EP2340270A2

EP2340270A2 - Radically curable compositions with reduced plasticizer absorption

Info

Publication number: EP2340270A2
Application number: EP09784048A
Authority: EP
Inventors: Steffen Maier; Max Hug; Andreas Kramer; Fabio Cirillo
Original assignee: Sika Technology AG
Current assignee: Sika Technology AG
Priority date: 2008-10-17
Filing date: 2009-10-16
Publication date: 2011-07-06
Also published as: EP2177553A1; WO2010043707A3; WO2010043707A2

Abstract

The present invention relates to elastic (meth)acrylate compositions comprising at least one radically polymerizable monomer and at least one polyurethane (meth)acrylate obtained from the reaction of a polyester polyol with a diisocyanate and a (meth)acrylic acid or a (meth)acrylic amide or a (meth)acrylic acid ester of Formula (I). Compositions according to the invention are suitable as adhesives, sealants or coatings, in particular for the gluing of substrates containing plasticizers. Said compositions exhibit the advantage that they absorb no plasticizers or only insignificantly small amounts thereof.

Description

RADICALLY HARD-COMPOSITE COMPOSITIONS WITH REDUCED SOFTWARE MACHINERY

Technical Field The invention relates to the field of elastic adhesives, sealants and coatings based on radically polymerizable monomers.

PRIOR ART Compositions Based on Radically Polymerizable

Monomers, in particular (meth) acrylate compositions, have long been used in the adhesive, sealing and coating technology. Also known is the use of (meth) acrylate-functionalized elastomers to increase the flexibility of such adhesives and sealants and coatings. For example, such compositions are described in

WO 02/070620 A1. The compositions described often have very good flexibility and impact properties and are widely used. However, in the bonding, sealing or coating of plasticizer-containing materials, these compositions have the property of absorbing plasticizers exiting the substrate. In certain applications, this property is undesirable.

The increase in the crosslinking density which is often effective for reducing the plasticizer absorption of adhesives, sealants or coatings in this case is not suitable, since this reduces the elasticity of the composition.

Presentation of the invention

It is therefore an object of the present invention to provide elastic (meth) acrylate compositions which absorb no or only insignificantly small amounts of plasticizer.

Surprisingly, it has now been found that compositions according to claim 1 solve this problem. By using specific polyurethane (meth) acrylates based on polyester polyols, it is possible to prepare compositions which absorb no or only insubstantially small amounts of plasticizer, in particular from the substrates which are bonded, coated or coated with the (meth) acrylate composition. The use of polyurethane (meth) acrylates based on polyester polyols is in no way obvious to the person skilled in the art.

Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims.

Brief description of the drawings

Reference to the drawings embodiments of the invention will be explained in more detail. The same elements are provided in the various figures with the same reference numerals. Of course, the invention is not limited to the illustrated and described embodiments.

FIG. 1 shows a schematic representation of a window profile with glued-in

Insulating glass pane in cross section; Figure 2 is a schematic representation of two bonded substrates.

In the figures, only the elements essential for the immediate understanding of the invention are shown.

Ways to carry out the invention

The present invention is a composition comprising a) at least one free-radically polymerizable monomer M, and b) at least one polyurethane (meth) acrylate PUMA, which is obtainable from the reaction of a polyester polyol P with a diisocyanate and a (meth) acrylic acid or a (meth) acrylamide or a (meth) acrylic ester of the formula (I).

In this case, the radical R ^{1 is} a hydrogen atom or a methyl group.

The radical A is an (n + 1) -valent hydrocarbon radical having 1 to 6, in particular having 2 to 4, carbon atoms.

Y is O or NR ² , where R ^{2 is} a hydrogen atom or a monovalent hydrocarbon radical having 1 to 6 C atoms. In particular, Y is O.

The index n stands for a value of 1 to 3, in particular for 1.

Substance names beginning with "poly", such as, for example, polyisocyanate, polyurethane, polyester or polyol, in the present document refer to substances which formally contain two or more of the functional groups occurring in their name per molecule.

The term "polymer" in the present document comprises, on the one hand, a collective of chemically uniform, but different in terms of degree of polymerization, molecular weight and chain length macromolecules, which was prepared by a polyreaction (polymerization, polyaddition, polycondensation) Such a group of macromolecules from polyreactions, ie compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on predetermined macromolecules and which may be chemically uniform or chemically nonuniform.The term also includes so-called prepolymers, ie reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules. The term "polyurethane polymer" encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups.Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, Polyether polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.

By "molecular weight" is meant in this document always the number average molecular weight M _n .

The radically polymerizable monomer M is especially selected from the group consisting of methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, cyclohexyl (meth) acrylate, isobromyl (meth) acrylate and trimethylcyclohexyl (meth) acrylate , Preferably, the radically polymerizable monomer M is a methacrylate.

The proportion of free-radically polymerizable monomer M is preferably 10 to 90 wt .-%, in particular 25 to 75 wt .-%, preferably 30 to 65 wt .-%, of the total composition.

Furthermore, the composition comprises at least one polyurethane

(meth) acrylate PUMA, which is obtainable from the reaction of a polyester polyol P with a diisocyanate and a (meth) acrylic acid or a (meth) acrylamide or a (meth) acrylic ester of the formula (I).

Particularly suitable polyesterpolyol P are polyesters which carry at least two hydroxyl groups and are prepared by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols. Particularly suitable are polyester polyols which are prepared from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6. Hexanediol, neopentyl glycol, glycerol, 1, 1, 1-trimethylolpropane or Mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic, glutaric, adipic, trimethyladipic, suberic, azelaic, sebacic, dodecanedicarboxylic, maleic, fumaric, dimer fatty, phthalic, phthalic, isophthalic, terephthalic, terephthalate, Hexahydrophthalic acid, trimellitic acid and trimellitic anhydride or mixtures of the abovementioned acids, as well as polyester polyols from lactones such as ε-caprolactone.

Preferably, the polyester polyol P is an aliphatic polyester polyol.

Further preferably, the polyester polyol P is a polyester diol. Suitable polyester diols are, in particular, those which are prepared from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acid or from lactones such as ε-caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol , 1, 6-hexanediol, dimer fatty acid diol and 1, 4-cyclohexanedimethanol as a dihydric alcohol.

Also suitable as polyester polyols P are also polyether polyester polyols, in particular copolymers of the abovementioned polyester polyols and polyether polyols. For this purpose, suitable polyether polyols are, for example, those which are polymerization products of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule having two or more active Hydrogen atoms such as water, ammonia or compounds with multiple OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols , Pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1, 1, 1-trimethylolethane, 1, 1, 1 Trimethylolpropane, glycerol, aniline, and mixtures of the foregoing Compounds which can be used are both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and reported in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.

Particularly suitable are polyoxyethylene polyols and polyoxypropylene polyols, in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols.

Also particularly suitable are so-called ethylene oxide terminated ("EO" endcapped) polyoxypropylene polyols, the latter being specific polyoxypropylene polyoxyethylene polyols obtained, for example, by pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, upon completion of the polypropoxylation reaction alkoxylated with ethylene oxide and thereby having primary hydroxyl groups .Preferred in this case are polyoxypropylenepolyoxyethylenediols and polyoxypropylenepolyoxyethylenetriols.

Particularly suitable are polyester polyols P having a molecular weight of 400 to 12,000 g / mol, in particular 1,000 to 6,000 g / mol, preferably 20,000 to 5,500 g / mol.

The polyester polyols P are preferably amorphous polyester polyols, in particular those which are liquid at room temperature (23 ^° C.). Further preferred are polyester P having a low glass transition temperature (T _9), in particular a glass transition temperature in the range from -80 ⁰ C to 0 ⁰ C, especially from -70 ⁰ C to -50 ⁰ C. Such polyester polyols are compared to inter alia crystalline or solid polyester polyols, because they can be easier to incorporate in the existing free-radically polymerizable monomer M. In principle, all diisocyanates are suitable as diisocyanates. In particular, 1,6-hexamethylene diisocyanate (HDI) ₁ 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI) are suitable, 1,1-dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-S, S-thymethyl-S-isocyanatomethylcyclohexane (= isophorone diisocyanate or IPDI), perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1, 3 and 1, 4 Bis- (isocyanatomethyl) -cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3-xylylene diisocyanate, m- and p-tetramethyl-1,4-xylylene diisocyanate , Bis (1-isocyanato-1-methylethyl) naphthalene, 2,4- and 2,6-toluene diisocyanate (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate ( MDI) ₁ 1, 3- and 1, 4-phenylene diisocyanate, 2,3,5,6-tetramethyl-i, 4-diisocyanatobenzene, naphthalene-1, 5-diisocyanate (NDI) ₁ S ^ '- DimethyM ^' - dii Socyanatodiphenyl (TODI), oligomers and polymers of the aforementioned isocyanates, as well as any mixtures of the aforementioned isocyanates.

Preference is given to aliphatic and cycloaliphatic diisocyanates. Most preferred is 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).

Furthermore, to produce the polyurethane (meth) acrylate, PUMA requires (meth) acrylic acid or (meth) acrylamide or a (meth) acrylic ester of the formula (I).

Hydroxyalkyl (meth) acrylates are particularly suitable as (meth) acrylic esters of the formula (I). In particular, the (meth) acrylic ester of the formula (I) is selected from the group consisting of hydroxypropyl acrylate (HPA), hydroxypropyl methacrylate (HPMA) ₁ hydroxybutyl acrylate (HBA) or hydroxybutyl methacrylate (HBMA). Preferred are hydroxyethyl acrylate (HEA) and hydroxyethyl methacrylate (HEMA). Also suitable is a monohydroxypoly (meth) acrylate of a polyol, preferably of glycerol or trimethylolpropane. In a first process, the reaction of the polyesterpolyol P with the diisocyanate and (meth) acrylic acid or (meth) acrylamide or a (meth) acrylic ester of the formula (I) can be carried out by using the polyesterpolyol P and the diisocyanate by customary processes, for example Temperatures of 50 ⁰ C to 100 ⁰ C, optionally with the concomitant use of suitable catalysts, are reacted, it being important to ensure that the isocyanate groups are present in relation to the hydroxyl groups in a stoichiometric excess. The isocyanate-terminated polyurethane polymer resulting from this reaction is then reacted with (meth) acrylic acid, (meth) acrylamide or with a (meth) acrylic ester of the formula (I) to give the polyurethane (meth) acrylate PUMA.

Within the scope of this described preparation of the polyurethane (meth) acrylate PUMA, it is obvious to the person skilled in the art that with the reaction of the isocyanate-terminated polyurethane polymer resulting from the reaction of the polyester polyol P with the diisocyanate, with (meth) acrylic acid an acyl carbamate results and this is reacted under suitable reaction conditions after a decarboxylation to a (meth) acrylamide groups terminated compound. In the reaction of the isocyanate-terminated polyurethane polymer with (meth) acrylamide, on the other hand, compounds which have acylurea groups are formed. Compounds of these two types are also referred to herein as polyurethane (meth) acrylates.

In a second process, the polyester polyol P can be reacted with the diisocyanate, wherein the hydroxyl groups are present in a stoichiometric excess over the isocyanate groups. The hydroxyl-terminated polyurethane polymer resulting from this reaction can be esterified with (meth) acrylic acid to give the polyurethane (meth) acrylate PUMA. Another method for producing the polyurethane (meth) acrylate

PUMA is to react in a first step, the (meth) acrylic acid, the (meth) acrylamide or the (meth) acrylic acid ester of Fromel (I) with at least one diisocyanate, which is used in an amount that the Isocyanate groups are present in excess of the hydroxyl groups. In a subsequent reaction, the resulting isocyanate group-containing intermediate is reacted with at least one polyester polyol P to form the polyurethane (meth) acrylate PUMA. Also possible is the preparation of the polyurethane (meth) acrylate

PUMA by esterification of (meth) acrylic acid with a polyester polyol P, wherein the polyester polyol is in stoichiometric excess. In a subsequent reaction, the partially esterified polyester polyol P reacts with a diisocyanate to give the polyurethane (meth) acrylate PUMA.

The proportion of polyurethane (meth) acrylate PUMA is preferably 1 to 80 wt .-%, in particular 3 to 50 wt .-%, preferably 5 to 40 wt .-% ₍ of the total composition.

Furthermore, the composition may further comprise at least one radical generator. The radical generator is in particular a peroxide, a hydroperoxide or a perester, in particular a peroxide or a perester.

Since the composition according to the invention is preferably also stable on storage in air, this must be taken into account when choosing the radical generator. In particular, the composition thus contains no compounds which form radicals at room temperature under the influence of atmospheric oxygen or are converted to spontaneously reacting radical formers. The composition according to the invention preferably contains no hydrazone compounds, in particular those which do not react at room temperature under the influence of atmospheric oxygen to give spontaneously free-radical-forming hydroperoxides. Preferred hydroperoxides are at room temperature to some extent stable hydroperoxides such as cumene hydroperoxide. The composition according to the invention preferably contains no hydroperoxides which spontaneously form radicals at room temperature and thus impair the storage stability of the composition. Most preferably, the free radical generator is dibenzoyl peroxide. Typically, the composition further comprises at least one catalyst for radical formation. This catalyst is especially a tertiary amine, a transition metal salt or a transition metal complex. For example, such suitable tertiary amines are aromatic amines, in particular selected from the group consisting of N, N-dimethylaniline, N, N-diethylaniline, N, N-bis (hydroxyalkyl) aniline such as N, N-bis (2-hydroxyethyl) aniline, N, N-alkylhydroxyalkylaniline such as N-ethyl-N-hydroxyethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N-methyl-N-hydroxyethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine and also alkoxylated N, N-bis- (hydroxyethyl) -p-toluidines, N-ethoxylated p-toluidine, N, N-bis (2-hydroxyethyl) -xylidine, N-alkylmorpholine and mixtures thereof. Transition metal salts and transition metal complexes are, for example, salts and complexes of cobalt, nickel, copper, manganese or vanadium.

Other preferred catalysts for radical formation are described, for example, in Sections [0041] - [0054] of US 2002/0007027 A1, the entire disclosure of which is hereby incorporated by reference.

The catalyst for the radical formation is usually used in an amount of 0.01 to 3 wt .-%, in particular from 0.1 to 2 wt .-%, based on the composition.

For example, molecules which under the influence of heat or of electromagnetic radiation form radicals which then lead to the polymerization of the composition can also be used as radical formers. Typically these are thermally activatable free radical generators and photoinitiators.

Suitable thermally activatable free-radical initiators are those which are still sufficiently stable at room temperature but already form radicals at a slightly elevated temperature, for example azo-bis-isobutyronitrile (AIBN). As a photoinitiator radical generators are referred to, which under the

Influence of electromagnetic radiation to form radicals. Particularly suitable is a photoinitiator which, upon irradiation with an electromagnetic radiation of the wavelength of 230 nm to 400 nm radicals forms and is liquid at room temperature. For example, such photoinitiators are selected from the group consisting of α-hydroxyketones, phenylglyoxylates, monoacylphosphines, diacylphosphines, phosphine oxides and mixtures thereof.

The composition may furthermore additionally comprise at least one adhesion promoter, in particular a (meth) acrylic acid, a metal (meth) acrylate or a (meth) acrylate of the formula (II).

In this case, the radical R ^{4 is} either a hydrogen atom or a methyl group. The subscript u stands for a value of 1 to 15, in particular of 1 to 5, preferably of 1 to 3. The index q stands for a value of 1 to 3 and the index s for a value of 3 minus q.

Preferred metal (meth) acrylates are metal (meth) acrylates of

Calcium, magnesium or zinc, which have a hydroxyl group and / or (meth) - acrylic acid or (meth) acrylate as a ligand or anion. Particularly preferred metal (meth) acrylates are zinc di (meth) acrylate, calcium di (meth) acrylate, Zn (OH) (meth) acrylate and magnesium di (meth) acrylate.

Preferred (meth) acrylates of the formula (II) are 2-methacryloyloxyethyl phosphate, bis (2-methacryloyloxyethyl) phosphate and also tris (2-methacryloyloxyethyl) phosphate and mixtures thereof.

Further suitable adhesion promoters are silanes, in particular organofunctional silanes. Particularly suitable are (meth) acryloxy- alkyltrialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, glycidyloxyalkyl trialkoxysilane and the like. For example, such suitable silanes are commercially available under the trade name Dynasylan ^® MEMO from Evonik Degussa GmbH, Germany. The proportion of the optional adhesion promoter to the total composition is preferably between 0.01 and 12 wt .-%, in particular between 0.5 and 8 wt .-%.

Furthermore, the composition may additionally contain at least one core-shell polymer. Core-shell polymers consist of an elastic core polymer (core) and a rigid shell polymer (shell). Particularly suitable core-shell polymers consist of a rigid shell of a rigid thermoplastic polymer grafted onto a core of crosslinked elastic acrylate or butadiene polymer.

Particularly suitable core-shell polymers are those which swell in the free-radically polymerizable monomer M, but do not dissolve therein. Preferred core-shell polymers are the so-called MBS polymers commercially for example under the trade name Clearstrength ^® from Arkema Inc., USA, or Paraloid ^® from Rohm and Haas, USA, is. The core-shell polymers are preferably used in an amount of from 0.01 to 30% by weight, in particular from 10 to 25% by weight, based on the total composition.

The composition may further contain additional solid or liquid toughening agents. A "toughener" is here and hereinafter understood to mean an addition to a polymer matrix which, even at low additions of from 0.1 to 15% by weight, in particular from 0.5 to 8% by weight, based on the total weight of the composition Increases the toughness and thus is able to absorb higher bending, tensile, impact or impact stress before the matrix penetrates or breaks In addition to the core-shell polymers described above, suitable solid tougheners are, for example, organic ion-exchanged layered minerals. as known to the person skilled in the art under the terms Organoclay or Nanoclay; polymers or block copolymers, in particular the monomers styrene, butadiene, isoprene, chloroprene, acrylonitrile and methyl methacrylate, and chlorosulfonated polyethylene; and amorphous silica.

As liquid toughness is particularly suitable liquid rubbers, as under the trade names Hypro ^® CTBN ETBN or

VTBNs are commercially available from Emerald Performance

Materials, LLC, USA, as well as epoxy resin modified liquid rubbers of the

Type Hypro ^® CTBN.

Furthermore, the composition may additionally at least one

Contain filler. Particularly suitable are natural, ground or precipitated calcium carbonates (chalks), which are optionally coated with fatty acids and / or derivatives thereof, in particular stearates, montmorillonites, bentonites, barium sulfate (BaSO ₄ , also called barite or barite), calcined kaolins, quartz powder , Aluminum oxides, aluminum hydroxides, silicic acids, in particular pyrogenic silicic acids, modified castor oil derivatives and polymer powder or polymer fibers. Preferred are calcium carbonates, most preferred are coated calcium carbonates.

The filler is usually used in an amount of 0.01 to 50 wt .-%, in particular from 10 to 30 wt .-%, preferably 15 to 20 wt .-%, based on the total composition.

The composition may additionally contain at least one epoxy resin having on average more than one epoxide group per molecule. Preferably, these are diglycidyl ethers of bisphenol A, bisphenol F and bisphenol A / F. The term "A / F" refers here to a mixture of acetone with formaldehyde, which is used as starting material in its production.Preferably, the epoxy resin is an epoxy liquid resin. Solid resin.

Suitable liquid epoxy resins are, for example, under the trade names Araldite ^® GY 250, Araldite ^® PY 304, Araldite ^® GY 282 from Huntsman International LLC, USA, or DER ^® 331 or DER ^® 330 of The Dow Chemical Company, USA, or under the trade name Epikote ^® 828 or Epikote ^® 862 from Hexion Specialty Chemicals Inc, USA, are commercially available.

The composition may, if appropriate, additionally

Contain ingredients. Such additional constituents are, in particular, dyes, pigments, inhibitors, UV and heat stabilizers, antistatics, flame retardants, biocides, plasticizers, waxes, leveling agents, adhesion promoters, thixotropic agents, spacers and other common raw materials and additives known to the person skilled in the art.

The composition is preferably a two-component composition, wherein two components K1 and K2 are stored separately from each other until application. Typically, the first component K1 includes in particular those ingredients of the described composition which have radically polymerizable groups. The second component K2 contains in particular the radical formers. Furthermore, in a two-component composition, other constituents, especially those which would interfere with the storage stability of the composition by reaction with each other, can be stored separately.

In described two-component compositions, component K1 preferably has the free-radically polymerizable monomer M, the polyurethane (meth) acrylate PUMA and further optional constituents such as adhesion promoters, core-shell polymers, catalysts for radical formation, impact modifiers, metal oxides, pigments and fillers and the component K2 the radical starter and optionally present pigments, fillers and epoxy resins. The volume ratio when mixing K1 to K2 is in particular in the range from 1: 1 to 10: 1. In certain cases, it may be beneficial to use the two components

To color K1 and K2 differently. As a result, the mixing quality can be checked during the mixing of the components and mixing errors can be achieved recognize early. Likewise, this measure can qualitatively check whether the intended mixing ratio has been observed.

Such a two-component composition is typically stored in a package having two separate chambers. The component K1 is in this case in one chamber and the component K2 is present in the other chamber of the package. Suitable packages are, for example, double cartridges, such as twin or coaxial cartridges, or multi-chamber tubular bags with adapters. Preferably, the mixing of the two components K1 and K2 takes place with the aid of a static mixer, which can be placed on the package with two chambers.

Such suitable packages are described, for example, in US 2006/0155045 A1, WO 2007/096355 A1 and in US 2003/0051610 A1, the entire disclosure of which is hereby incorporated by reference.

In a large-scale plant, the two components K1 and K2 are typically kept separate from one another in barrels or hobbocks and during application, for example by means of gear pumps, pressed out and mixed. The composition can be applied to a substrate by hand or in an automated process by means of robots.

The curing of the composition according to the invention takes place by a free-radical polymerization reaction of the free-radically polymerizable monomers M and optionally further free-radically polymerizable

Ingredients in the composition. The process, especially the

Speed, which leads to the curing of the composition

Reaction, can be adjusted by the choice of ingredients used. Typically, the cure of the composition proceeds in the

Way that the composition despite a long open time already at an early stage receives a high initial strength. Furthermore, the invention relates to the use of a composition, as described above, as an adhesive, sealant or as a coating. In particular, the composition according to the invention is suitable for the bonding, sealing or coating of substrates consisting of plasticized materials. For example, these are plastics, building materials such as concrete or gypsum, or even painted substrates such as metals. Furthermore, the composition according to the invention is also suitable for bonds, seals or coatings in which the cured composition comes into contact with other plasticizer-containing adhesives, sealants and / or coatings. Preferably, the composition according to the invention is suitable for gluing in window construction, where glass is glued to plasticized PVC frame and / or where the adhesive is directly adjacent to a plasticizer-containing seal. Such a preferred application is shown for example in FIG.

Figure 1 shows a schematic representation of a window profile with glued insulating glass in the partial cross-section. In this case, an insulating glass pane consisting of glass panes 1, spacers 3 with primary seal 4 and secondary seal 5, glued to a window frame 2 made of polyvinyl chloride (PVC). In this case, the adhesive 6 is in direct contact with the plasticizer-containing window frame 2. Furthermore, the adhesive is in direct contact with the secondary seal 5, which often consists of a plasticizer-containing silicone sealant. Both the window frame 2 and the secondary seal 5 can sweat out plasticizer, which could then affect the adhesive 6. Other sources of plasticizer may be, for example, the primary seal 4, which connects the spacer 3 with the glass sheets, or any other existing seals, such as sealing lips 7. The inventive composition has the advantage that they no or only negligible amounts of plasticizer receives and therefore is not affected. So a constant and durable adhesive connection can be guaranteed. Also suitable is the composition according to the invention for bonding plasticized materials to materials which contain no plasticizers and / or which, on contact with plasticizers, can absorb them and can thereby be impaired in their properties. In such a use, the inventive composition, in addition to its function as an adhesive, sealant or as a coating, also serves as a softening barrier.

Figure 2 shows a schematic representation of two glued

Substrates, one of which consists of a plasticized material 8 and one of a non-plasticized material 9. Due to the property of the inventive adhesive 6, no plasticizer is a migration of plasticizers from the plasticizer-containing material 8 to the non-plasticized material 9 by the adhesive prevented through.

The substrate on the surface of which the composition is applied may have been previously treated with suitable pretreatment agents or cleaners. Such pretreatments include, in particular, physical and / or chemical cleaning methods, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents, or flame treatment or plasma treatment, in particular air plasma treatment at atmospheric pressure. Particularly suitable is the pretreatment or cleaning of the

Substrates with Sika ^® Cleaner P or Sika ^® ADPrep which are commercially available from Sika Switzerland AG.

The composition according to the invention is used in particular in a method of bonding two substrates S1 and S2 comprising the steps of i) applying a composition according to the above description to a substrate S1; ii) contacting the applied composition with a second

Substrate S2 within open time; or i ') applying a composition as described above to a substrate S1; ii ') applying a composition according to the preceding

Description on a substrate S2; iii ') joining the two composite substrates S1 and S2 within open time; or i ") Applying a composition according to the above description between two substrates S1 and S2, wherein the second substrate S2 consists of the same or a different material as the substrate S1 In the case of a two-component composition, before step i), or i '), ii') and i "), at least partial mixing of the two components.

Also possible is a method of bonding two substrates S1 and S2 comprising the steps i '") applying a component K1 according to the preceding

Description on a substrate S1; ii '") applying a component K2 according to the preceding

Description on a substrate S2; iii '") joining the two provided with one component K1 or K2 substrates S1 and S2.

In such a method, the two components K1 and K2 mix during the joining of the substrates. This method is particularly suitable for gluing over very thin adhesive layers.

In particular, the composition according to the invention is also used in a method of sealing or coating a substrate S1 comprising the steps i "") applying a composition according to the preceding

Description on a substrate S1; ii "") curing of the composition.

In the case of a two-component composition, before step i "'), at least partial mixing of the two components takes place.

Further, the present invention includes a cured composition obtainable from a previously described composition by a curing process. In particular, the composition is a two-component composition such that the cured composition is obtainable by at least partial mixing of the two components K1 and K2.

The invention likewise encompasses articles which have been bonded, sealed or coated by a previously described method. These articles are preferably a building, in particular a building construction or civil engineering, or an industrial good or a consumer good, in particular a window, a household machine, a sanitary object, a tool or a means of transport, in particular an automobile, a bus , a truck, a train or a ship. Such articles are preferably also add-on parts of industrial goods or means of transport, in particular also module parts, which are used on the production line as modules and in particular are glued or glued on. Preferably, the articles are windows, doors, gates, flaps, hatches and the like.

Examples

Preparation of the compositions

The constituents listed in Table 1 were mixed together in the stated parts by weight in a dissolver at a temperature of not more than 80 ° C. and stirred until a macroscopically homogeneous paste was obtained. Immediately after mixing of all ingredients, the test specimens were prepared. Production of Polyurethane Methacrylates PUMA 'and PUMA "based on Polvestern

There were 200 g of polyester diol (Dynacoll ^® 7230 from Evonik Degussa GmbH, Germany; calculated M _n = 3,500 g / mol; hydroxyl number 27 to 34 mg KOH / g) and 23 g of i-isocyanato-SS ^ trimethyl δ-isocyanatomethyl-cyclohexane (IPDI; Desmodur ^® I, Bayer MaterialScience AG) terminated in the presence of dibutyltin dilaurate at 90 ° C to a polyurethane polymer isocyanate groups reacted with a titrimetrically determined free isocyanate group content of 1.0 wt .-%. Subsequently, 18.1 g of hydroxyethyl methacrylate (HEMA), commercially available, was added under the trade name Rocryl ^® 400 from Rohm and Haas, USA, which reacts with the free isocyanate groups of the polyurethane methacrylate PUMA '. Obtained is a colorless liquid with an NCO content of <0.05 wt .-%. The polyurethane methacrylate PUMA "was prepared analogously to PUMA 'with a polyester diol (Dynacoll ^® 7250 from Evonik Degussa GmbH, Germany; calculated M _n = 5,500 g / mol; OH number from 18 to 24 mg KOH / g). This produced 200 g of polyester diol, 17.3 g of IPDI and 11.7 g of HEMA, giving a colorless liquid having an NCO content of <0.15% by weight.

Preparation of a Polyurethane Methacrylate PUMA REF Based on a Polvether

There were 758 g of polyether diol (calculated M _n = 4'00O g / mol, OH number 14.0 ± 1.5 mg KOH / g) and 45.5 g of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI ; Desmodur ^® I, Bayer MaterialScience AG) terminated in the presence of dibutyltin dilaurate at 90 ⁰ C to an isocyanate polyurethane polymer having a titrimetrically determined free isocyanate groups reacted to from 1.0 wt .-%. Subsequently, 26.54 g of hydroxyethyl methacrylate (HEMA), commercially available, was added under the trade name Rocryl ^® 400 from Rohm and Haas, USA, which with the free isocyanate groups to the polyurethane methacrylate REF reacts. Obtained is a colorless liquid with an NCO content of <0.05 wt .-%.

Description of the test methods The tensile strength and the elongation at break were determined according to DIN

EN 53504 (pulling speed: 200 mm / min) on films with a layer thickness of 2 mm, which cured in standard atmosphere (23 ± 1 ⁰ C, 50 ± 5% relative humidity). The samples were directly after storage for one day at 23 ⁰ C ( "Od DIDP"), and after 7 days (Jd DIDP ") and after 30 days (,, 3OD DIDP") and after a year ( "DIDP 365d") in storage diisodecyl (DIDP) tested. During storage, the specimens were completely covered with DIDP.

The plasticizer absorption was determined from the weight gain of films with a layer thickness of 2 mm, which, measured under standard conditions (23 ± 1 ⁰ C, 50 ± 5% relative humidity) aushärteten after these 7 days ( "7d DIDP") and 30 days ( "3Od DIDP") and one year ("365d DIDP") were stored in diisodecyl phthalate (DIDP) (weight gain versus "Od DIDP"). During storage, the specimens were completely covered with DIDP. Before the samples were weighed, they were dry-rubbed with a cloth.

Table 1 Compositions 1 and 2 and Reference Example Ref1 in parts by weight and the results; a catalyst for radical formation (tertiary amine based on toluidine). LIST OF REFERENCE NUMBERS

1 glass pane

2 window profile

3 spacers

4 primary seal

5 secondary seal

6 glue

7 sealing lip

8 plasticizer-containing material

9 non-plasticized material

Claims

claims

1. Composition comprising a) at least one radically polymerizable monomer M, and b) at least one polyurethane (meth) acrylate PUMA, which is obtainable from the reaction of a polyester polyol P with a diisocyanate and a (meth) acrylic acid or a (meth) acrylamide or a (meth) acrylic ester of the formula (I)

wherein the radical R ^{1 is} a hydrogen atom or a methyl group; the radical A for an (n + 1) -valent hydrocarbon radical having 1 to 6

C atoms stands;

Y is O or NR ² , where R ^{2 is} a hydrogen atom or a monovalent hydrocarbon radical having 1 to 6 C atoms; and the index n stands for a value of 1 to 3.

2. Composition according to claim 1, characterized in that the composition additionally contains at least one free radical generator, in particular a peroxide, a hydroperoxide or a perester, most preferably dibenzoyl peroxide.

3. Composition according to one of the preceding claims, characterized in that the free-radically polymerizable monomer M is selected from the group consisting of methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, cyclohexyl

(meth) acrylate, isobornyl (meth) acrylate and trimethylcyclohexyl (meth) acrylate.

4. Composition according to one of the preceding claims, characterized in that the free-radically polymerizable monomer M is a methacrylate.

5. A composition according to any one of the preceding claims, characterized in that the polyester polyol P has a molecular weight of 400 to 12'OOO g / mol, in particular 1 O00 to 6'00O g / mol, preferably 2'00O to 5'500 g / mol , having.

6. A composition according to any one of the preceding claims, characterized in that the polyester polyol P is an aiiphatic polyester polyol.

7. Composition according to one of the preceding claims, characterized in that the polyester polyol P is a polyester diol.

8. A composition according to any one of the preceding claims, characterized in that the diisocyanate is an aliphatic or a cycloaliphatic diisocyanate, in particular 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI).

9. A composition according to any one of the preceding claims, characterized in that the (meth) acrylic acid ester of the formula (I) is selected from the group consisting of hydroxypropyl acrylate

(HPA), hydroxypropyl methacrylate (HPMA), hydroxybutyl acrylate (HBA) or hydroxybutyl methacrylate (HBMA), hydroxyethyl acrylate (HEA) and hydroxyethyl methacrylate (HEMA).

10. A composition according to any one of the preceding claims, characterized in that the composition additionally contains at least one tertiary amine or a transition metal salt or a transition metal complex as a catalyst for the radical formation.

11. A composition according to any one of the preceding claims, characterized in that the proportion of polyurethane (meth) acrylate PUMA 1 to 80 wt .-%, in particular 3 to 50 wt .-%, preferably 5 to 40 wt .-%, of the total composition is.

12. A composition according to any one of claims 2 to 11, characterized in that the composition is bicomponent.

13. A composition according to claim 12, characterized in that the first component K1 contains the radically polymerizable monomer M and the polyurethane (meth) acrylate PUMA; and the second component K2 contains the radical generator.

14. Use of a composition according to any one of claims 1 to 13 as an adhesive, sealant or as a coating, in particular for the bonding or sealing or coating of substrates consisting of plasticized materials.

15. A cured composition obtainable from a composition according to any one of claims 1 to 13 by a curing process.