can also be formulated. Usual and preferred are 0 to 30 parts by weight based on 100 parts by weight of binder, more preferably 0 to 10 parts by weight.
  • the Stabilmaschinesaddiitve are z. B. available from Great Lakes and Ciba Specialty Chemicals among the
  • Water scavengers / desiccants may inorganic oxides such. As CaO, etc., zeolites and / or monomeric, oligomeric and / or cooligomere silanes, z. For example, be DYNASYLAN® ®, Silquest ®, ®, etc. DYNASIL. To be favoured VTMO, MTMS 1 6490 and / or DYNASIL ® A used.
  • the formulation of storage-stable products without water scavenger / desiccant requires a predrying of the fillers and pigments. Usual and preferred are 0 to 20 parts by weight based on 100 parts by weight of binder, more preferably 0 to 10 parts by weight.
  • adhesion promoters common monomeric and oligomeric organosilanes can be used such.
  • DYNASIL ® (Degussa AG) used preferably alpha- and gamma-AMEO, -AMMO, -DAMO, -1411, -TRIAMO, -1505, etc., more preferably alpha- and gamma-AMMO, 1146, alpha- and gamma- GLYMO, etc. or their mixtures.
  • the primer affects the hardness of the crosslinked product. It can also be formulated no bonding agent. Before applying the product, priming the substrate is recommended. Epoxies, phenolic resins, titanates, zirconates, aromatic polyisocyanates, etc. can also be used as adhesion promoters. Usual and preferred are 0 to 20 parts by weight based on 100 parts by weight of binder, more preferably 0 to 5 parts by weight.
  • thixotropic agent can be microcrystalline polyamide waxes (eg. As Disparlon® ®, Crayvallac ®, thixatrol ®, etc.), silicas (eg. As Aerosil ®, Cab-O-Sil ®, HDK ®, etc.), hydrogenated caster oil
  • microcrystalline polyamide waxes eg. As Disparlon® ®, Crayvallac ®, thixatrol ®, etc.
  • silicas eg. As Aerosil ®, Cab-O-Sil ®, HDK ®, etc.
  • hydrogenated caster oil e. As Disparlon® ®, Crayvallac ®, thixatrol ®, etc.
  • silicas eg. As Aerosil ®, Cab-O-Sil ®, HDK ®, etc.
  • hydrogenated caster oil e. As Disparlon® ®, Crayvallac ®, thixatrol ®
  • thixotropic agent eg Casterwax from CasChem, Thixcin ® from Rheox, etc.
  • metal soaps such as calcium stearate, aluminum stearate, barium stearate, etc.
  • surface-treated clays and kaolins etc.
  • no thixotropic agent can be formulated.
  • the proportion of the thixotropic agent in the formulation is preferably 0 to 50 parts by weight based on 100 parts by weight, more preferably 0 to 15 parts by weight.
  • Crosslinking catalysts are the common organic tin, lead, mercury and bismuth catalysts, eg. Dibutyltin dilaurate (e.g. BNT Chemicals GmbH), dibutyltin diacetate, dibutyltin diketonate (e.g.
  • reaction products of organic tin compounds e.g. Dibutyltin dilaurate with Kieselklareestern (z. B. DYNASIL ® A and 40), are used as crosslinking catalysts.
  • titanates eg tetrabutyl titanate, tetrapropyl titanate, etc.
  • zirconates eg tetrabutylzirconate, etc.
  • amines eg butylamine, diethanolamine, octylamine, morpholine, 1,3-diazabicyclo [5.4.
  • DBU undezen-7
  • the proportion of the crosslinking catalyst in the formulation is preferably 0.01 to 20 parts by weight based on 100 parts by weight of binder, more preferably 0.01 to 10 parts by weight.
  • tackifier As a tackifier (Tackifier) can be used for z. B. pressure-sensitive adhesives are added. This can z. B. rosin acid ester (rosin, turpentine, etc.), phenolic resins, aromatic hydrocarbon resins, xylene phenolic resins, coumarin resins, petroleum resins, low molecular weight polystyrene, 1, 2-polybutadienes having a molecular weight of about 1000 to 3000, also hodroxy-terminated, Polyvest ® , Polyoil ® LCB 110 and LCB 130, etc.
  • substrates for pressure-sensitive adhesives z. As bands, sheets, foils, labels, etc. come into question.
  • the pressure-sensitive adhesive may be applied in situ, as a solution (eg, dispersion, emulsion, etc.), as a hotmelt, etc. on materials such as paper, cloth, textiles, metal foils, plastic films, glass fiber reinforced plastics, etc. at room temperature or also elevated temperature, for. B. in the presence of water or humidity, are applied.
  • the proportion of the tackifier in the formulation is preferably 0 to 100 parts by weight based on 100 parts by weight of binder, more preferably 0 to 50 parts by weight.
  • The% free NCO groups can, for. B. by titration (ASTM D 2572) or IR spectroscopy be determined.
  • NCO polyurethane prepolymer at 75 ° C 45.2 g (0:19 mole) of the secondary aminosilane g-n- butylaminopropyltrimethoxysilane, DYNASYLAN ® 1189 (MW 235 g / mol) are added. The mixture is then cooled to room temperature over the course of 2 hours and the silane-terminated polyurethane (polymer 1) is obtained.
  • the NCO content is 0% (IR spectroscopy).
  • Polymer 4 Polydiorganosiloxanurethan (polymer 4).
  • Silane-modified acrylate polymer polymer 5
  • the polymers 1, 2, 3 and 4 prepared in Examples 1 to 4 are each mixed with the silane-modified acrylate polymer (Polymer 5) in a ratio of 70% by weight to 30% by weight and 90% by weight to 10% by weight .-% intimately mixed under exclusion of moisture at 50 0 C for 1 h and then cooled to room temperature. The compatibility after storage under moisture exclusion is examined.
  • the polymer 3 is mixed with the polymer 5 in a ratio of 90 wt .-% to 10 wt .-% intimately with exclusion of moisture at 5O 0 C for 1 h and then cooled to room temperature.
  • the mixture is heated to 80 0 C and intimately mixed under vacuum for 2 h.
  • the silane-modified polymer 1 is mixed with the silane-modified polymer 5 in a ratio of 80 wt .-% to 20 wt .-% intimately with exclusion of moisture at 5O 0 C for 1 h and then cooled to room temperature.
  • the mixture thus prepared and, separately, the silane-modified polyurethane 1 are then mixed with 1.5
  • crosslinking catalyst Metal ® 740
  • the crosslinked binders are stored in a convection oven at 80 0 C for one week and the color change before and after storage with a
  • Chromameter ® CR 300 from Minolta Chromameter ® CR 300 from Minolta.
  • Binder formulation with polymer 1 and polymer 5 (weight ratio 80:20):
  • Binder formulation with Polymer 1 Before Storage: 4.0
  • the temperature resistance (here yellowing tendency) of the crosslinked binder based on polymer 1 can be improved by the addition of polymer 5.
  • the tensile peel test was conducted according to ASTM C 794 ("adhesion-in-peel").
  • the substrate selected was glass with isopropanol, detergent and 005/012258
  • the binder 1 is mixed with the binder 5 in a ratio of 80 wt .-% to 20 wt .-% intimately with exclusion of moisture at 5O 0 C for 1 h and then cooled to room temperature.
  • the mixture thus prepared and, separately, polymer 1 are then mixed with 1.5 parts by weight
  • Crosslinking catalyst (Metatin ® 740).
  • the formulated binders prepared in this way are doctored onto glass at a thickness of about 1.5 mm and then covered with an aluminum shield (hole size about 120 ⁇ m). Another 1.5 mm sealant (binder) is applied to the aluminum shield.
  • the specimens thus prepared are crosslinked at 23 0 C and 50% relative humidity for 14 days.
  • the cross-linked specimens are exposed to ultraviolet light for 350 hours in a QUV oven.
  • the glass side shows the ultraviolet light source.
  • the QUV test was carried out with a cycle of 4 h / 60 ° C / high humidity / light on and 4 h / 20 ° C / high humidity / light off.
  • the adhesion after ultraviolet light aging of the crosslinked binder with polymer 1 can be improved by adding polymer 5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Sealing Material Composition (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP05803039A 2004-11-17 2005-11-15 Feuchtigkeitshärtendes bindemittel Withdrawn EP1812525A1 (de)

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WO2006053724A1 (de) 2006-05-26
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