DE10062854A1 - Flexible and tough-elastic methacrylate adhesives - Google Patents

Abstract

The invention relates to a single or dual component adhesive compositions based on at least one (meth)acrylate monomer, at least one urethane (meth)acrylate, in addition to dissolved rubbers, and an initiator / activator system which can be used according to anaerobic or aerobic hardening mechanisms as single component adhesives, and used as dual component adhesives in the so-called A-B method. In comparison to known adhesives of said type, the inventive adhesives exhibit high flexibility and viscoplasticity, and are characterised by high tensile strength and a high T-peel resistance.

Description

The present invention relates to radically polymerizable Compositions based on (meth) acrylate compounds, and their Use for flexible and tough-elastic adhesives.

(Meth) acrylate adhesives are radically polymerizable adhesive mixtures which in addition to crosslinkable (meth) acrylate monomers, accelerators, Stabilizers, other additives for the adjustment of processing technology Properties such. Viscosity, thixotropy or for cheapening (eg fillers, Plasticizer). Such adhesives can be different Mechanisms are radically polymerized, in particular known 1-component anaerobic-curing adhesives that when exposed to oxygen the surrounding air or by saturating the adhesive mixture with oxygen Stable gases remain stable and cure only in the absence of oxygen. Furthermore, such (meth) acrylate adhesives are known which cure aerobically, d. H. they are storage stable in the absence of oxygen and harden only on access from oxygen. Furthermore, 2-component adhesive systems are known, so-called A-B systems, where the initiators and accelerators so on the Components A and B are distributed, that each component is stable on its own and only when the two components contact each other Curing process begins. Another possible curing of the radical polymerizable (meth) acrylate adhesives is the photopolymerization by Influence of high-energy radiation, in particular short-wave daylight or UV light, the latter compositions usually contain Photoinitiators.  

For viscosity adjustment, as well as for improving the mechanical Properties of the adhesives after curing such. Shrinkage, resistance, Aging behavior or temperature resistance, it is usual, the radical polymerizable (meth) acrylate adhesives high molecular weight polymers too add - z. B. on acrylate or methacrylate - or with Methacrylatprepolymeren such. As polyurethane dimethacrylates to put.

So describes z. B. WO 9514725 low-odor adhesive compositions, containing urethane groups containing (meth) acrylate compounds by Reaction of special polyester diols with diisocyanates and hydroxy-functional (meth) acrylate compounds were prepared. The special polyester diols are characterized by a C: O ratio of <2.1 and a C: H ratio <10 off. It is stated that these Adhesive compositions are particularly low odor and at Room temperature are liquid or pasty and elasticizing act.

JP-A-62062875 describes adhesive compositions containing C ₆ to C ₂₀ alkylene di (meth) acrylates as polyfunctional polymerizable monomers and monofunctional monomers copolymerizable therewith such. For example, methyl, ethyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl, benzyl or lauryl (meth) acrylate, and an elastomer having a secondary glass transition temperature up to 10 ° C and a polymerization initiator. As elastomers z. For example, polychloroprene rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, neoprene rubber, chlorosulfonated polyethylene rubber. Polymerization initiators UV sensitizers or photosensitizers, and redox catalysts are proposed. It is proposed to use these adhesives for bonding vehicle parts, electronic parts and building materials or machine parts.

JP-A-63000377 describes α-cyanoacrylate compositions having an unvulcanized elastomer having a Mooney viscosity ML _{1 + 30} of 15 to 60 at 70 ° C. Specifically, the use of a carboxylated acrylonitrile-butadiene copolymer elastomer having the tradename "Nipol 1072" is proposed.

In SU-A-911442 a photopolymerizable printing plate is included a layer of a solvent-based adhesive based on ethyl alcohol, an acrylonitrile-butadiene (meth) acrylic acid copolymer as a film-forming agent Component as well as ethylene glycol mono (meth) acrylate as crosslinking agent and a benzoin methyl ether described as a photoinitiator. Solvent-free Adhesive compositions are not disclosed in this document.

In view of this state of the art, the inventors have the task provided, radically curable adhesive compositions based on To develop (meth) acrylate compounds that are related to your mechanical Properties like shrinkage, shear strength, tough-elastic properties and Flexibility are improved without essential properties such as tensile shear strength or shear strength or storage stability to lose.

The achievement of the object of the invention can be found in the claims. It consists essentially in the provision of radically polymerizable compounds containing

• a) one or more (meth) acrylate monomers (e)
• b) optionally one or more urethane (meth) acrylate (s)
• c) one or more rubber (s) soluble in (meth) acrylic acid esters
• d) an initiator / activator system.

The acrylate or methacrylate monomers a) are selected from allyl acrylate, Allyl methacrylate, methyl acrylate, methyl methacrylate 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3- Hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, Benzyl methacrylate, phenylethyl methacrylate, 2-phenoxyethyl methacrylate,  Morpholinoethyl methacrylate, glycidyl methacrylate, piperidylacrylamide, Neopentylmethacrylat, cyclohexyl methacrylate, tert-butyl methacrylate and Tetrahydrofurfurylmethacrylat or mixtures thereof. Also Dimethacrylate, like z. TEGDMA (tetraethylene glycol dimethacrylate), TEDMA (triethylene glycol), Dimethacrylate), bisphenol A bis (hydroxypropyl methacrylate), tricyclodecane dimethacrylate are useful, especially in admixture with the aforementioned Mono (meth) acrylates. In preferred embodiments, however, the strong smelling, volatile compounds such. As methyl acrylate or Methyl methacrylate not used.

The urethane (meth) acrylate (s) or polyurethane (meth) acrylate (s) b) can be represented by the general formula I:

[H ₂ C = CR ¹ -C (= O) -OR ² -OC (= O) -NH-] _n R ³ (I)

wherein
R ¹ = hydrogen or a methyl group
R ² = a linear or branched alkyl group having 2 to 6 carbon atoms or alkylene oxides having 4 to 21 carbon atoms,
n = 1, 2 or 3, and wherein

• A) for n = 1 R ³ :
  • an aryl group having 6 to 18 carbon atoms,
  • a straight-chain or branched alkyl group having 1 to 18 carbon atoms or
  • - is a cycloalkyl group having 3 to 12 carbon atoms;
  • - for n = 2 R ³ :
    [-Q-NH-C (= O)] ₂ [{-OR ⁴ -OC (= O) -NH-Q'-NH-C (= O)} _m -OR ⁴ -O-],
    where m = 0 to 10, and
    R ⁴
    • a) a polycaprolactonediol residue,
    • b) a polytetrahydrofurfuryldiol radical or
    • c) is a diol residue derived from a polyester diol characterized by a C: O ratio of <2.6 and a C: H ratio of <10 and a molecular weight of 1000 to 20,000
  • - for n = 3, R ^{3 is} :
    [-Q-NH-C (= O) -O- ((CH ₂ ) ₅ -C (= O)) _p -] ₃ R ⁵ ,
    wherein R ^{5 is} a triol residue of a linear or branched trihydric alcohol containing 3 to 6 carbon atoms and p is 1 to 10 and
    Q and Q 'independently of one another are aromatic, aliphatic or cycloaliphatic groups containing from 6 to 18 carbon atoms, which are derived from diisocyanates or diisocyanate mixtures.

The compounds of the abovementioned formula (I) can be prepared by processes known per se in the art by reacting an acrylate (R ¹ = H) or methacrylate (R ¹ = CH ₃ ) containing hydroxyl groups in the ester group with isocyanate-containing compounds to form them from urethane troops.

The acrylates or methacrylates are therefore Hydroxyalkylacrylate or methacrylates, while the alkyl groups can be linear or branched and contain between 2 and 6 carbon atoms. It can  also the esters of acrylic acid and methacrylic acid with polyethylene glycol and / or Polypropylene glycol can be used.

Such acrylates or methacrylates contain 4 to 21 carbon atoms in the Ester group, corresponding to 2 to 10 ethylene oxide units and 1 to 7 Propylene oxide units. The preparation of such esters is known to those skilled in the art known.

Urethane (meth) acrylates of the formula (I) for n = 1 are known and can be prepared by known methods from the basic isocyanates by reaction with the corresponding hydroxyl-containing (meth) acrylates of the general formula

H ₂ C = CR ¹ -C (= O) -OR ² -OH

to be obtained.

Such methods are described, inter alia, in WO-A-86/01153 or US-A- 4,439,600.

Suitable acrylates or methacrylates are those for which R ^{2 contains} an ethylene, propylene, isopropylene, n-butylene, isobutylene group or ethylene oxide or propylene oxide units, wherein R ^{1 is} H or CH ₃ .

Preferably for the implementation of the isocyanates having the hydroxyl groups Acrylates or methacrylates are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy propyl acrylate, 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxy hexyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, Polypropylene glycol acrylate and polypropylene glycol methacrylate.

The straight-chain or branched alkyl groups having 1 to 8 carbon atoms for R ³ are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, , Neopentyl or the hexyl group. The cycloalkyl groups having 3 to 12 carbon atoms are preferably those selected from the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl groups.

As aromatic groups containing 6 to 18 carbon atoms, mention may be made in particular of the phenyl, 2-toluenyl, 4-toluenyl and the xylenyl group; these R ³ radicals are introduced by reaction of the hydroxyl group-containing (meth) acrylates with the corresponding isocyanates.

In the case of the compounds of the abovementioned general formula (I) in the case that n = 2, they are reaction products of the above Hydroxyl-containing acrylates or methacrylates with isocyanates, the are obtainable by reaction of suitable diols with diisocyanates. Both Diols are polycaprolactonediols, polytetrahydrofurfuryldiols and / or special polyester diols.

Polycaprolactone diols are obtainable by processes known per se Ring opening polymerization of caprolactone with suitable diols, wherein the Ratio of caprolactone to diol is 1 to 20, ie 2 to 40 mol Caprolactone per mole of diol is used. The molecular weight of Polycaprolactone diols is between 200 and 4000. As diols come in particular linear or branched divalent, 2 to 6 carbon atoms containing alcohols which are selected from ethylene glycol, 1,2- Propanediol, 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 2-methyl- 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2- or 1,6-hexanediol, 1,10-decane diol.

The aforementioned special polyester diols are described, for example, in WO 95/14725 on page 9 ff. in section c), which disclosed there Compositions are expressly part of this invention.

The polycaprolactone diols, polytetrahydrofurfuryldiols and / or special ones Polyester diols are then known in the art known methods reacted with aromatic, aliphatic or cyclic diisocyanates.  

Suitable diisocyanates, from which Q and independently Q 'are derived, are selected from 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'- Diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexyl diisocyanate, meta and para Tetramethylxylene diisocyanate, 3-isocyanatomethyl-3,5,5- trimethylcyclohexyl isocyanate (isophorone diisocyanate), hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, di- (2-isocyanatoethyl) - bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, 2,2,4- and 2,4,4-tri methylhexamethylene diisocyanate and mixtures thereof.

The molar ratio in the reaction of the diols with the diisocyanates may be in the Ratio of 1: 2 to 1: 1.1 vary.

For further details, in particular with regard to the detailed structure of Compounds of general formula (I) and the diols to be used is on DE-A-44 41 414 page 3 line 60 to page 5 line 5, the are expressly part of the present invention.

Another essential ingredient of the adhesive composition of the present invention is at least one rubber which is soluble in the aforementioned (meth) acrylic acid esters. Copolymers of acrylonitrile with butadiene and / or isoprene are preferably used for this purpose, which may optionally contain (meth) acrylic acid in a minor amount. The acrylonitrile content of the copolymers is between 10 and 50 wt .-% of the rubber compositions, preferably between 20 and 40 wt .-%, the (meth) acrylic acid content is between 0 and 1 wt .-%, preferably between 0.0 and 0 , 1 wt .-% of the rubber composition. In general, the abovementioned rubbers still contain olefinic double bonds, but it is also possible to use hydrogenated products of the abovementioned acrylonitrile-containing rubbers, so that the iodine value in accordance with DIN 53241 is between 0 and 350 g / ₂ . The suitable rubbers are high polymers, they have Mooney viscosities according to ASTM D 1646 ML _{1 + 4} at 100 ° C between 20 and 100.

Preferably, the composition according to the invention contains

• a) 80 to 10% by weight of the (meth) acrylate comonomer,
• b) 0 to 70% by weight, particularly preferably 10 to 60% by weight, of the polyurethane (Meth) acrylate,
• c) and from 1 to 20% by weight of the rubber soluble in (meth) acrylic acid esters, based on the total amount of polymerizable compounds.

The adhesive compositions of the invention are referred to as free-radical used polymerizable one- or two-component systems, they are in Essentially free of volatile solvents. In any case, an initiator and / or activator system used, which the polymerization of olefinic triggers unsaturated systems. The adhesive systems should be stable on storage, in Their application form they are particularly pasty to flowable. such Starters and / or activators for free-radically polymerizable adhesives known in principle.

So the 1-component systems can be both anaerobic and so on cure after an aerobic curing mechanism. The anaerobic adhesives are set so that the oxygen of the ambient air or in the Adhesive dissolved oxygen acts stabilizing, so that in the presence of Oxygen no curing of the adhesive takes place. In general, these include Initiator / activator systems peroxidic initiators and components of redox Activators. Examples of such anaerobic initiator / activator systems Curing adhesives are described for example in DE-A-311 133, the DE-A- 30 44 318, DE-A-24 41 943, EP-A-251 465 or EP-A-185 476 called. The initiator activator systems mentioned there are also part of the present invention.

Aerobic curing adhesive systems are available in the absence of oxygen as well as 1- Component systems stable in storage, in the case of oxygen access, the initiator Activated / activator system, so that the polymerization is triggered. such Initiator systems are described, for example, in WO 96/23036, WO 95/14725 or US Pat WO 99/27027.  

In the 2-component systems, one component is included next to the (Meth) acrylate compounds and optionally the rubber, the initiators and the second component contains besides the (meth) acrylate compounds and optionally the rubber, the accelerators / activators.

The two adhesive components are then either immediately before Apply to the parts to be mixed together or they will be separately on the Fügeteile applied and penetrate only when uniting the Fügeteile. The latter two-component system and the B process, details of all three curing processes of the radical, polymerizable (meth) acrylate adhesives are also available from G. Habenicht, "Glueing: Basics, Technology, Applications ", 3rd edition, Springer Verlag 1997 in the Chapters 2.1.1.2; Find 2.1.1.4 and 2.1.2.1.

To the flexibility and the tough-elastic properties of the cured To achieve adhesive effectively, it is necessary that the used Rubbers are dissolved in the adhesive mixture. This can be the one or the Rubber (e) either in one of the used (meth) acrylate compounds or a mixture of monomers can be dissolved, but it can in principle Other solvents may also be used, if necessary at a later date the manufacturing process can be removed by distillation again. The production the solutions in the various solvents can by conventional Dissolution methods both on a laboratory scale, eg. B. in a rotary evaporator, as also by stirring in a temperature-controlled boiler (at different Temperatures and stirring conditions), it can also by shaking in closed containers. In a preferred manner while the Rubber for dissolution cut into small pieces and into the solvent given.

To increase the storage stability (avoid premature polymerization during the storage time of the mixture) contain the adhesive compositions still known per se stabilizers, this is usually a Mixture of antioxidants and radical inhibitors. Below are some ty exemplary stabilizer components: pyrogallol, hydroquinone, Hydroquinone monomethyl ether, butylhydroxytoluene, triphenylphosphine and  Phenothiazine. Their quantity depends on the purpose. She can be in Individual case by professional considerations and / or by preliminary tests easy be determined. In general, the weight content of stabilizers at most 5 wt .-%, preferably 0.01 to 1 wt .-%, based on the total Composition. Too high an amount delays the desired one Polymerization during the curing of the adhesive.

In addition to the components already mentioned, the inventive Adhesive compositions contain other customary auxiliaries and additives such as B. soluble and / or insoluble fillers, thickeners, Thixotropic agents, pigments, soluble dyes and adhesion promoters. The prerequisite for this is, of course, that by selecting the auxiliary and Ensures that interference with the interaction of the initiator and Activator / accelerator components are excluded.

The compositions according to the invention are preferred as Sealing materials or adhesives used, they are low odor, flexible and tough-elastic. In their application form they are liquid to pasty and wise good moisture resistance. As mentioned above, you can be easily formulated as 1- or 2-component system and show Glass, ceramics, metals, plastics and cellulose containing materials, such as z. As wood excellent adhesion. This is reflected in particular by the determined tensile shear strengths on the various substrates according to DIN EN1465 as well as the shear strength according to DIN 54452 and angle peeling Strengths according to DIN 53282.

The following examples serve to illustrate more preferred Embodiments of the invention, wherein the selection of examples no Limitation of the scope of the subject invention is intended to represent.

Examples

The amounts mentioned in the following examples are parts by weight, if not stated otherwise.  

For A / B adhesives, the A and B components were prepared by cutting the rubber into small pieces and stirring to about 80 ° C in a portion of the monomer mixture of the A and B components, respectively, until the rubber sags had completely dissolved in the monomer mixture for about 4 hours, then the remaining formulation ingredients were added. The amounts of the positions 4) to 6) in component A or 4) to 7) in component B each refer to a batch according to Example 1 to 13.

Component A

AL = L <1) monomer AL = L CB = 3 <2) PUMA @ AL = L CB = 3 <3) NBR polymer @ 4) CUHP 80 2.91 g 5) Tributylamine 0.42 g 6) APH 0.73 g

Component B

AL = L <1) monomer AL = L CB = 3 <2) PUMA @ AL = L CB = 3 <3) NBR polymer @ 4) GR-80 24.00 g 5) BSI 0.70 g 6) Octa Solingen copper 0.007 g 7) Dryer 69 2.65 g

NBR used: Nipol 1072, Nipol 1472, Nipol DN 219 W, Breon NX 775 (all from Zeon)
Monomers: HPMA (hydroxylpropyl), THFMA (tetrahydrofurfuryl), IPGMA (isopropylidene glycerol) methacrylate

In the above examples, the following abbreviations were used:
PUMA = polyurethane methacrylate,
PUMA 54 = is the PUMA prepared in WO 95/147245 on page 33, V,
PUMA 148 = is the PUMA named in the same font on page 34
NBR = nitrile butadiene rubber (acrylonitrile butadiene rubber)
CUHP 80 = 80% cumene hydroperoxide,
APH = acetylphenyl hydrazine,
GR 80 = 3- [2- (methacryloyloxy) ethoxycarbonyl] propionic acid
BSI = o-sulfobenzoic acid imide,
Dryer 69 = Co- / Zr-octoate

In the table, SF = angle peel strength measured on steel specimens. Tensile shear strength was tested on PVC, PC (polycarbonate), ABS (acrylonitrile butadiene-styrene), Plexiglas (Plexi), PA (polyamide), Fe (steel) and aluminum (Alu) test specimens determined. The given values are in MPa, an "M" means material breakage "KB" means cohesive failure and "AB" means Adhesive failure.

From the above numbers it is clear that the invention Toughened adhesives have excellent strength values. there were the A and B components for the tested bonds in the Mixing ratio 1: 1 mixed and applied to the substrate and the second substrate half added thereto, the strength values were after 72 hours at Room temperature siege determined.

Claims (10)

1. one- or two-component free-radically polymerizable adhesive composition containing

• a) one or more (meth) acrylate monomers (e)
• b) optionally one or more urethane (meth) acrylate (s)
• c) one or more rubber (s) soluble in (meth) acrylic acid esters
• d) an initiator / activator system

2. Adhesive composition according to claim 1, characterized in that the rubber (s) c) is / are selected from copolymers of acrylonitrile with butadiene and / or isoprene and optionally (meth) acrylic acid with a Acrylonitrile content between 10 and 50% by weight, preferably between 20 and 40% by weight and a (meth) acrylic acid content of between 0.0 and 1% by weight, preferably between 0.0 and 0.1% by weight. 3. An adhesive composition according to claim 1 or 2, characterized in that the / the rubber (s) c) an iodine value according to DIN 53241 0-350 g has / have I _2/100 g. 4. adhesive composition according to claim 1 to 3, characterized the (meth) acrylate monomer (s) a) is present in an amount of from 10 to 80% by weight, the urethane (meth) acrylate (s) b) in an amount of 10 to 70% by weight and the soluble rubber (s) c) in an amount of 1 to 20% by weight are included. 5. Composition according to at least one of the preceding claims, characterized in that the urethane (meth) acrylate (s) b) correspond to the general formula (I):
(H ₂ C = CR ¹ -C (= O) -OR ² -OC (= O) -NH-) _n R ³ (I)
wherein
R ¹ = hydrogen or a methyl group
R ² = a linear or branched alkyl group having 2 to 6 carbon atoms or alkylene oxides having 4 to 21 carbon atoms and n = 1, 2 or 3,
where R ^{3 is} n = 1:
an aryl group of 6 to 18 carbons,
a straight-chain or branched alkyl group having 1 to 18 carbon atoms or
a cycloalkyl group having 3 to 12 carbon atoms;
R ³ for n = 2 is:
[-Q-NH-C (= O)] ₂ [{-OR ⁴ -OC (= O) -NH-Q'-NH-C (= O)} _m -OR ⁴ -O-]
where m = 0 to 10,
R ⁴

• a) a polycaprolactonediol residue,
• b) a polytetrahydrofurfuryldiol radical or

R ³ for n = 3 is:
[-Q-NH-C (= O) -O- ((CH ₂ ) ₅ -C (= O)) _p -] ₃ R ⁵ ,
wherein R ^{5 is} a triol residue of a linear or branched trihydric alcohol containing 3 to 6 carbon atoms and p is 1 to 10 and
Q and Q 'independently of one another are aromatic, aliphatic or cycloaliphatic groups containing from 6 to 18 carbon atoms, which are derived from diisocyanates or diisocyanate mixtures. 6. The composition according to claim 5, characterized in that R ^{2 is} selected from ethylene, propylene, i-propylene, n-butylene, i-butylene, ethylene oxide or propylene oxide units. 7. The composition of claim 5 or 6, characterized in that for n = 1 R ^{3 is} selected from methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, Pentyl, hexyl, phenyl, xylyl, tolyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. 8. Composition according to one or more of claims 5 to 7, characterized characterized in that Q and Q 'are derived independently Diisocyanates selected from 2,4-toluene diisocyanate, 2,6- Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'- Dicyclohexyl diisocyanate, meta and para tetramethyl xylene diisocyanate, 3 Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), Hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, Di (2-isocyanatoethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, 2,2,4- and 2,4,4-Trimethylenehexamethylene diisocyanate and mixtures thereof. 9. Composition according to one or more of claims 1 to 8, characterized in that the (meth) acrylate monomer (s) a) is / is selected are made of allyl acrylate, allyl methacrylate, methyl acrylate, methyl methacrylate, 2- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 or 3 Hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, 6- Hydroxyhexylacrylate, 6-hydroxyhexylmethacrylate, benzylmethacrylate, Phenylethyl methacrylate, 2-phenoxyethyl methacrylate, Morpholinoethyl methacrylate, glycidyl methacrylate, piperidylacrylamide, Neopentylmethacrylat, cyclohexyl methacrylate, tert-butyl methacrylate and Tetrahydrofurfurylmethacrylat or mixtures thereof.   10. The composition according to one or more of claims 1 to 9, characterized characterized in that the activator system is a peroxide activator system.