DE19848483A1 - Transparent adhesive, useful for the bonding of plastics and/or metals, contains a phosphorous containing compound having at least an olefinically unsaturated group and a P-OH group - Google Patents

Abstract

A transparent adhesive having high shear strength contains a phosphorous containing compound having at least an olefinically unsaturated group and a P-OH group. A transparent adhesive (I) having a high shear strength comprises: (A) 5-90 wt.% of a reactive diluent; (B) 10-95 wt.% of a (pre)polymer that is soluble in (A) (whereby (A)+(B)=100 wt.%); (C) a phosphorous containing compound having at least an olefinically unsaturated group and at least a P-OH group; (D) a radical initiator; and (E) optionally up to 100 pts.wt. (with respect to 100 pts.wt. (A)+(B)) of conventional additives. An Independent claim is included for a process for the preparation of a low odor, aerobically curing adhesive (I) by mixing components (A) - (D) and optionally (E) together.

Description

The invention relates to transparent adhesives with high Tensile shear strength based on acrylates or methacryla ten. Deos further, the invention also includes methods for Manufacture of these adhesives and their use.

Adhesives based on (meth) acrylates have been around for a long time known. The published patent application DE 17 19 179 describes for example liquid adhesive mixtures for plastics, to improve the tensile shear strength acrylic or Contain methacrylonitriles. The nitriles used are questionable from the point of view of health protection. The in the Examples of this publication described adhesive mixtures are due to their high percentage of nitrile or not transparent on di-isopropyl xantogen.

A low transparency of the adhesive joint is for many users not annoying, especially if the adhesive joint after the adhesive is provided with a varnish or the like. High quality ge and aesthetically demanding objects where the Transparency plays an important role in the purchase decision plays, such as furniture made of artificial glass, ver however, long that an adhesive ver is used, which creates a transparent adhesive joint.

EP-A-0 591 879 discloses a method for Bonding of amorphous plastics with the (meth) acrylate is hardened with the aid of microwaves. The through this Adhesive joint obtained process is transparent, but the tensile strength is too low for many applications.

In view of these problems, the present inventor based on the task of a transparent adhesive to be specified with high tensile shear strength.  

Since in particular the liability of the known acrylic glass adhesive materials on metal substrates is insufficient, it is Object of the invention to provide an adhesive which adheres excellently to metal substrates and at the same time does not lose its transparency.

Furthermore, it was an object of the invention to provide an adhesive for To make available to those who are not harmful to health Contains substances such as nitriles.

These and others will not be resolved in more detail explained, but from the introductory discussion of the State of the art easily accessible or from Conductable tasks through an adhesive with the characteristics of claim 1. Advantageous modifications of the he Adhesive according to the invention are in the on claim 1 back-related claims placed under protection. Terms Lich the method provides the subject of claim 9 a solution to the problem on which the invention is based, while. Claim 10 a special use of the inventions protects the adhesive according to the invention.

The fact that a transparent adhesive

• A) 5-90% by weight of one or more reactive diluents ner;
• B) 10-95% by weight of one or more (pre) polymers, which are soluble in component A);

components A) and B) giving 100% by weight;

• A) one or more phosphorus-containing compounds with at least one olefinically unsaturated Group and at least one P-OH group;
• B) one or more radical formers;

and optional

• A) up to 100 parts by weight, based on 100 parts by weight of components A) and B), usual additives

exists, it is not easily predictable to improve the tensile shear strength of a transparent adhesive. At the same time, by suitable selection of the individual components according to type and amount, adhesives according to the invention with an overall excellent range of properties can be produced:

• - complete hardening even of very thin adhesive layers on different substrates (metals and Plastics), so that after 1 h to 24 h the adhesive is no longer sticky even in contact with air;
• - Fast curing when using accelerators possible; Drip time may be preferred depending on the application vary between 5 and 60 min;
• - very high adhesive strength on surfaces of metals, like steel, brass, copper and aluminum, be it that they are smooth and have only been degreased with acetone or are chromated (yellow, olive and white or blue with egg ner cleaning by ethanol) or that they are corundum are radiant; and
• - good adhesion to plastics such as PMMA, ABS, PVC and PC.

Preferred embodiments of the adhesive according to the invention are characterized in that component C) in an amount in the range of 0.01 to 0.30 parts by weight, ins particularly in the range of 0.02 to 0.10 parts by weight to 100 parts by weight of components A) and B) becomes.  

Furthermore, adhesives are preferred whose component A) consists of

• 1. 60 to 100 parts by weight of (meth) acrylate
• 2. 0 to 40 parts by weight of polyvalent (meth) acrylate
• 3. 0 to 40 parts by weight of comonomer

is constructed.

Mixtures which are characterized thereby are particularly preferred records that the proportion of components A) in the range from 55 to 85% by weight, based on the weight of the components ten A) and B).

Furthermore, mixtures that are there are particularly useful are characterized by that the proportion of components B) in the range from 15 to 45% by weight, based on the weight of components A) and B).

In particular, the reactive diluent has a mixture Methyl methacrylate, GDMA and / or TEDMA.

Adhesive mixtures according to the invention are particularly suitable gene in which HEMA phosphate and / or HMCP phosphate as Be Part of components C) is used.

With regard to component B), syrups are based on (Meth) acrylate is particularly useful.

The invention also relates to a method for the production position of a transparent adhesive with high tensile strength which is characterized in that the Components A) to D) and optionally E) with one another mixes.

The adhesives according to the invention are used before used for bonding plastics and metals.

Under transparent adhesives, mixtures according to An say. 1 can be understood, whose yellowness index is smaller  than 2.5, preferably less than 2.0 and very particularly be is preferably less than 1.5. The yellowness index is on known and becomes according to ASTM D 1925 "Standard Testmethod for Yellowness Index of Plastics ".

The tensile shear strengths can be determined in accordance with DIN 53283 become. The obtained with adhesives according to the invention Adhesives have tensile shear strengths, which are usually greater than 10, preferably greater than 15 and very particularly are preferably greater than 20 MPa.

Component A)

Component A) is formed by reactive diluents where in these connections represent at least one have ethylenically unsaturated bond.

Particularly preferred reactive diluents are (meth) acrylates. Within the scope of the invention, both methacryla te as well as acrylates are understood. The (meth) acrylates can have one or more double bonds. (Meth) acrylates, the two or more reactive double bonds have in the context of the invention as polyvalent Designated (meth) acrylates.

The alcohol residue may contain heteroatoms, for example in the form of ether, alcohol, carboxylic acid, ester and Urethane groups.

To within the scope of the invention with particular success as a reak (Meth) acrylates that can be used as diluents u. a.

Alkyl (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, pentyl ( meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isooctyl (meth) acrylate, tetradecyl (meth) acrylate, etc .;
Alkyl (meth) acrylates derived from unsaturated alcohols, such as. E.g. oleyl (meth) acrylate, 2-propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, etc .;
Amides and nitriles of (meth) acrylic acid, such as N- (3-dimethylaminopropyl) (meth) acrylamide, N- (diethylphosphono) (meth) acrylamide, 1- (meth) acryloylamido-2-methyl-2-propanol, N- ( 3-di.butylaminopropyl) (meth) acrylamide, Nt-butyl-N- (diethylphosphono) (meth) acrylamide, N, N-bis (2-diethylaminoethyl) (meth) acrylamide, 4-methacryloylamido-4-methyl-2- pentanol, (meth) acryloylamidoacetonitrile, N- (methoxymethyl) (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N-acetyl (meth) acrylamide, N- (dimethylaminoethyl) (meth) acrylamide, N-methyl -N-phenyl (meth) acrylamide, N, N-diahyla (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide;
Aminoalkyl (meth) acrylates such as tris (2- (meth) acryloxyethyl) amine, N-methylformamidoethyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 2-ureidoethyl (meth) acrylate;
other nitrogen-containing (meth) acrylates, such as N - ((meth) acryloyloxyethyl) diisobutyl ketimine, 2- (meth) acryloyloxyethylmethylcyanamide, cyanomethyl (meth) acrylate, 2,2,6,6-tetramethylpiperidyl (meth) acrylate;
Aryl (meth) acrylates, such as nonylphenyl (meth) acrylate, benzyl (meth) acrylate, 2-naphthyl (meth) acrylate, phenyl (meth) acrylate, it being possible for the aryl radicals to be unsubstituted or substituted up to four times;
carbonyl-containing (meth) acrylates, such as 2-carboxyethyl (meth) acrylate, carboxymethyl (meth) acrylate, N- (2- (Nieth) acryloyloxyethyl) -2-pyrrolidinone, N- (3- (meth) acryloyloxypropyl) -2-pyrrolidinone , N- (meth) acryloylmorpholine, oxazolidinylethyl (meth) acrylate, N - ((meth) acryloyloxy) formamide, acetonyl (meth) acrylate, N- (meth) acryloyl-2-pyrrolidinone;
Cycloalkyl (meth) acrylates, such as cyclobutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloocayl (meth) acrylate, 3-vinylcyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate , Bornyl (meth) acrylate, cyclopenta-2,4-dienyl (meth) acrylate, isobornyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate;
Glycol di (meth) acrylates such as 1,4-butanediol (meth) acrylate, methylene (meth) acrylate, 1,3-butanediol (meth) acrylate, triethylene glycol (meth) acrylate, 2,5-dimethyl-1,6-hexanediol (meth) acrylate, 1,10-decanediol (meth) acrylate, 1,2-propanediol (meth) acrylate, diethylene glycol (meth) acrylate, ethylene glycol (meth) acrylate;
Hydroxylalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
(Meth) acrylates of ether alcohols, such as tetrahydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1-butoxypropyl (meth) acrylate, 1-methyl- (2-vinyloxy) ethyl (meth) acrylate, cyclohexyloxymethyl (meth) acrylate, methoxymethoxyethyl (meth) acrylate, benzyloxymethyl (meth) acrylate, furfuryl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, allyloxymethyl (meth ) acrylate, 1-ethoxybutyl (meth) acrylate, methoxymethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate;
(Meth) acrylates of halogenated alcohols, such as 2,3-dibromopropyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 1,3-dichloro-2-propyl (meth) acrylate, 2-bromoethyl (meth) acrylate, 2 -Iodoethyl (meth) acrylate, chloromethyl (meth) acrylate;
Oxiranyl (meth) acrylates, such as 10,11-epoxyundecyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, 2,3-epoxybutyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, glycidyl (meth ) acrylate;
Phosphorus, boron and / or silicon-containing (meth) acrylates, such as 2- (dibutylphosphono) ethyl (meth) acrylate, 2,3-butylene (meth) acryloylethylborate, 2- (dimethylphosphato) propyl (meth) acrylate, methyldiethoxy (meth) acryloylethoxysilane, 2- (ethylene phosphito) propyl (meth) acrylate, dimethylphosphinomethyl (meth) acrylate, dimethylphosphonoethyl (meth) acrylate, diethyl (meth) acryloylphosphonate, diethylphosphatoethyl (meth) acrylate, dipropyl (meth) acryloyl phosphate;
sulfur-containing (meth) acrylates, such as thiomethyl (meth) acrylate, thiocyclohexyl (meth) acrylate, thiophenyl (meth) acrylate, ethylsulfinylethyl (meth) acrylate, 4-thiocyanatobutyl (meth) acrylate, ethylsulfonylethyl (meth) acrylate, thiocyanatomethyl (meth) acrylate , Methylsulfinylmethyl (meth) acrylate, bis ((meth) acryloyloxyethyl) sulfide;
Tri (meth) acrylates such as trimethyloyl propane tri (meth) acrylate, glycerol tri (meth) acrylate;
Tetra (meth) acrylates, such as pentaerythritol tetra (meth) acrylate.

The compounds mentioned come alone as component A) or in mixtures of two or more as reactive reactants thinner in the adhesive mixtures according to the invention.

Particularly preferred reactive diluent components include ren within the scope of the invention u. a. Alkyl (meth) acrylates, the derived from saturated alcohols, like Me ethyl (meth) acrylate, ethyl (meth) acrylate, isopro pyl (meth) acrylate, n-propyl (meth) acrylate, Butyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, isooctyl (meth) acrylate, tetrade cyl (meth) acrylate etc., allyl acrylate, allyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2- or  3-hydroxypropyl acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl (meth) acrylate, glycidyl (meth) acrylate, neopen tyl (meth) acrylate, isobornyl (meth) acrylate, cyclohe xyl (meth) acrylate, tert-butyl (meth) acrylate, tetrahydrofur furyl (meth) acrylate, maleic acid mono-2- (meth) acryloyloxyethyl ester, (7,7,9-trimethyl-4,13-dioxo-3, 14-dioxa-12-diazahexanedecane-1,16-dioldi (meth) acrylate), 3- [2 - ((Meth) acryloyloxy) ethoxycarbonyl] propionic acid or Mixtures of these.

Polar monomers, for example those with hydroxyl groups, can be used to improve liability. However, the amount of such polar Mo is expediently limited nomere to increase sensitivity to water swelling not increase unnecessarily. Pola are particularly preferred re, especially hydroxyl-containing monomers in one Quantity from 0.1 to 20 wt .-%, based on the sum of A) + B) limited.

Of particular interest as a component of component A) are methacrylates which act as crosslinking agents. These include di-, tri- and multi-functional connections. Difunctional (meth) acrylates and trifunctional (meth) acrylates are particularly preferred.

• a) Difunctional (meth) acrylates
  Compounds of the general formula:
  wherein R is hydrogen or methyl and n is a positive integer between 3 and 20, such as. B. Di (meth) acrylate of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol, compounds of the general formula:
  wherein R is hydrogen or methyl and n is a positive integer between 1 and 14, such as. B. di (meth) acrylate of ethylene glycol, diethylene glycols, triethylene glycols, tetraethylene glycols, dodecaethylene glycols, tetra decaethylene glycols, propylene glycols, dipropylene glycols and tetradecapropylene glycols; and glycerol di (meth) acrylate, 2,2'-bis [p- (γ-methacryloxy-β hydroxypropoxy) phenylpropane] or bis-GMA, bisphenol-A-dimethacrylate, neopentylglycol di (meth) acrylate, 2,2'- Di (4-methacryloxypolyethoxyphenyl) propane with 2 to 10 ethoxy groups per molecule and 1,2-bis (3-methacryloxy-2-hydroxypropoxy) butane.
• b) trifunctional or multifunctional (meth) acrylates
  Trimethylolpropane tri (meth) acrylates and pentaerythritol tetra (meth) acrylate.
• c) urethane (meth) acrylates
  Reaction products of 2 moles of hydroxyl group-containing (meth) acrylate monomer with one mole of diisocyanate and reaction products of a urethane prepolymer having two NCO end groups with a methacrylic monomer which has a hydroxyl group, as described, for. B. are represented by the general formula:
  wherein R _{1 represents} hydrogen or a methyl group, R _{2 represents} an alkylene group and R _{3 represents} an organic radical.

The mentioned crosslinking monomers are either which alone or in the form of a mixture of several monomers ren used.

Particularly advantageous monomers used in the adhesive according to the invention include, in particular, trimethyl olpropane trimethacrylate (TRIM), 2,2-bis-4 (3-methacryloxy-2-hydroxypropoxy) phenylpropane (bis-GMA), 3,5-dioxaoctamethylene dimethacrylate (TEDMA ) and / or 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diaza-hexadecane-1,16-dioxy-dimethacrylate (UDMA) as well as diacryl 121 (AKZO) and the like Products, e.g. B. the general formula

R ¹ , R ² = H, alkyl (preferably H, CH ₃ )
R ³ , R ⁴ = alkyl or
O-alkyl _n

e.g. B.

with n = 1 to 100 and m = 1, 2 or 3.

If as part of component A) crosslinkers from the Groups (a) - (c) are used, which aromatic Re is an amount in the range of 0.1-20% by weight, based on the sum of A) + B), particularly Cheap. The range from is particularly advantageous 0.1-10% by weight for aromatic crosslinking agents. Lies their proportion over 20 wt .-%, the weather stability Suffer. If this does not matter, there are also quantities of more than 20% by weight.  

Methyl has a special mixture of reactive thinners methacrylate, GDMA and / or TEDMA, GDMA for Gly koldimercaptoacetat and TEDMA for 3,6-Dioxaoctamethylene dimethacrylate.

The proportion of polyvalent (meth) acrylates is under Be taking into account the above information in principle unlimited. However, it has been found that their proportion is preferred to 40% by weight, based on the weight of component A), should be limited, otherwise mechanical properties or adversely affect the polymerization behavior can be influenced.

Component A) can also other comonomers contain copolyme with the above (meth) acrylates are risky. These include a. Vinyl ester, Vinyl chloride, vinylidene chloride, vinyl acetate, styrene, sub substituted styrenes with an alkyl substituent in the screen chain, such as B. α-methylstyrene and α-ethylstyrene, sub substituted styrenes with an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogen nated styrenes, such as monochlorostyrenes, Dichlorostyrenes, tribromostyrenes and tetrabromostyrenes, Vinyl and isopropenyl ether, maleic acid derivatives, as in for example maleic anhydride, methyl maleic anhydride, Maleimide, methyl maleimide, phenyl maleimide and cyclohe xylmaleimide, and dienes, such as 1,3-butadiene, Divinylbenzene, diallyl phthalate and 1,4-butanediol divinyl ether.

The proportion of the comonomers is 40% by weight of the component A) limited, otherwise the mechanical properties the polymerized coatings adversely affect can be flowed. The share of vinyl aromatics is here limited to 30% by weight of component A) because higher An parts to a segregation of the system and thus to one Can cause turbidity. It can also occur at higher proportions len on. Vinyl aromatics to reduce weather resistance  come. The proportion of vinyl esters is also up 30% by weight of component A) is limited, since this is at low Harden temperatures insufficiently and become too green tend to shrink.

All of the above monomers, which are in component A) are commercially available.

Accordingly, component A) is particularly preferred

• 1. 60 to 100 parts by weight of (meth) acrylate
• 2. 0 to 40 parts by weight of polyvalent (meth) acrylate
• 3. 0 to 40 parts by weight of comonomer

built up.

The amount of component A) can be in an inventive Vary glue over a wide range. Depending on the type is a smaller proportion (5% by weight based on A) + B)) or a larger proportion (up to 90% by weight on A) + B)) appropriate. If the amount of A) is below 5 wt .-%, then there is a risk that polymeric compo no longer dissolve the adhesive sufficiently. If the amount of reactive diluent is over 90% by weight, then can sufficient polymerization may not occur or that the shrinkage is too great.

Particularly favorable properties with regard to shrinkage and viscosity arise with adhesives with reactive kept thinner between 55 and 85 wt .-%, based on the Weight of components A) and B).

Component B)

To modify the viscosity of the adhesive according to the invention material mixture and the flow properties as well as esp seren hardening or other, especially mechanical egg  Properties of the adhesive contains polymers or Prepolymers which, according to the invention, in component A) must be soluble or swellable so that no clouding occurs.

According to the invention, inter alia, poly (meth) acrylates, Epoxy (meth) acrylates, aliphatic polyurethane methacrylates, Polyurethane acrylates or mixtures thereof as components te B) suitable. The (pre) polymers mentioned can also be used as Copolymers are used.

After the polymerization of components A), the (pre) polymer must be compatible with the resulting polymer AA). The characterization of the polymer blend can according to known criteria carried out (see this Krik-Othmer Encyclopedia of Chemical Technology, 3 ^rd Ed Vol 18, Be th 457-460, J. Wiley & Sons, 1982;.... J. Brandup, EH Immergut , polymer Handbook, 2 ^nd Ed. III, page 211, Wiley Interscience, 1975). With the polymer mixtures of AA) and B), only a refractive index and a single glass temperature are observed.

In the event that the polymers AA) and B) in their distinguish chemical structure, can be used to assess the Compatibility among other things the occurrence of the LCST (Lower Critical Solution Temperature) are used, their Existence on a segregation of a clear, transparent Polymer solution based in two phases by heating is induced, the mixture becoming cloudy.

The mixtures of the polymer AA) and the components ten B) have LCST values that are above the temperatures to which the adhesive joint is exposed. Preferably the LCST values are at least 20 ° C above this temperature structures that occur, for example, during processing ten.

Of particular interest for the invention include rem (pre) polymers based on (meth) acrylate (group B1),  polymeric crosslinkers (group B3), phenoxy resins (group B4) as well as bulk or emulsion polymers (group B5).

Group B1)

This group includes in particular polymers and prepoly mers, so-called syrups, based on (meth) acrylates.

These polymers are made up of the monomers that just if used as components of component A) can. The polymers obtained by polymerizing (Meth) acrylates and / or the above-mentioned comonomers hold, can also be used as a mixture the.

The polymerization can be either free radical or ionic take place, but preferably radical generating In itiators used. Examples of these initiators are un ter component D) described.

The (pre) polymers used should last for a long time span can be stored. This generally assumes that they do not polymerize or are free of residual amounts of initiator or radical formers.

The production of (pre) polymers based on (Meth) acrylates are well known in the art and described for example in the publication DE-A-28 43 759 ben to which express reference is made. The (Pre) polymers are generally commercially available.

Prepolymers and component A) can be the same or different the monomer and / or comonomer compositions sen. In particular, within the scope of the invention Glass temperature of a prepolymer to be used Copolymerization of methyl methacrylate and emollient Acrylates can be set specifically.  

Here, according to the invention with prepolymer is a pure bottom lymer or oligomer, possibly with low residual monomer hold, but not a syrup of polymer and monomer understand.

Particularly preferred prepolymers for the invention include Copolymers of methyl methacrylate with acrylates. Especially ders preferred thereof is a copolymer of MMA and n-butyl acrylate.

Group 2

Another group as part of components B) of is of particular interest is formed by TPU binders. The component of group B2) can consist of one or more TPU's exist.

Basically every polyester-based or po comes lyether-based polyurethane in question, insofar as it isn't right is active and thermoplastic. Within the scope of the invention under "not reactive" with regard to the polyurethane Component B2) understood a polymeric material which contains no free unreacted isocyanate groups. This has the consequence that the polyurethane has no significant chemical reaction with any component of the invention shows adhesive mixture according to the invention. A polyurethane, which does not meet these criteria can also be found in For the purposes of the invention, but only if it is treated or reacted in such a way that it complies with the Sufficiently met the requirements mentioned. At for example, you can use a polyurethane, which is Isocya free has natgruppen, with a monofunctional alcohol or similar compounds react to the free To eliminate isocyanate groups. It goes without saying that the reagent has no free olefinic double bonds should introduce.  

The term "thermoplastic" means in the sense of the inven with regard to polyurethanes that they do not swell or networked, and that they are in the invention Do not crosslink the adhesive formulation significantly.

Basically, polyurethanes meet the requirements "non-reactive" and "thermoplastic" essentially meet lichen linear, although a priori ramifications not out are closed as long as the resulting polymer is not in acrylic monomers insoluble gel forms. Larger ver degrees of branching, which is an insoluble, essentially three dimensional matrix polymer, prevent errei chung the objectives of the invention, and polyurethanes of Such nature is therefore not in the range of the present the invention.

The formation of polyester urethanes and polyether urethanes is based on the reaction of Isocyanate groups containing active hydrogen atoms Compounds containing hydroxyl groups. To form a High molecular weight polymers are preferably di functional reagents used, although lower proportions of connections with higher functionality, which leads to Bil leads to a certain degree of branching, or from ge lower proportions of monofunctional compounds, resulting in Chain termination leads, to some extent, to regulation and Allow control of molecular weight. Education sol cher polymer is known per se, and many polyurethanes, which meet these requirements according to the invention, are commercially available, or many are commercially available Liche polyurethanes can the Erfor be adapted.

The reactive, organic, polyfunctional polyols useful in the formation of polyether urethanes which can be used according to the invention and which can be reacted with suitable isocyanates include, inter alia, the polyalkylene ethers, thioether glycols and ether thioether glycols of the general formula (CI)

HO RX _n H (CI),

where R is one or more alkylene radicals with up to 10 carbons Substance atoms means X oxygen or sulfur or one Is a mixture of both and n represents an integer. It it is far preferred that n is a natural integer which is so large that the molecular weight of the polyal kylene ether glycol, polyalkylene thioether glycol or polyal kylene ether thioether glycol at least 500, preferably is between 500 and approximately 10,000.

Preferred polyalkylene ether glycols are u. a. Polyethylene lenglycol, polypropylene glycol, polybutylene glycol, poly tetramethylene glycol, polyhexamethylene glycol and the like. These are, for example, by acid-catalyzed poly condensation of the corresponding monomeric glycols or by condensation of low alkylene oxides, as in for example, ethylene oxide, propylene oxide and the like, get either with itself or with glycols, such as B. ethylene glycol, propylene glycol and the like.

Polyalkylene arylene ether thioethers and ether thioether glycols, which molecular weights range from about 500 to about 10,000 and which of the above. general formula correspond, differ from those already described NEN polyalkylene glycols in that they contain arylene radicals, such as B. phenylene, naphthylene and anthrylene residues, ent neither substituted or unsubstituted, instead of one against - but not all - alkylene radicals. This means that in the o. g. Formula R a mixture of alky represents len and arylene residues. In this case it did found to be particularly favorable that such material en a molecular weight of at least 500 for each sol Chen arylene radical.  

Another class of reactive, organic, polyfunctional ler polyols used in the preparation of the invention usable polyurethanes can be applied are the essentially linear polyester, which is a plurality contain isocyanate-reactive hydroxyl groups. While the production of polyesters suitable for this purpose is known per se, for better understanding noted that polyesters of this type in general by condensation of polyhydroxy compounds, in general mine of saturated aliphatic diols, such as as ethylene glycol, 1,2-propanediol, 1,3-propanediol, butane diol-1,3, butanediol-1,4, pentanediol-1,2, pentanediol-1,5, 1,3-hexanediol, 1,6-hexanediol, diethylene glycol, dipropy lenglycol, triethylene glycol, tetraethylene glycol and the like Chen, are also available, also by condensation of Mixtures of the diols mentioned with one another and from Mi of the diols mentioned with minor amounts of Polyols which have more than two hydroxyl groups, preferably saturated aliphatic polyols, such as. B. Glycerol, trimethylolethane, trimethylolpropane, pentaeryth riotol, sorbitol and the like, with a polycarboxylic acid or a polycarboxylic anhydride, generally one Dicarboxylic acid or a dicarboxylic anhydride, which ent are not saturated or which are exclusively benzene Contain double bonds, such as oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pime linseic acid, suberic acid, azelaic acid, sebacic acid, malein acid, phthalic acid, cyclohexanedicarboxylic acid and endomethy lentetrahydrophthalic acid and the like and their isomes ren, homologues and other substituted derivatives for example chlorine derivatives or with mixtures of such Acids with each other and with unsaturated dicarboxylic acids or unsaturated dicarboxylic acid anhydrides, such as wise maleic acid, fumaric acid, citraconic acid and itaconic acid re and similar, as well as with polycarboxylic acids with three or more carbonyl groups, for example aconitic acid and similar.  

The within the scope of the invention in the manufacture of Polyu rethanes used, essentially linear polyester have molecular weights in the range between 750 and about 3000 on. In addition, they preferably have low ones Acid numbers, for example, are acid numbers, which one Value of about 60, essentially not to The acid numbers are preferably and preferably in one range as low as possible, for example at 2 or we Accordingly, the essentially linear Polyesters generally have relatively high hydroxyl numbers, d. H. in the range of between about 30 to about 700. At Representation of this polyester is usually a bottom lyol excess used over the polycarboxylic acids to ensure that the resulting, essentially li Middle polyester chains have a sufficient amount of reactiv ven have hydroxyl groups.

To another class of suitable organic, po The polyalkylene belongs to lyfunctional polyoyl compounds ether polyols, which have more than two reactive hydroxyl groups contain pen, such as the polyalkylene ether trio le, polyalkylene ether tetrols, etc., for example, by Reaction of polyols, such as glycerol, trime ethyl ethane, trimethylol propane, pentaeritritol, dipentaeri tritol, sorbitol, etc. with low alkylene oxides such as for example ethylene oxide, propylene oxide and the like, he are true.

Nitrogen-containing, polyfunctional polyols can also be used as polyol reagents. Such materials include inter alia the polyester amides, which can usually be used in the production of polyurethane resins, ie those compounds whose molecular weight is in the range between 750 to about 3000 and have the acid numbers which ring in the range from 60 to so low as possible, that means two or less, and whose hydroxyl numbers are in the range from 30 to about 700. Polyamino alcohols with a relatively high molecular weight can also be used, such as, for example, hydroxypropylated alkylenediamines of the general formula (C.II)

(HOH ₆ C ₃ ) ₂ NRN (C ₃ H ₆ OH) ₂ (C.II),

where R is an alkylene radical having 2 to 6 carbon atoms, including radicals such as N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, as well as higher analog compounds, such as, for example, hydroxypropylated polyalkylene polyamines of the general formula (C.III)

where R is the meaning given in the preceding formula can accept.

Like the individual connections mentioned, Mi different reactive, organic, po lyfunctional polyols as described hereinbefore have been written to manufacture for the inven useful polyurethanes. In particular re can be seen that when using polyols with more than two hydroxyl functionalities have to be taken care of, that no insoluble gel polymers result, which in for example by an excess of branches or Crosslinking is possible during the polymerization. Similar Considerations play a role in the selection of organic Polyisocyanates a role, as detailed below becomes.

As in the case of the polyol reagents, the polyurethane compounds can vary over a wide range, organic polyisocyanates being used, including aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4-t-butyl-m phenylene diisocyanate, 4 Methoxy-m-phenylene diisocyanate, 4-phenoxy-m-phenylene diisocyanate, 4-chloro-m phenylene diisocyanate, toluyl diisocyanate (either as a mixture of the isomers, for example the commercially available mixture of 80% 2,4-toluene diisocyanate and 20% 2, 6-tolyl diisocyanate or as individual isomers themselves), m-xylylene diisocyanate, p-xylylene diisocyanate, cumyl-2,4-diisocyanate, durene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1,8-naphthylene diisocyanate, 2,6- Naphthylene diisocyanate, 1,5-tetrahydronaphthylene diisocyanate, pp'-diphenyl diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4-diphenylhexane-1,6-diisocyanate, "bitolylene diisocyanate"(3,3'-dimethyl-4,4'- biphenylene diisocyanate at), "dianisidine diisocyanate"(3,3'-dimethoxy-4,4'-biphenylene diisocyanate) and polymethylene polyisocyanates of the general formula (C.IV) below include:

wherein n is an integer between 0 and about 5, and like compounds;
aliphatic diisocyanates such as methylene diisocyanate, ethylene diisocyanate, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and decamethylene diisocyanates, 2-chlorotrimethyl diisocyanate, 2,3-dimethyltetramethylene diisocyanate and the like, and tri- and higher Isocyanates such as benzene-1,3,5-triisocyanate, toluyl-2,4,6-triisocyanate, diphenyl-2,4,4'-triisocyanate, triphenylmethane-4,4 ', 4 "triisocyanate and the like.

Mixtures of two or more of the organic Po mentioned Lyisocyanates can also be used to invent the invention  according to useful polyurethane resins by reaction with either ethers and / or esters as described above have been received.

The polyurethanes mentioned can be known per se Establish the process. These include a. the so-called called prepolymer technology, as is usually the case with Production of polyurethane resins is practiced, wherein Polyol and polyisocyanate under essentially anhydrous Conditions are mixed, d. H. with usually not more than 0.2% by weight of water, based on the Ge total weight of the mixture, and everywhere a mola Use excess polyisocyanates over the polyols det, the mixture obtained at a temperature in the range of between room temperature and about 100 ° C rea is allowed to yaw for a time in the range of 20 min to about 8 hours and then the resulting prepolymer mixture to a temperature in the range of about room temperature is cooled to about 60 ° C.

This technique usually gives polymers with free Isocyanate groups, which are produced in a conventional manner by reaction with monofunctional organic alcohols, phenol, thiol, Amine or other similar monofunctional reagents be eliminated after the end of the polymerisation tion reaction.

Particular preference among the substances of component B2) enjoy thermoplastic polyurethanes (TPU), which by implementation of

• a) organic, preferably aromatic diisocyanates,
• b) polyhydroxyl compounds with molecular weights of 500 up to 8000 and
• c) chain extenders with molecular weights of 60 to 400 in the presence of  
• d) catalysts,
• e) auxiliaries and / or additives,

getting produced.

The following applies to the starting materials (a) to (c), catalysts (d), auxiliaries and additives (e) which can be used for this:

• a) As organic diisocyanates (a) come for example aliphatic, cycloaliphatic and preferably aroma table diisocyanates into consideration. In particular mentioned by way of example: aliphatic diisocyanates, such as Hexamethylene diisocyanate, cycloaliphatic diisocyanate such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and -2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding corresponding isomer mixtures and preferably aromatic Diisocyanates, such as 2,4-tolylene diisocyanate, mixtures from 2,4- and 2,6-tolylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate. Mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate, urethane modified liquid 4,4'- and / or 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanato diphenylethane (1,2) and 1,5-naphthylene diisocyanate. Before hexamethylene diisocyanate is preferably used, Isophorone diisocyanate, 1,5-naphthylene diisocyanate, Diphenylmethane diisocyanate isomer mixtures with one 4,4'Diphenylmethane diisocyanate content greater than 96% by weight and in particular 4,4'-diphenylmethane diisocyanate.
• b) As higher molecular weight polyhydroxyl compounds (b) with molecular weights of 500 to 8000 are preferably polyetherols and polyesterols. However, hydroxyl-containing polymers, for example polyacetals, such as polyoxymethylenes and, above all, water-insoluble formals, for example. B. polybutane diol formal and polyhexanediol formal, and polycarbonates, especially those made from diphenyl carbonate and hexanediol-1,6, produced by transesterification, with the above-mentioned molecular weights. The polyhydroxyl compounds must be at least predominantly linear, ie they have a difunctional structure in the sense of the isocyanate reaction. The polyhydroxyl compounds mentioned can be used as individual components or in the form of mixtures.
  Suitable polyetherols can be prepared by reacting one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with a starter mole containing two active hydrogen atoms. As alkylene oxides such. B. called: ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide. Before preferred application find ethylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide. The alkylene oxides can be used individually, alternately in succession or as a mixture. Examples of suitable starter molecules are: water, amino alcohols, such as N-alkyl-diethanolamine, for example N-methyl diethanolamine, and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. Possibly. Mixtures of starter molecules can also be used. Suitable polyetherols are also the hydroxyl-containing polymerization products of tetrahydrofuran (polyoxytetramethylene glycols).
  Preference is given to using polyetherols of 1,2-propylene oxide and ethylene oxide in which more than 50%, preferably 60 to 80% of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block; e.g. B. in particular polyoxytetramethylene glycols.
  Such polyetherols can be obtained by e.g. B. to the starter molecule, the propylene oxide-1,2 and then the ethylene oxide polymerized or first copolymerized all of the propylene oxide-1,2 in a mixture with part of the ethylene oxide and then polymerized the rest of the ethylene oxide or gradually a part first of the ethylene oxide, then the entire propylene oxide-1,2 and then the rest of the ethylene oxide, polymerized to the starter molecule.
  The essentially linear polyetherols have molecular weights of 500 to 8000, preferably 600 to 6000 and in particular 800 to 3500. They can be used both individually and in the form of mixtures with one another.
  Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, cork acid, azelaic acid and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, e.g. B. in the form of a succinic, glutaric and adipic acid mixture. Mixtures of aromatic and aliphatic dicarboxylic acids can also be used. For the preparation of the polyesters it may be advantageous to use the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters with 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid chlorides instead of the dicarboxylic acids. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2nd , 2-dimethylpropanediol-1,3, propanediol-1,3 and dipropylene glycol. Depending on the desired properties, the polyhydric alcohols can be used alone or, if necessary, in mixtures with one another.
  Also suitable are esters of carbonic acid with the diols mentioned, in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexane, condensation products of ω-hydroxycaproic acid and preferably polymerization products of lactones, for example optionally substituted ω-caprolactones.
  Preferred polyesterols used are dialkyl glycol polyadipates having 2 to 6 carbon atoms in the alkylene radical, such as, for. B. ethanediol polyadipate, 1,4-butanediol polyadipate, ethanediol-butanediol-1,4-polyadipate, 1,6-hexanediol-neopentylglycol polyadipate, polycaprolactones and especially 1,6-hexanediol-1,4-butanediol polyadipate .
  The polyesterols have molecular weights from 500 to 6000, preferably from 800 to 3500.
• c) As chain extenders (c) with molecular weights from 60 to 400, preferably 60 to 300, preferably aliphatic diols having 2 to 12 carbon atoms, preferably 2, 4 or 6 carbon atoms, such as, for. B. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms are also suitable, such as, for. B. terephthalic acid bis-ethylene glycol or 1,4-butanediol, hydroxyalkylene ether of hydroquinone, such as. B. 1,4-di- (β-hydroxyethyl) hydroquinone, (cyclo) aliphatic diamines, such as. B. 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, isophorone diamine, ethylene diamine, 1,2-, 1,3-propylene diamine, N-methyl -propylene diamine-1,3, N, N'-dimethyl-ethylenediamine and aromatic diamines, such as. B. 2,4- and 2,6-tolylene-diamine, 3,5-diethyl-2,4- and -2,6-toluenediamine and primary ortho-di-, tri- and / or tetraalkyl-substituted 4,4 '- Diamino-diphenylmethane.
  To adjust the hardness and melting point of the TPU, the components (b) and (c) can be varied in relatively wide molar ratios. Molar ratios of polyhydroxyl compounds (b) to chain extenders (c) from 1: 1 to 1:12, in particular from 1: 1.8 to 1: 6.4, have proven successful, the hardness and melting point of the TPU increasing Ge stops increasing diols.
  To produce the TPU, the components (a), (b) and (c) are reacted in the presence of any catalysts (d), auxiliaries and / or additives (e) in amounts such that the equivalence ratio of NCO- Groups of diisocyanates (a) to the sum of the hydroxyl groups or hydroxyl and amino groups of components (b) and (c) 1: 0.85 to 1.20, preferably 1: 0.95 to 1: 1.05 and in particular 1: 0.98 to 1.02.
• d) Suitable catalysts, which in particular the Reak tion between the NCO groups of the diisocyanates (a) and the hydroxyl groups of structural components (b) and (c) accelerate, the be according to the prior art knew and usual tertiary amines, such as. B. Trie thylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) - ethanol, diazabicyclo (2,2,2) octane and the like as well especially organic metal compounds such as titanium acid esters, iron compounds such as B. iron (III) - acetylacetonate, tin compounds, e.g. B. tin diacetate, Tin dioctoate, tin dilaurate or the tin dialkyl salts  aliphatic carboxylic acids such as dibutyltin diacetate, Di butyltin dilaurate or the like. The catalysts who usually in amounts of 0.001 to 0.1 part used per 100 parts of polyhydroxyl compound (b).

In addition to catalysts, structural components (a) to (c) auxiliaries and / or additives (e) are also incorporated become. Lubricants, inhibito, may be mentioned, for example stabilizers against hydrolysis, light, heat or ver coloring and plasticizers.

More information on the above-mentioned auxiliary and Zu Substitutes are in the specialist literature, for example mono graphiE: by J.H. Saunders and K.C. Fresh "high poly mers ", volume XVI, polyurethane, part 1 and 2, publisher Inter science publishers 1962 or 1964 or DE-OS 29 01 774 refer to.

The TPU polymers can be used in an amount of up to 20 percent by weight (wt / wt) based on 100 wt .-% of the com components A) and B) included in the adhesive of the invention his.

An adhesive composition containing more than 20% by weight of TPUs is mostly inhomogeneous and therefore cloudy because component B2) does not detach sufficiently leaves. Preferred amounts are between about 3 and 10% by weight.

Group B3)

Component B) of an adhesive according to the invention comprises furthermore one or more crosslinkers based on (Pre) polymers, especially polymers and copolymers, with lateral acrylate and / or methacrylate functions, that have multiple functional groups that are within the scope  of the present invention subsumed under group B3 become.

Of particular interest for the invention include rem crosslinker based on polyurethane (meth) acrylates, so-called PUMA's (group B3a), epoxy resins (group B3c), poly ethers (group B3d) and low molecular weight crosslinkers (Group B3e).

Group B3a)

These include a. isocyanate-functional prepolymers, in which by means of hydroxy-functional compounds, such as. B. Hydroxyethyl acrylate, hydroxyethyl methacrylate, alkyl alcohol, Ethanol, etc., olefinic double bonds introduced become.

The isocyanate-functional prepolymers which are used in the Implementation of the invention are also suitable known. Typically, such prepolymers are adducts or condensation products of polyisocyanate compounds genes that have at least two free isocyanate groups, and monomeric or polymeric polyols with at least two Hydroxy groups, including mixtures of such Po lyole. The reaction between the polyisocyanate and the Po lyols is made using an excess amount of polyi socyanat carried out to ensure that the reacti onprodukt at least two free, unreacted isocyanate has groups.

In the manufacture of the used according to the invention Isocyanate-functional prepolymers be usable polyols preferably have an average molecular weight of about 300 to about 3000. Suitable polyols include polyal kylene glycols, such as polyethylene glycols, polyether polyols, such as the compounds obtained by addition polymerization of Ethylene oxide and a polyol such as trimethylol propane in an egg relationship to the provision of unconverted  Hydroxyl groups were produced in the product, organi cal hydroxylated elastomers that have a glass transition temperature (Second order glass transition temperature) below about 5 ° C, such as poly (butadiene-styrene) polyols and Po ly (butadiene) polyols, polyester polyols as described by poly merization of polyols, e.g. B. Diethylene glycol, Trimethy lolpropane or 1,4-butanediol, with polycarboxylic acids such as Phthalic acid, terephthalic acid, adipic acid, maleic acid or Succinic acid, in a ratio to providing unreacted hydroxyl groups in the product were put; Glyceride esters of hydroxylated fatty acids, such as castor oil, glycerol monoricinoleate, blown linseed oil or blown soybean oil; as well as polyester polyols as they for example by polymerizing a lactone, such as ε-caprolactone.

Polyisocyanates which can be reacted with polyols to form isocyanate-functional prepolymers which are used according to the invention can be any monomeric, ie non-polymeric, isocyanate compounds with at least two free isocyanate groups, including aliphatic, cycloaliphatic and aromatic Links. Typical representatives of polyisocyanates include, but are not limited to:
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, m- and p-phenylene diisocyanate, polymethylene poly (phenyl isocyanate), hexamethylene diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate and other aliphatic, cycloaliphatic and aromatic polyisocyanates, including mixtures of such polyisocyanates. Cycloaliphatic and aromatic polyisocyanates are often preferred.

Crosslinkers from subgroup B3a) which can be used with particular success in the adhesive mixture according to the invention include, among other things, one or more of the compounds of the general formula B3a.I which can be polymerized by free radicals

(H ₂ C = CR ¹ -C (= O) -OR ² -OC (= O) -NH-) _n R ³ (B3a.I)

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

[-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 polycaprolactone diol residue
b) a polytetrahydrofurfuryl diol residue
or where R ³ for n = 3:

[-Q-NH-C (= O) - ((CH ₂ ) ₅ -C (= O)) _p -] ₃ R ⁵

wherein R ^{5 is} a triol residue of a 3 to 6 carbon atoms containing, linear or branched trihydric alcohol and p = 1 to 10 and
Q and Q 'independently of one another contain 6 to 18 carbon atoms containing aromatic, aliphatic or cycloaliphatic groups derived from diisocyanates or diisocyanate mixtures.

The compounds of the formula (B3a.I) can be prepared by processes known per se in the prior art by reacting an acrylate (R ¹ = H) or methacrylate (R ¹ = CH ₃ ) containing compounds containing isocyanate groups in the ester group forming a urethane group. The hydroxyalkyl acrylates or methacrylates contain alkyl groups, which can be linear or branched and contain between 2 to 6 carbon atoms. According to the invention, the esters of acrylic acid and methacrylic acid with polyethylene glycol and / or polypropylene glycol can also 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 the person skilled in the art.

In the compounds of the general formula (B3a.I) for the If n = 2, they are reaction products of hydroxyl-containing acrylates or methacryla ten with isocyanates, which are obtainable by reaction of suitable diols with diisocyanates.

Suitable (meth) acrylates containing hydroxyl groups obey the general formula B3a.1I

H ₂ C = CR ¹ -C (= O) -OR ² -OH (B3a.1I),

wherein
R ¹ = hydrogen or methyl and
R ² = ethylene.

Suitable acrylates or methacrylates are those for which R ^{2 contains} an ethylene, propylene, isopropylene, n-butylene, isobutylene group or 4 to 7 ethylene oxide or propylene oxide units.

Preferred for the implementation of the isocyanates with the Hydroxyl-bearing acrylates or methacrylates who but the hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, polyethylene long glycol acrylate, polyethylene glycol methacrylate, polypropy long glycol acrylate and polypropylene glycol methacrylate.

The straight-chain or branched alkyl groups with 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.

For cycloalkyl groups with 3 to 12 carbon atoms it is preferably those that are selected from the cyclopropyl, cyclobutyl, cyclopentyl, cyclohe xyl and cycloheptyl group.

As aromatic, containing 6 to 18 carbon atoms Groups are in particular the phenyl, 2-toluenyl, 4-Toluenyl and the xylenyl group to be mentioned by Reaction of the (meth) acrylates containing hydroxyl groups is introduced with the corresponding isocyanates.

The diols are a) polycaprolactone diols, b) polytetrahydrofurfuryl diols and c) special polyester diols. The molar ratio in the reaction of the diols with the diisocyanates can vary in the ratio from 1: 1 to 1: 1.1.

• a) Polycaprolactone diols are obtainable by processes known per se by ring-opening polymerization of caprolactone with suitable diols, the ratio of caprolactone to diol being 1 to 20, that is to say 2 to 40 moles of caprolactone per mole of diol. The molecular weight of the polycaprolactone diols is between 200 and 4000.
  Suitable diols are in particular linear or branched divalent alcohols containing 2 to 6 carbon atoms, 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-decanediol.
  The reaction products of the diol and the caprolactone are then reacted with aromatic, aliphatic or cyclic di isocyanates by methods known to those skilled in the art. Suitable diisocyanates, from which Q and, independently thereof, 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 pa-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 -en-2,3- dicarboxylate, 2,2,4- and 2,4,4-trimethylene hexamethylene diisocyanate and mixtures thereof.
  The reaction product of the diol, the caprolactone and the diisocyanate is then reacted with the hydroxyl-containing acrylate or methacrylate to give polyurethane (meth) acrylate by processes known per se.
• b) The structure of the polytetrahydrofurfuryldiol conductive compounds of formula I for n = 2 in principle according to the same scheme as under a) be wrote. First, polytetrahydrofurfuryl diol is used one of the diisocyanates mentioned under a) for Re brought action and the reaction product from it with the already mentioned hydroxyl-containing acrylics ten or methacrylates of the formula B3a.II to the polyurethane han (meth) acrylate implemented. Regarding the procedure on the implementation of diols with diisocyanates relevant specialist literature known to the person skilled in the art grasslands. The molecular weight of the products is between between 200 and 4500.
• c) Particularly good results can be obtained in the context of the invention with PUMA's, which are derived from special polyester diols.
  It is therefore extremely useful to use compounds of the general formula B3a.III
  [H ₂ C = CR ¹ -C (= O) -OR ² -OC (= O) -NH-Q-NH-C (= O)] ₂ [{-OR ^4a -O- C (O =) - NH-Q'-NH-C (O =)} _m -OR ^4a -O-] (B3a.III)
  wherein
  m = 0 to 10,
  R ¹ = hydrogen or methyl group,
  R ² = a linear or branched alkylene radical with 2 to 6 carbon atoms or an alkylene oxide with 4 to 21 carbon atoms,
  Q and Q 'are, independently of one another, 6 to 18 carbon atoms containing aromatic, aliphatic or cycloaliphatic groups which are derived from the underlying diisocyanate or diisocyanate mixture and
  R ^{4a is derived} from a polyester diol with a C: O ratio of <2.6, a C: H ratio <10 and a molecular weight of 1,000 to 20,000.

By using the polyurethane (meth) acrylates of the general my formula B3a.III are particularly good properties, achieved in particular with regard to the hydrophobization. These polyurethane (meth) acrylates have a special ela stifying effect on.

R ⁴ corresponds to polyester diol residues derived from polyester diols, which are characterized by a C: O ratio of <2.6, preferably <3.0, and a C: H ratio of <10 Polyesterdiole by a molecular weight of 1000 to 20,000, in particular from 1000 to 10,000.

These special polyester diols are produced by reacting long-chain diols, especially Di merdiol. (hydrogenated dimer fatty acid) with shorter chain 4 to  Dicarboxylic acids containing 8 carbon atoms or their Anhydrides, especially succinic acid or succinic acid reanhydride. The polyester diols can also be made by implementing short-chain 4 to 8 coals Diols containing atoms, in particular 1,6-hexanediol with long-chain fatty acids, especially dimer fatty acid Mixture of dimerized fatty acids from acyclic and Cyclic dicarboxylic acids with an average of 36 carbons atoms of matter. But it can also be mixtures of long-chain Diols with shorter chain diols are used, such as in particular mixtures of hexanediol and polyethylene glycol or from dimer diol and diethylene glycol.

In general, particularly preferred diols are linear or branched C ₂ -C ₄₄ -alkyldiols such as ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butanediol, neophenyl glycol, 1 , 2- or 1,6-hexanediol, 1,10-decanediol, 1,12-octadecanediol. Cyclic C ₆ -C ₄₄ -alkyldiols are also suitable.

Also preferred are diols containing ether groups, such as for example di, tri or tetraethylene or -propylene glycol or its oligomeric homologues.

Generally preferred as dicarboxylic acid are linear or branched C ₂ -C ₄₄ -alkyldicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azealic acid, nonandicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid or their technical mixtures. Unsaturated C ₄ -C ₄₄ dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or aconitic acid can also be used for the reaction with the diols.

The esterification can be carried out according to methods known per se Presence of a catalyst in a suitable solution medium at elevated temperature with azeotropic removal of the water of reaction. As a catalyst Tin (II) octoate and preferred solvent xylene.  

The polyester diols obtained in this way are then mixed with one of the Implemented diisocyanates mentioned above under a) and finally with the hydroxyl groups already mentioned under a) pen containing acrylates or methacrylates for polyurethane han (meth) acrylate implemented. One or more of these on the special polyester diol based polyurethane Han (meth) acrylates can be mixed with activators and optionally other conventional additives as an adhesive composition tongue can be used.

In the compounds of the general formula (B3a.I) for the If n = 3, the products are reaction products of the above-mentioned hydroxyl-containing acrylates or methacrylates with isocyanates that are available by reacting suitable 3 to 6 carbon atoms containing, linear or branched trivalent alcohol fetch (triplets) with caprolactone and subsequent reaction with diisocyanates.

Polycaprolactone triols are known per se obtainable by ring opening polymerization of caprolactone with suitable triplets, the ratio of Caprolac ton of triol is 1 to 10, i.e. 3 to 30 mol of Caprolac ton with a mole of triol.

As a triplet are particularly those that come into question are selected from glycerin, 1,2,4-butanetriol, trimethylolpro pan (2-hydroxymethyl-2-ethyl-1,3-propanediol) and trimethyl olethane (2-methyl-2-hydroxymethyl-1,3-propanediol).

The reaction products from the triol and the caprolactone are then by methods known to those skilled in the art implemented with the diisocyanates mentioned under a). On finally the reaction product from the triol, the Ca prolacton and the diisocyanate according to Ver drive with the hydroxyl-containing acrylate or Methacrylate converted to polyurethane (meth) acrylate.  

Group B3c)

Suitable compounds of group B3c) are made Epoxy compounds in the presence of a cyclic acid implemented drids with hydroxy-functional (meth) acrylates, so that at least one di (meth) acrylate is formed.

The formation of the epoxides useful here is described schematically by the expression AH _n + n EPCl. Depending on the ratio AH _n : EPCl, the products formed can also be of higher molecular weight or only partially epoxidized.

H-Acidic compounds are used as AH _n , such as bisphenol-A, hydrogenated bisphenol-A radical, tetrabromobisphenol-A, hydroquinone, aliphatic alcohols of the formula HO- (CH ₂ ) _n -OH with n = 2 to 10 and their Isomers, tetrahydrophthalic acid, hexahydroghtalic acid, isocyanuric acid, bis hydantoin, aniline, p-aminophenol, glyoxaltraphenol, cyclohexanol, trimethylolpropane, polyether polyols based on 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4- Butanediol, which depending on the starter molecule can carry up to 8 terminal OH groups (PEG with n = 1-570; PPG with n = 1-103; each head / tail, head / head, and / or tail / tail linked; PTMG with n = 1-20), polyols based on (meth) acrylate / styrene / hydroxy (meth) acrylate copolymers with combinations, as indicated in the overview below.

Polyester polyols, consisting of the components listed in the following overview

2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3- pentanediol, tricyclodecanedimethanol, 2-ethyl-2- hydroxymethyl-1,3-propanediol, glycerin, hydroxypivalin Neopentyl glycol ester, pentaerythritol, 2-methyl-2-propyl 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-sec-butyl-2-methyl, 1,3-propanediol, 3-hexyne-2,5-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 1,2-pentanediol, pinacol, 1,2,4-butanetriol, 2-hydroxymethyl-2-methyl-1,3-propanediol, Ditrimethylolethane, Ditrimethylolpropane, Erythritol, Threi tol, D-, L-, D, L-threitol, ribitol, arabinitol, D-, L-, D, L-  Arabinitol, xylitol, allitol, dulcitol, sorbitol, glucitol, D-, L-, D, L-glucitol, mannitol, D-, L-, D, L-mannitol, altritol, D-, L-, D, L-altritol, iditol, D-, L-iditol, maltritol, Lactitol, isomalt.

The from these H-acidic compounds and epichlorohydrin he Urgent oxides are available in the presence of a cyclic Acid anhydride with a hydroxy-functional (meth) acrylate implemented so that at least one di (meth) acrylate is formed.

Acid anhydrides are compounds of the general formula (B3c.I)

-C (O) - (CH ₂ ) _n C (O) O- (B3c.I)

with n = 1-19 (but preferably 1-3, esp. bev. 2) to Use, but also phthalic anhydride, hexahydrophthalic acid reanhydride, maleic anhydride, 1,2-cyclohex-4- Acid anhydride, citraconic anhydride, itaconic acid anhydride drid, 2-methylene glutaric anhydride.

As the basis for the hydroxyl-containing (Meth) acrylate serve the above. Polyols except for one OH group are esterified with (meth) acrylic acid, preferred however, hydroxyethyl (meth) acrylate, Hydroxypro pyl (meth) acrylate, hydroxybutyl (meth) acrylate with all Isomers. Hydroxypropyl (meth) acrylate is particularly preferred.

An at least difunctional (meth) acrylate of the formula (B3c.II) is formed

With
R ¹ = H, Me esp. Bev. H
R ² = alcohol residue d. (Meth) acrylates esp. Bev. (CH ₂ ) ₃
R ³ = rest of the acid anhydride, especially bev. (CH ₂ ) ₂
R ⁴ = alcohol residue d. Epoxy resin esp. Bev. BPA;
Compounds of the general formula (B3c.III)

EP-O - [- AO-CH ₂ -CH (OH) -CH ₂ -O-] _n -AO-EP (B3c.III)

with EP = glycidyl ether unit, n = 0 to 105 (better n = 0.03 to 6; preferably n = 0.10 to 0.6) and A = bisphenol A.

Group B3d)

These include (meth) acrylic esters of dihydric alcohols of the formula (B3d.I)

with R ¹ = H, Me
R ² = the diol residues mentioned above under B3c
such as B. bisphenol-F, bisphenol-A, hydrogenated bisphenol A, tetrabromobisphenol-A, hydroquinone, glyoxaltraphenol, ali patic diols including their isomers of the formula
HO- (CH ₂ ) -OH with n = 1-10, polyethylene glycol of the formula
HO- (CH ₂ CH ₂ O) -H, n = 2-570, polypropylene glycol 1,2- and 1,3-, head / head, tail / tail, head / tail-linked of the formula HO- (C ₃ H ₆ -O) -H with
n = 2-103, polytetramethylene glycol and isomers of the formula HO- (C ₄ H ₈ -O) -H with
n = 1-20, polyester diols based on the following table.

Neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, tricyclo decanedimethanol, hydroxypivalinneopentyl glycol ester, 2- Methyl 2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- propanediol, 2-sec butyl-2-methyl-1,3-propanediol, cyclo hexanedimethanol, 3-hexyne-2,5-diol, 2,5-dimethyl-3-hexyne 2,5-diol, pinacol.

Group B3e)

(Meth) acrylic esters with alcohols with a functionality <2 of the formula (B3e.I)

with R ¹ = H, Me
R ² = above polyol residues
n ≧ 3
such as B.
Glyoxalt graphenol, trimethylol propane, PEG with starter alcohol bring a functionality of 3-8 and n = 3-570, PPG with starter alcohols a functionality of 3-8 and n = 3-103, polyols based on copolymers as listed in the table

Polyester polyols based on d. Raw materials as listed in the table below

Trimethylolpropane, pentaerythritol and homologues with n = 1-4, 1,2,4-butanetriol, trimethylolethane ditrimethy lolpropane, ditrimethylolethane, erythritol, threitol, D- Threitol, L-Threitol, D, L-Threitol, Ribitol, Arabinitol, D-  Arabinitol, L-arabinitol, D, L-arabinitol, xylitol, allitol, Dulcitol, sorbitol, glucitol, D-glucitol, L-glucitol, D, L- Glucitol, mannitol, D-mannitol, L-mannitol, D, L-mannitol, Altritol, D-Altritol, L-Altritol, D, L-Altritol, Iditol, D- Iditol, L-Iditol, D, L-Iditol, Maltritol, Lactitol, Isomalt.

The adhesive mixture according to the invention can have one or more have more crosslinkers B). In particular, it can also several crosslinkers from one and the same group B3a) to B3e) or different groups.

Group B5)

Substances of group B5) can be used in the adhesive according to the inven contains up to 10 parts by weight his. Here, the quantity for the compo refers nente B5) on the sum of components A) and B).

Substances from group B5) in the adhesive are preferred of the invention to improve the 0 values of the tensile shear strengths of bonds under various external Conditions used. In addition, these substances can Group B5) to round off the entire range of properties serve the adhesive system.

As substances of group B5), one or more substance and / or emulsion polymers are considered risks in the context of the invention. These have molecular weights M _W of <500,000.

Group B5a)

The bulk polymers that can be used include, among others rem all homopolymers, copolymers or terpolymers produced by polymeri sation of unsaturated compounds available in bulk are.  

A copolymer is preferred as bulk polymer B5a) sat, which is obtained by polymerizing at least two mono mersorten in substance is available.

Under the bulk or bulk polymerization, a poly understood merization process in which monomers without Lö be polymerized so that the polymer ons reaction takes place in bulk or in substance. in the In contrast, the polymerization is in emulsion (so-called emulsion polymerization) and the polymerization in the dispersion (so-called suspension polymerization) see the organic monomer with protective colloids and / or stabilizers is suspended in the aqueous phase and more or less coarse polymer particles are formed become. A special form of polymerization in heterogeneous ner phase is the bead polymerization, which is essentially suspension polymerization is to be expected.

Substance copolymers which can preferably be used in the invention sate can be mass-polymerized by Gemi obtained from a number of components i) to iii).

Component i) of bulk polymer B5a)

For component i), which is used to obtain a preferred Substance copolymer (component B5a)) are used can, it is one or more (meth) acrylates. The term "(meth) acrylates" basically Esters of acrylic acid as well as esters of methacrylic acid ver stood, which over a polymerizable vinyl dop feature in the molecule.

Component i) can consist of one or more methacrylics. These can optionally have one or more acrylates. Therefore, in a special variant of the invention B5a) is a copolymer which can be obtained by substance polymerization of a mixture,
wherein

• a) off
  • 1. 35-90 parts of one or more methacrylates of the general formula B5a.I
    where R ^{1 is} a linear or branched alkyl radical having 1 to 12 carbon atoms,
  • 2. 0-25 parts of one or more acrylates of the general formula B5a.II
    wherein R ^{2 is} a linear or branched alkyl radical having 1 to 12 carbon atoms, and
  • 3. 0-50 parts of one or more i1) and / or i2) copolymerizable unsaturated compounds

consists,
where parts i1), i2) and i3) add up to 100.

Among the compounds of the formula B5a.I, those in which R ^{1 is} methyl, ethyl and / or n-propyl are particularly preferred in the context of the invention. Mixtures of compounds in which, in the general formula BSa.II R ^2, methyl, ethyl, n-propyl, n-butyl. and / or n-pentyl.

Component ii) of bulk polymer B5a)

Another for bulk polymerization for generation the copolymers B5a) of essential Be Component ii) are 0.01 to 5 parts, preferably <0.2 to 5 parts, molecular weight regulator. This includes the reason after all compounds familiar to the person skilled in the art which form part of the Re gelation of the molecular weight in bulk polymerization are settable. Not included in an exhaustive list  ren this u. a. 4-methyl-2,4-diphenylpentene (1) (1,1 '- (1,1- dimethyl-3-methlene-1,1-propenediyl) bisbenzene, α-methylstyrene) or aliphatic mercapto compounds, such as B. ethyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, Methyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, Trimethylolpropane trimercaptoacetate, glycol dimercaptoacetate, Pentaerythritol tetrakis mercaptoacetate, 1-propanethiol, 2-propanethiol, n-dodecyl mercaptan (1-dodecanethiol), tert-dodecyl mercaptan.

Of the above compounds, n-dodecyl mercaptan is particularly preferred. The amount of molecular weight regulator is set within the scope of the invention so that Co result in polymers that form the desired moles the corresponding viscosity numbers sen.

Component iii) of bulk polymer B5a)

Another component that consists of up to two parts in the Mi can be present, which is used to generate the before drafted substance copolymers with utility for the Er invention (component B5a)) are used are lipophilic radical polymerization initiators. Although the Polyme risk response in principle to any expert common way (for example by radiation or the like) can be solved is an initiation with appropriate lipophilic polymerization initiators preferred. The radi Kalische polymerization initiators are especially the because of lipophilic, so that they are in the mixture of sub Solve punch polymerization. For usable connections ge hear alongside the classic azo initiators such as AIBN or 1,1-azobiscyclohexane carbonitrile, u. a. aliphatic per oxyverloindungen such. B. tert-amyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert.- Amylperoxy-2-ethylhexanoate, tert-butylperoxy-2- ethylhexanoate, tert-amylperoxy-3,5,5, -trimethylhexanoate, Ethyl 3,3-di (tert-amylperoxy) butyrate,  tert-butyl perbenzoate, tert-butyl hydroperoxide, decanoyl peroxide, lauryl peroxide, benzoyl peroxide and any Mi of the compounds mentioned. Of the aforementioned Compounds, lauryl peroxide is very particularly preferred.

Features in an extremely useful embodiment the preferred usable bulk polymer in that B5a) is a copolymer which is characterized by bulk polymers sation is available from 35 to 90 parts i1), 0 to 25 parts i2), 0 to 40 parts i3), 0.2 to 5 parts ii) and 0.1 to 2 parts iii), wherein i1) + i2) + i3) 100 parts (wt / wt) must result. Copolyme are particularly useful risks from 50 to 80 parts i1), 0 to 20 parts i2), 0 to 40 parts i3), 0.2 to 5 parts ii) and 0.1 to 2 parts iii), where i1) + i2) + i3) must give 100 parts (wt / wt) sen.

Finally, it is in yet another embodiment preferred if as i1) methyl methacrylate, as i2) n-butyl acrylate, as ii) n-dodecyl mercaptan and as iii) Lauryl peroxide is used.

Group B5b)

The emulsion polymers that can be used are preferably based Risks on methyl methacrylate (MMA). MMA based Emulsion polymers are those polymers based on are available by way of emulsion polymerization, wherein the majority (50 to 100 wt .-% of the monomers) of the polymerizable constituents of an emulsion polymer system is methyl methacrylate (MMA).

The emulsions useful according to the invention preferably have onpolymerisate Tg's in the range of 50 to about 180 ° C. Emulsion polymers with Tg's are even more preferred Range from 70 to <120 ° C. Prove particularly useful emulsion polymers with Tg's of <80 ° C.  

The emulsion polymers described in the present inven application can be used effectively Techniques and processes manufactured to which the subject conventional emulsion polymerization techniques belong.

Basically can be in emulsion polymerization usually use poorly water-soluble monomers zen, but it can also be water-soluble monomers as in for example, acrylamide methacrylic acid or hydroxyethyl methacrylate and others polymerized in emulsion and copo be lymerized. To obtain an invention usable emulsion polymer can all the expert common monomers are used, which can be after polymerize known emulsion polymerization process to let.

The groups or classes of monomers which can be used successfully include, for example, α, β-unsaturated carboxylic acids, alkyl (C ₁ -C ₂₄ ) esters of α, β-unsaturated carboxylic acids, unsaturated di- or polycarboxylic acids and their esters, mono-, Di- or polyester of α, β-unsaturated carboxylic acids or carboxylic acid mixtures of di- or polyols, α, β-unsaturated aldehydes, vinyl halides, α-olefins, vinyl ethers, styrenes and / or vinyl aramates.

Representatives of these classes which can be used advantageously ren u. a. Styrene and alkyl-substituted styrenes such as o-, m- and p-methylstyrenes, α-methylstyrene, p-ethylstyrene and p-tert-butylstyrene; Vinyl aromatics such as vinyl naphthali no; ethylenically unsaturated monocarboxylic acids and their Esters such as acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, chloroethyl acrylate, methacrylic acid, Me ethyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, n-octyl methacrylate, dodecyl methacrylic lat, stearyl methacrylate and 2-ethylhexyl methacrylate; Deri  vate of ethylenically unsaturated monocarboxylic acids and de ren esters such as ethylenically unsaturated dicarboxylic acids and their derivatives such as fumaric acid esters; 1.4- Butanediol dimethacrylate.

Of these vinyl monomers are styrene, o-, m- and p-methylstyrene, acrylates, methacrylates and vinyl acetates prefers. Acrylates and methacrylics are very particularly preferred latex and / or styrene. Methyl is of the greatest interest acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate and / or n-butyl acrylate.

The monomers mentioned can be used either alone or in Mi combination of two or more copolymerized with each other become. Mixtures containing MMA are particularly preferred point. Mixtures that are 50 or more weight percent MMA.

The nature of the radical generator required to carry out the emulsion polymerization process to obtain a polymer of component B5b) is not subject to any particular restriction. Above all, what can be used according to the invention are water-soluble radical formers, such as sodium peroxodisulfate, or else water-soluble azo initiators or water-soluble peroxides and hydroperoxides as starters for the polymerization reaction. Preferred catalysts are peroxidic radical initiators such as alkali persulfates or ammonium persulfates, perborates, H ₂ O ₂ , organic hydroperoxides such as t-butyl hydroperoxide, or esters such as t-butyl perbenzoate.

These radical formers are often used along with reductions agents such as sodium sulfide, sodium formaldehyde sulfoxylate or other, used. The combination of peroxidic Catalysts with reducing agents to a redox Catalyst is preferred with reducing agents such as natri ummetabisulfate, water-soluble thiosulfates, sulfites, tertiary amines such as triethanolamine, thioureas and  Salts of polyvalent metals, such as. B. sulfates of cobalt, Iron, nickel and copper.

Catalysts which are particularly preferred in the context of the invention gates for the production of on emulsion polymers, ins special of MMA-based emulsion polymers, are alkali or ammonium persulfates.

So-called "cold start systems" are also preferred. When starting with such systems, heating is not required to start the polymerization. For example, it can be started by redox catalysis, e.g. B. with a Sy stem from peroxide, reducing agent and catalyst. A specific example includes:

• Persulfate as peroxide,
• - Rongalit (sodium formaldehyde sulfoxylate) as a reduction medium and
• - Iron (II) sulfate as a catalyst.

In general, the iron salt is only used in catalytic amounts (approx. 1% based on persulfate). The use of EDTA as a complexing agent for the iron has also proven to be advantageous. Further information on the "cold start procedure" can be found in the following literature references, to which reference is made for the purposes of the disclosure:
EP Crematy; J. Polymer Sci., A-1, 7 (11), 3260 (1969);
JW Goodwin et al .; Coll. Polym. Sci., 257, 1 (1979);
IW Fordham et al .; J. Am. Chem. Soc., 73, 4855 (1951).

To the heat of polymerization in emulsion polymerization to control procedures, one often uses ver various feed processes, such as the emulsion feed, the Monomer feed, separate feed of monomer and others Excipients such as emulsifiers and. Ä.

The emulsion homo- or copo usable according to the invention Lymerisate are also batch and seed latex  available. These special techniques are u. a. there to be used to get the heat of polymerization released water to be able to control, but also to z. B. the part adjust the size of the dispersion spots.

To produce the usable within the scope of the invention Emulsion polymers also become emulsifiers and dispersants goals needed. Here are cationic, anionic, am photere and non-ionic compounds in use. Be anionic dispersing agents are particularly preferred. Examples of anionic dispersing aids are Products such as alkali salts of longer-chain fatty acids, Al kyl sulfates such as sodium lauryl sulfate, alkyl sulfonates, alky gated aryl sulfonates such as sodium or potassium isopropylbene benzenesulfonate, alkali salts of sulfosuccinic acid such as natri umoctyl sulfone succinate, sodium N-methyl-N-palmitoyl laurate or others such as alkali salts of alkylaryl polyethoxyethanol sulfates or sulfonates with z. B. 1-5 oxoethylene units to call.

Suitable cationic dispersants are e.g. B. Lau rylpyridinium chloride, cetyldimethylammonium acetate or higher alkyldimethylammonium chlorides with alkyl = C ₆ to C ₁₈ .

Suitable neutral dispersing aids are e.g. B. alkyl phenoxypolyethoxyethanol with an alkyl chain length of C ₇ to C ₁₈ and with 4-50 oxoethylene units, for. B. heptyl phenoxypolyethoxyethanol; Polyethoxyethanolverbindungen of methylene bridged alkylphenols, sulfur-containing connec tions, the z. B. be obtained by condensation of 4-50 ethylene oxy units with higher alkyl mercaptans; Polyether polyols of higher alkyl carboxylic acids, analogous to ethylene oxide condensates, higher fatty alcohols, polyether po lyol derivatives of etherified or esterified polyhydroxy compounds with a hydrophobic alkyl chain, e.g. B. sorbitol monostearate with 4-50 oxoethylene units or oxopropylene units.

A combination of anionic and neutral emulsifiers is possible.

The emulsion polymerization can be carried out at temperatures of 0-100 ° C, preferably at 30-90 ° C. Man can polymerize with or without pressure.

The easiest way to obtain the emulsion copolymers is by using Re action of the aqueous suspension or emulsion of the mixture the monomers to be copolymerized and the catalysts with intensive mixing at room temperature or he manufactured at high temperature. But others can too Emulsion polymerization process using continuous Feed of monomer pre-emulsion (s) and catalyst solution ar prepare, be used. The amount of catalyst required is usually between 0.01 and 3% peroxide and same or less amount of the reduction catalyst tors, based on the content of monomers in the suspension or emulsion. The copolymers obtained can in one Concentration of 5-60% in the aqueous phase disper be emulsified or emulsified, usually the salary is between 30 and 50%. If necessary, batch Transfer reagents are added. Other auxiliaries such as sodium hydroxide, buffer, rheological additives, stabilizers lisators are possible and will be used by the specialist depending on the ge desired effect used. Depending on the desired property shaft of the dispersion or the solids to be isolated the raw materials described above are combined niert and according to one of the above-mentioned procedures or Kom polymerized combinations of the same.

The dispersions or emulsions obtained can be used for Wei processing with thickeners, flow aids agents, preservatives, defoamers, processing auxiliaries, antioxidants and. a. be transferred.

The order of addition of the reagents is shown in the spoken procedures relatively uncritical. You can go every Mon nomeren either mix and continuously into the reak  Introduce tion solution with vigorous stirring, or you can individual monomers separated the reaction solution during the Add reaction and at the same time that to the Polyme necessary peroxidic and / or redox catalysis goals in a desired concentration, preferably of Add 0.01 to 3%, based on the monomer concentration or all components can be added to the aqueous phase be and the reaction is carried out in a one-pot process guided.

There are more details on emulsion polymerization e.g. B. Houben Weyl, Vol. 20, Part 1, pp. 218-313 (1987) ent acceptable. Reference is made to this for the purpose of disclosure taken.

A preferred emulsion copolymer is an MMA / n-butyl acrylate emulsion copolymer which, for. B. is available in the following manner:
A pre-emulsion is made from:

500 g of demineralized water and 3.0 g of Na Triumdioctylsulfosuccinat submitted and stirring at 200 U / min speed warmed to 80 ° C ± 1 ° C. Just before Dosie tion of the pre-emulsion, 0.042 g of ammonium peroxodisulfate and 0.024 g of sodium bisulfite was added and the pre-emulsion metered in over 4 h at 80 ° C ± 1 ° C. After 30 minutes after freak for post-catalysis, another 0.042 g of ammonia umperoxodisulfate and 0.024 g sodium bisulfite, dissolved in 60 ml of water. After a further 30 min filtered a 1.25 µm filter.  

The viscosity numbers of the emulses useful according to the invention Sion polymers are preferably VZ <50, preferably two se 50 <VZ <100.

As mentioned, the molecular weights Mw are preferably included 50,000 to 150,000.

The particle size of the homo- and copolymers is coming moves in the range from 20 to 2000 µm (for the secondary part chen = powder) and in the range of 10 to 2000 nm, preferred between 50 and 2000 nm for primary particles.

Copolymers with a higher proportion of are also preferred MMA according to the information previously given about the glass running temperature.

Component C)

Component C) of the adhesive according to the invention comprises phosphorus-containing compounds. This component is essential ell and serves to improve the liability.

Phosphorus-containing compounds which can be used with particular success as additives in the context of the invention include, among other compounds, derivatives of phosphinic acid, derivatives of phosphonic acid and derivatives of phosphoric acid which have at least one -POH group and at least one organic radical , which is characterized by the presence of at least one olefinically unsaturated group, which is preferably terminally arranged. In particular, such olefinically unsaturated organophosphorus compounds of the general formula (CI)

wherein each R independently of one another is the same or different means a divalent organic radical which is connected to the phosphorus atom directly via a carbon-phosphorus bond, the divalent organic radical being a divergent unsubstituted organic radical or a diva lently substituted organic radical which is at least easily substituted with halogen, hydroxyl, amino, alkyl radical with 1 to 8, preferably 1 to 4, carbon atoms and / or aryl radical; at least one X stands for CH ₂ = C <and the other X is a functional group, selected from the group consisting of hydrogen, hydroxyl, amino, SR 'groups, where R' is an organic radical, halogen and CH ₂ = C <;
of the general formula (C.II)

where R. corresponds to the definition in formula (C. I), R ^{1 is} hydrogen or R ² -X, where R ^{2 is} a divalent organic radical which is bonded directly to the oxygen radical via an oxygen-carbon bond , wherein the diva lente organic radical is an unsubstituted divalent organic radical or a substituted divalent organic radical which has at least one substituting group from the class of substituents consisting of halogen, hydroxyl, amino, alkyl radicals having 1 to 8 carbon atoms, preferably 1 up to 4 carbon atoms, and aryl radicals which have at least one radical which contains at least one aromatic nucleus; and wherein X corresponds to the definition in formula (CI), with the proviso that at least one X radical CH ₂ = C <must be;
of the general formula (C. III)

wherein R ^{1 has} the meaning given for formula (CI), with the condition that at least one R ¹ group contains at least one CH ₂ = C <radical.

Of particular interest as an additive to the adhesives according to the invention is the group of phosphorus-containing compounds of the formula (C.IV)

wherein R ^{3 is} hydrogen, halogen, alkyl group having 1 to 8, preferably 1 to 4, carbon atoms or CH ₂ = CH-;
R ^{4 is} hydrogen, an alkylg 34128 00070 552 001000280000000200012000285913401700040 0002019848483 00004 34009 group with 1 to 8, preferably 1 to 4, carbon atoms, or a haloalky group with 1 to 8, preferably 1 to 4, carbon atoms; A ent is neither -R ⁵ O- or (R ⁶ O) _n , wherein R ^{5 is} an aliphatic or cycloaliphatic alkylene group having one to nine, preferably two to six, carbon atoms and R ^{6 is} an alkylene group having one to seven, preferably two is up to four carbon atoms, n is an integer from two to ten and m is one or two, preferably one.

In the different formulas (CI) to (C.IV), the divalent organic radicals R and R ^{2 can have} a compound structure, that is to say the radical can have at least one or a number of at least two unsubstituted or substituted hydrocarbon groups (m) which are the Rows -O-, -S-, -COO-, -NH-, -NHCOO- contain or are separated by these groups, and the grouping (R ⁷ O) _p , wherein R ^{7 is} one of two to seven, preferably alkylene group containing from two to four carbon atoms and p is an integer from two to ten. Preferably the divalent radical is an alkylene radical having a straight chain or ring of one to 22, preferably one to nine carbon atoms in any non-repeating unit. It should be noted that divalent radicals having a connecting structure have two or more such straight chains or rings. The divalent radicals can be saturated or unsaturated, aliphatic, cycloaliphatic or aromatic, and can include mixtures thereof in link structures and generally have from one to about 22 carbon atoms in each chain or ring of carbon atoms.

In the different formulas (CI) to (C.III), representative XR and XR ² radicals include, but are not limited to, lower alkenyl, cyclohexenyl, hydroxy lower alkenyl, halogen lower alkenyl, carboxy lower alkenyl, lower alkyl, amino -Lower alkyl, hydroxy lower alkyl, mercapto lower alkyl, alkoxy lower alkyl, halogen lower alkyl, diphosphonomethylamino lower alkyl, phenylhydroxyphosphonmethyl, aminophenylhydroxyphosphonomethyl, halophenylhydroxyphosphonomethyl, phenylamino phosphonmethyl, halophenylmethylphosphonomethylphosphonomethyl -, Niederalkylhydroxyphosphonmethyl-, halogen-Niederalkylhydroxyphosphonmethyl- and amino Niederalkylhydroxyphosphonmethyl radicals; the term "lower" refers to a group of one to eight, preferably one to four, carbon atoms.

Phosphorus-containing compounds with vinyl groups are preferred over such compounds with allyl groups, monoesters of phosphinic acid, phosphorous acid and phosphoric acid which have a vinyl or allyl group, in particular vinyl group, as an unsaturated group are preferred. Representative phosphorus-containing compounds include, but are not limited to, metaphosphoric acid, 2-methacryloyloxyethyl phosphate, bis (2-methacryloyloxyethyl) phosphate, 2-acryloyloxyethyl phosphate, bis (2-acryloyloxyethyl) phosphate, methyl (2-methacryloyloxy) phosphate , Ethyl methacryloyloxyethyl phosphate, methyl acryloyloxyethyl phosphate, ethyl acryloyloxyethyl phosphate, compounds according to formula (C.IV), in which R ^{3 is} hydrogen or methyl and R ^{4 is} a propyl, isobutyl, ethylhexyl, halogen propyl, halogenisobutyl or haloethylhexyl radical Vinylphosphonic acid, cyclohexene-3-phosphonic acid, alpha-hydroxybutene-2-phosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-methyl-1,1-diphosphonic acid, 1-amino-1- phenyl-1,1-diphosphonic acid, 3-amino-1-hydroxypropane-1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), gamma-aminopropylphosphonic acid, gamma-glycidoxypropylphosphonic acid, phosphoric acid mono-2-aminoethyl ester, allylphosphonic acid , Allylphosphinic acid, beta-methacryloyloxyethylphosphinic acid, diallylphosphinic acid, bis- (beta-methacryloyloxyethyl) phosphinic acid and Al lylmethacryloyloxyethylphosphinic acid.

Preferred phosphorus-containing compounds are HEMA phosphate and HMCP phosphate, where HEMA is for hydroxyethyl methacrylate is available and HMCP phosphate is available in two stages implementation. Based on HEMA, this is the first Step transesterified with caprolactone. The caprolactone modified HEMA is then used in a second stage Diphosphorus pentoxide converted to HMCP phosphate.

The general formula for HMCP phosphate is:

where A, one or n structural elements of the formula

is; with m = one  integer between 2 and 10, preferably m = 4, 5 or 6 and n can be up to 5.

Substituted compounds with are also conceivable

with any radicals R ^x , R ^y , each element R ^x , R ^y can be varied independently of one another and each element (CR ^x R ^y ) can be different from the adjacent element.

The amount of components C) is critical. Since the inventor The adhesive according to the invention should be transparent set amount does not exceed a certain upper limit This amount is of the chosen phosphorus-containing Connection dependent and can be done by a specialist with a few rou experiments are determined. The specified in the examples give values can serve as a guide.

Generally, the amount added is in the range of 0.01 to 0.30 parts by weight per 100 parts by weight of the com components A) and B), preferably in the range from 0.02 to 0.1 parts by weight.

Component D)

Component D) is an essential component of it adhesive composition according to the invention. In particular acts it is within the scope of the invention a system for bil free radicals.

If the polymerization of components A) for example is initiated by microwaves, as u. a. in EP-A-0 591 879, the use of Ra dical formers are sufficient. The radical formers include other peroxy compounds, such as perester, Percarbonates, peroxyanhydrides, ketone hydroperoxides or Hy  droperoxides, as well as 3-azo compounds. Are radical formers thus, for example, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perpivalate, 2,2-bis (tert-butyl peroxy) butane, tert-amyl perneodecanoate, tert-amyl perpivalate, diisopropyl peroxydicarbonate, dicyclo hexylperoxydicarbonate, bis (4-tert.- Butylcyclohexyl) peroxydicarbonate, cumene hydroperoxide, 1,4-diisopropylbenzene monohydroperoxide, dicyclohexyl peroxide, Dilauroyl peroxide, dioctanoyl peroxide, dibenzoyl peroxide, Me ethyl ethyl ketone, and azo compounds, such as 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane-1-nitrile), azo bis- (isobutanol), azobis (isobutyl acetate), 2,2'-azobis (isobutyric acid amide), 2,2'-azobis (2-methylbutane) or 2,2'-azobis- [2- (2-imidazolin-2-yl) propane].

The amount of radical formers can vary widely ieren. For example, amounts in the range are preferred from 0.1 to 15% by weight, based on the amount of the components ten A) and B) are used.

If the adhesive system according to the invention at room temperature reactive redox coupling catalysts sator uses the at least one oxidizing agent and contain at least one reducing agent, which in Zim temperature with each other to form free, at the Adhesives according to the invention for introducing additives Polymerization reactions of effective radicals with one another can react. In essence, all known ones oxidizing and reducing co-reacting with each other tel used in the practice of the present invention become.

the oxidizing agents include those previously used mentioned peroxides, organic salts of transition metals such as cobalt naphthenate, and containing an unstable chlorine atom Compounds such as sulfonyl chloride. Wed. mixtures of oxidizing agents are used.  

Representative reducing agents close - without restriction kung on this - sulfinic acids, azo compounds such as azoisobut tersäur ~ edinitril, alpha-aminosulfones such as bis- (Tolylsulfonomethyl) amine, bis- (tolylsulfonomethyl) ethylamine and bis- (tolylsulfonomethyl) benzylamine, tertiary amines such as Diisopropyl-p-toluidine, dimethylaniline, dimethyl-p-toluidine and DIPPT = diisopropylene-p-toluidine e.g. B. in combination with dibenzoyl peroxide and aminaldehyde condensation product te, such as B. the condensation products of aliphatic Aldehydes such as butyl aldehyde with primary amines such as aniline or butylamine. These reducing agents can also be used as Mixture can be used.

The use of known accelerators or promoters can bring benefits.

Particularly preferred - because effective and in general readily available - redox coupling catalyst systems result when combining DEPT = dihydroxyethyl-p-toluidine and dibenzoyl peroxide.

The redox catalyst systems are preferred with the whose components of the adhesive are premixed so that the hardness only after all components have been mixed.

In the event that an A / B system is to be used, are oxidizing and reducing agents in the A system or B system or vice versa of an A / B adhesive works. Depending on the reactivity of the redox coupling catalyst Different procedures are known to the person skilled in the art fig.

As already mentioned above, the quantities of the components are te D), which ge in the adhesive system of the invention are mixed within wide limits. The amount is in Frame of the invention chosen so that the invention Glue a pot life in the range of a few seconds to hours, based on normal curing conditions of Temperature and humidity. Preferably the amount of  Redox catalyst system so large that the pot life between a few minutes and several hours. Preferably the reducing agent (s) in quantities in the range from about 0.05 to about 10, preferably from about 0.1 to about 6% by weight, based on 100% by weight of the sum of the components A) and B) used.

Component E)

Component E) is optional. This includes a large number of additives commonly used in adhesives. Examples are:
Setting agents, antistatic agents, antioxidants, accelerators, biostabilizers, mold release agents, flame retardants, lubricants, dyes, flow improvers, lubricants, adhesion promoters, hardeners, initiators, inhibitors, catalysts, light stabilizers, optical brighteners, organic phosphites, weathering protection agents, waxes and plasticizers.

These optional additives can be used in varying amounts Adhesive according to the invention may be included. Some additives are particularly preferred in the context of the invention, as in for example, the additives from groups E1) to E5).

Group E1)

Additives of particular interest are also among others Waxes or paraffins.

Methacrylate adhesives tend to air when hardened hibition. This results in the top layer of adhesive to a greater extent that can come into contact with air eats sticky and doesn't get stuck like the rest of the Adhesive mass. These properties do not deteriorate the adhesive effect, but are unimportant from the perspective of the processor wishes. To prevent or improve this behavior  tens paraffins and / or waxes can therefore the adhesive can be added, which is preferred in its concentration are close to the solubility limit. As it progresses Polymerization exceeds the solubility limit a fine paraffin film forms on the surface, which acts to inhibit the air from the upper resin layers prevents sam and thus to a dry adhesive surface che leads. By evaporating monomers on the top area, the paraffin concentration is also increased and exceeded the solubility limit so that a paraffin film is created.

Or in other words, deals with waxes and paraffins it is generally nonpolar substances that are in the Loosen liquid, uncured adhesive. With increasing Crosslinking during the polymerization takes its contract with the adhesive so that it has a second phase form and migrate to the surface of the adhesive joint. You will then be able to watch a closed film on the Joint surface, and can counteract the adhesive shut off above atmospheric oxygen. By this exclusion the oxygen becomes the polymerisation of the adhesive supported on its surface. In particular, reduced the addition of waxes and / or paraffins thus the glue the surface of the adhesive joint, as the inhibi can be counteracted by oxygen.

In principle, all substances are suitable that the above be written behavior of a homogeneous surface layer Show if the solubility limits are undershot.

Suitable waxes include paraffin, mi crocrystalline wax, carnauba wax, beeswax, lano lin, whale oil, polyolefin waxes, ceresin, candelilla Wax and the like.

However, paraffins have proven to be particularly suitable. These consist mainly of straight-chain hydrocarbons of the general formula C _n H _{2n + 1} with n = 10-70 and a proportion of iso- and cycloalkanes / paraffins from 0 to 60%. These waxes obtained from the vacuum distillation cuts of light and medium-sized lubricating oils have the advantage that they are extremely unreactive under the conditions prevailing in methacrylate adhesives. They are insoluble in water and hardly soluble in low molecular weight aliphatic alcohols and ethers. They are more soluble in ketones, chlorinated hydrocarbons, white spirit, benzene, toluene, xylene and higher aromatics. The solubility decreases with a higher melting point, ie with an increasing molar mass of the wax. The softening points of the macrocrystalline paraffins are between 35 and 72. The commercially available products show viscosities at 100 ° C between 2 and 10 mm ² / s.

Completely refined and deoiled waxes have proven to be preferred for use in the methacrylate adhesives according to the invention, in particular of the A / B type. The oil content of these types is a maximum of 2.5%. Products with a softening point between 40 and 60 ° C and a viscosity at 100 ° C of 2.0 to 5.5 mm ² / s are given particular preference. Of these products, 0.1 to max. 2 wt .-% based on the weight of the total recipe used.

The waxes and / or paraffins can usually be used in quantities from 0.1 to 5% by weight, preferably 0.3 to 2.5% by weight to the total weight of components A) and B) become. Exceeds the amount of wax added and / or paraffin an amount of 5 wt .-% clearly, so this has an adverse impact on the strength of the Kle have exercise.

Group E2)

Another group of special additives is the group of inhibitors E2).  

Inhibitors are added to the polymerizable adhesive mixture to protect against undesired, premature curing. These act as radical chain termination reagents to trap the radicals usually present and considerably increase the shelf life of the adhesive preparations. If curing is initiated intentionally by adding organic peroxides, the inhibitors added have the advantage that they can be run over quickly. Mainly 1,4-dihydroxybenzenes are used. However, differently substituted dihydroxybenzenes can also be used. In general, such inhibitors can be represented using the general formula (E2.I)

wherein
R ^{1 is} a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl , sec-butyl, tert-butyl, Cl, F or Br;
n is an integer ranging from one to four, preferably one or two; and
R ^{2 is} hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl.

However, compounds with 1,4-benzoquinone as the parent compound can also be used. These can be described with the formula (E2.II)

wherein
R ¹ denotes a linear or branched alkyl radical having one to eight carbon atoms, halogen, aryl or hydroxy, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso -Butyl, sec-butyl, tert-butyl, Cl, F or Br; and
n is an integer in the range from one to four, preferably one; is a or two.

Phenols of the general structure (E2.III) are also used

wherein
R ^{1 is} a linear or branched alkyl radical with one to eight carbon atoms, aryl or aralkyl, propionic acid ester with 1 to 4-valent alcohols, which may also contain hetero atoms such as S, O and N, preferably an alkyl radical with one to four carbon atoms, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.

Another advantageous class of substances are hindered phenols based on triazine derivatives of the formula (E2.IV)

with R = compound of the formula (E2.V)

wherein
R ¹ = C _n H _{2n + 1}
with n = 1 or 2.

Connections 1,4- Dihydroxybenzene, 4-methoxyphenol, 2,5-dichloro-3,6- dihydroxy-1,4-benzoquinone, 1,3,5-trimethyl-2,4,6-tris- (3,5- di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-ditert. butyl-4- methylphenol, 2,4-dimethyl-6-tert. butylphenol, 2,2-bis [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl-1- oxoperopoxymethyl) 1,3-propanediyl ester, 2,2'-thiodiethyl bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5- Bis (1,1-dimethylethyl-2,2-methylenebis (4-methyl-6- tert.butyl) phenol, tris- (4-tert.butyl-3-hydroxy-2,6- dimethylbenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tris (3,5- ditert.butyl-4-hydroxy) -s-triazine-2,46- (1H, 3H, 5H) trione or tert-butyl-3,5-dihydroxybenzene used.  

Based on the weight of the total formulation of the adhesive is the proportion of the inhibitors individually or as Mi generally 0.0005-1.3% (wt / wt).

Group E4)

Of particular interest among the possible additives is also the group of antioxidants and heat stabilizers E4).

These compounds are known per se to the person skilled in the art. Examples for a large number of possible additives are: Irganox 1330 (1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, Vulkanox BHT (2,6-di tert.butyl-4-methylphenol), 4-tert-butylpyrocatechol, compounds of the general formula E4.I)

wherein n is an integer in the range from 1 to 4, R ^{1 is a} substituted or unsubstituted, linear or branched alkyl radical having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, an aryl radical or halogen, preferably chlorine, fluorine or bromine , means, and R ^{2 is} hydrogen or a substituted or unsubstituted, linear or branched alkyl radical having 1 to 8 carbon atoms, preferably having 1 to 4 carbon atoms, Irganox 1010 (3,5-bis (1,1-dimethylethyl- 2,2-methylenebis (4-methyl-6-tert-butyl) phenol), Irganox 1035 (2,2'-thiodiethylbis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) , Irganox 1076 (octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, topanol O, Cyanox 1790 (tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -5-triazine-2,4,6- (1H, 3H, 5H) trione), Irganox 1098 and the like.

Group E5)

Of particular interest among the possible additives is also the group of accelerators E5).

Since the addition of certain additives to the fiction moderate adhesive, such as phosphorus-containing Connections to the polymerizable acrylic adhesive mix can have a delaying effect optionally the addition of an accelerating connection be made. The amount of be added accelerating connection can be directly proportional the amount of delayed connection in space amounts in the range from 0.01 to 10% by weight, preferably 0.1 to 5 wt .-%, based on the sum of Weight of components A) and B) are used.

In general, preferred accelerators include aminbe accelerator count. Among others are Dimethylani lin (n-DMA), diethylaniline (DEA), dimethylaminomethylphenol (DMP10), 2-, 4-, 6- tris (dimethylaminomethyl) phenol (DMP30, Ancamine K54, Actiron NX3), dimethyl-p-toluidine (DMPT), N, N-bis (2-hydroxyethyl) p-toluidine (DEPT) and dihydroxy propyl-p-toluidine preferred.

A preferred type of accelerator corresponds to tertiary amines of the general formula (E5.I)

where Z is a methylene group, Y is hydrogen, a hydroxy, an amino, a halogen, an alkyl group with 1 to 8,  preferably 1 to 4 carbon atoms and an alkoxy group pe with 1 to 8, preferably 1 to 4 carbon atoms, a = 0 or 1 and b = 1 or 2.

Particularly preferred amines to accelerate curing tion process when adding unsaturated organic Phosphorus compounds as an additive to the adhesive according to the invention Mixtures are dihydroxyethyl-p-toluidine and Dihydroxyisopropyl-p-toluidine.

Ultimately, the invention also includes the use of the Adhesive for bonding art described herein substances or metals, especially the bond of plastics with metals.

The invention is illustrated below by examples and ver similar examples are explained in more detail.

Examples 1 to 6 and Comparative Example 1

The in the tables (Comparative Example 1 and Examples 1 to 6) specified amounts of PMMA syrup are included 90 wt .-% of the amount of MMA submitted. Then the stated amounts of phenylpolydimethylsiloxane (PDMS), Mercaptan regulator (GDMA) and 5 wt .-% of the amount of MMA mixed and then added to the mixture of PMMA syrup and MMA stirs. The amounts of UV Absorber, diisopropylol-p-toluidine (solid) and the ver remaining 5 wt .-% of the specified amount of MMA are together added and dissolved in a water bath. This solution becomes given above mixture. Then ge stir until the composition is homogeneous. Possibly are given in the tables (Examples 1 to 6) Amounts of HEMA or HMCP phosphate added and stirred.

Then 20 g of these mixtures are mixed with 0.6 g of Agovit Weighing hardener liquid in a PU bowl and  Blended for 30 seconds. Agovit hardener liquid is a Han Product of the Agomer company. Agovit hardener liquid ent holds component D according to this application. In particular this is benzoyl peroxide, dissolved in a plasticizer shung. After that, the following are immediately described Measurements carried out.

Comparative Example 1)

Example 1)

Example 2)

Example 3

Example 4)

Example 5)

Example 6

Examples 7 to 12 and Comparative Example 2

The in the tables (Comparative Example 2 and Examples 7 to 12) specified amounts of PMMA syrup are included 90 wt .-% of the amount of MMA submitted. Then be successively the amounts of TEDMA given in the tables and citric acid softener. Then who the specified amounts of PDMS, GDMA and 5 wt .-% of MMA amount mixed and then in the mixture of PMMA Syrup, MMA, TEDMA and citric acid softener stirred in. The amounts of UV absorber, Di isopropylol-p-toluidine (solid) and the remaining 5 % By weight of the stated amount of MMA is combined and dissolved in a water bath. This solution becomes the previously described given a mixture. The mixture is then stirred until the Zu composition is homogeneous. If necessary, the amounts given in the tables (Examples 7 to 12) HEMA or HMCP phosphate added, stirring again becomes.

Then 20 g of these mixtures are mixed with 0.6 g of Agovit Weighing hardener liquid in a PU bowl and 30 Seconds blended. Subsequently, the successor described measurements carried out.  

Comparative Example 2)

Example 7)

Example 8)

Example 9)

Example 10)

Example 11)

Example 12)

Examples 13 to 18 and Comparative Example 3

The in the tables (Comparative Example 3 and Examples 13 to 18) specified amounts of PMMA syrup are included 90 wt .-% of the amount of MMA submitted. Then the in the amount of TEDMA indicated in the tables. On it the specified amounts of PDMS, GDMA and 5 wt .-% of the amount of MMA mixed and then in the mixture made of PMMA syrup, MMA and TEDMA. The one in the table len specified amounts of W absorber, diisopropylol-p toluidine (solid) and the remaining 5% by weight of the given amount of MMA are put together and in a water bath solved. This solution becomes the mixture described above given. It is then stirred until the composition is homogeneous. If necessary, then in the table len (Examples 13 to 18) specified amounts of HEMA or HMCP phosphate added, stirring again.  

Then 20 g of these mixtures are mixed with 0.6 g of Agovit Weighing hardener liquid in a PU bowl and 30 Seconds blended. Subsequently, the successor described measurements carried out.

Comparative Example 3)

Example 13)

Example 14)

Example 15)

Example 16)

Example 17)

Example 18)

Examples 19 to 24 and Comparative Example 4

Those in Examples 19 to 24 and Comparative Example 4 adhesive systems produced were A / B Systems. This implies that an A system and a B system are provided, which are then in a ratio of 1: 1 mixed wt / wt and as a mixture to the bonds be set.

The in the tables (Comparative Example 4 and Examples 19 to 24) specified amounts of PMMA syrup are included 90 wt .-% of the amount of MMA submitted. Then the stated amounts of PDMS, GDMA and 5% by weight of the MMA amount mixed and then into the mixture of PMMA syrup and MMA stirred in. The amounts of W- Absorber, dihydroxyethyl-p-toluidine (component A only) and the remaining 5 wt .-% of the specified amount of MMA put together and dissolved in a water bath. This solution will added to the mixture described above. Then will stirred until the composition is homogeneous. Given  if then, the in the tables (component B of the Examples 19 to 24) indicated amounts of HEMA or HMCP Phosphate added, stirring again.

Then components A and B are mixed, after which 20 g these mixtures with 0.6 g of Agovit hardener liquid in egg Weighed in a PU bowl and blended for 30 seconds the. Then the following are immediately described measurements.

Comparative Example 4)

Example 19)

Example 20)

Example 21)

Example 22)

Example 23)

Example 24)

2.) Exam methods 2.1.) Tensile shear strength

The tensile shear strength was checked in accordance with DIN 53 283 (September 1979). A material testing machine from Zwick, type 1474, was used as the tensile testing machine. AlCuMg ₂ pl (Bondur F 44) was selected as the test specimen material. The glued test specimens had dimensions of length x width x thickness of 100 × 25 × 1.6 mm. The test strips were degreased before gluing and roughened with 100 corundum sandpaper. Gluing was carried out with an overlap length of 12 mm, which results in an adhesive area of 300 mm ² . The test was carried out 24 hours after bonding at 23 ° C. with a pulling speed of 15 mm / min. Average values of the tensile shear strength from 3 tests are given.

2.2.) Turbidity

To measure the turbidity by adding the Phos phate, the Vellowness Index certainly.

For this purpose, plates with a thickness of 3 mm were cast from the adhesives of Examples 1 to 24 and Comparative Examples 1 to 4. The measurement method for determining the turbidity is carried out in accordance with DIN 5033 "color measurement". The yellowness index YI is calculated according to ASTM D 1925 "Standard Testmethod for Yelowness Index of Plastics", comparable to the yellowness index G according to DIN 6167 "Description of the yellowing of almost white or colorless materials". The measuring device used is called Pier Electronic H ₂ O. The geometry is 0 degrees / d. The measurement conditions are illuminant C, 2-degree observer. Type C light means daylight from 380-760 nm according to DIN 5033 and French NORM CIE 15.

The yellowness index was based on 2 measurements certainly. The mean of both is given Measurements.

3. Results

The examples show that an unexpectedly high adhesive bond extremely small amounts of component C) er can be aimed. These small amounts only lead to egg an insignificant or no enlargement of the yel lowness index, or the turbidity.

Claims (10)

1. Transparent adhesive with high tensile shear strength consisting of

• A) 5-90% by weight of one or more reactive diluents;
• B) 10-95% by weight of one or more (pre) polymers which are soluble in component A);

components A) and B) giving 100% by weight;

• A) one or more phosphorus-containing compounds with at least one olefinically unsaturated group and at least one P-OH group;
• B) one or more radical formers;

and optional

• A) up to 100 parts by weight, based on 100 parts by weight of components A) and B), of conventional additives.

2. adhesive according to claim 1, characterized, that component C) in an amount in the range of 0.01 to 0.30 parts by weight, especially in the range of 0.02 to 0.10 parts by weight based on 100 parts by weight of components A) and B) is added. 3. Adhesive according to claim 1 or 2, characterized in that component A)

• 1. 60 to 100 parts by weight of (meth) acrylate
• 2. 0 to 40 parts by weight of polyvalent (meth) acrylate
• 3. 0 to 40 parts by weight of comonomer

is constructed. 4. Adhesive according to one or more of the preceding Expectations, characterized, that the proportion of components A) in the range from 55 to 85% by weight, based on the weight of components A) and B). 5. Adhesive according to one or more of the preceding Expectations, characterized, that the proportion of components B) in the range from 15 to 45% by weight, based on the weight of components A) and B). 6. Adhesive according to one or more of the preceding Expectations, characterized, that a mixture is used as component A), the Has methyl methacrylate, GDMA and / or TEDMA. 7. Adhesive according to one or more of the preceding Expectations, characterized, that HEMA phosphate or HMCP phosphate as a component of components C) is used. 8. Adhesive according to one or more of the preceding Expectations, characterized, that component B) is a polymer or syrup based of (meth) acrylate. 9. Process for making a low-odor, aerobic curing adhesive according to one or more of the above arising claims, characterized, that components A) to D) and optionally E) mixes with each other.   10. Use of the adhesive according to claims 1 to 8 for bonding plastics or metals or Plastics with metals.