EP1781746A2

EP1781746A2 - Bonding agent and nanoparticles with barrier properties

Info

Publication number: EP1781746A2
Application number: EP05761663A
Authority: EP
Inventors: Annabelle Guilleux; Sara Wagner; Kamil Kalus
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2004-08-06
Filing date: 2005-06-24
Publication date: 2007-05-09
Also published as: CN101014673A; DE102004038274A1; JP2008509235A; KR20070044002A; WO2006015659A3; WO2006015659A2; BRPI0514140A; US20070178263A1

Abstract

The invention relates to a bonding agent with barrier properties, comprising: A) at least one compound which is fluid in a range of 18 °C to 100 °C, preferably 20 °C to 80 °C, with at least one reactive functional group which may be hardened by radiation as component (A), B) at least one compound with at least one reactive functional group which may be hardened by radiation and with at least one COOH-group as component (B) and C) at least one nanoscale filer as component (C), preferably selected from the group of oxides, nitrides, halides, sulphides, carbides, tellurides, selenides of the second to fourth main group, transition elements, lanthanides and/or the group of polyorganosiloxanes. The bonding agent is used as a radiation-hardening bonding agent in coating agents, fillers, sealers or adhesives. The invention further relates to a method for the production of composite films with barrier properties against CO2, O2, N2, water vapour and flavourings using said bonding agents and composite films made by said method.

Description

"Binders with barrier properties II"

The invention relates to binders having barrier properties, to their use for bonding, coating and sealing, to a process for producing composite materials using the binders of the invention having barrier properties and to the use of these composite materials for packaging.

Many goods require protection from the ambient air or the surrounding atmosphere for transport or storage, while others, in particular highly water-containing goods, must be protected from drying out. They must therefore be packaged in a manner which is suitable as completely as possible to exclude all or certain components of the ambient atmosphere or to prevent the diffusion of water or aroma into the ambient atmosphere and thus dehydration or flavor change of the packaged goods.

For example, while propellants and heating fuels are transported and stored in appropriate containers, flexible packaging is frequently used in the field of medical application (pharmaceuticals, ampoules) and in the food / beverage industry. A particularly critical component of the ambient atmosphere is oxygen. The presence of oxygen in many packaged goods, such as food or pharmaceuticals, lead to oxidative spoilage or germination, which can also spoil the packaged goods. For the production of flexible packaging, polymer films made of thermoplastic films are widely used. These polymer films or films are usually made by simple molding techniques such as extrusion or blow molding. Since the entire range of requirements for a modern packaging film can not be met satisfactorily by a polymer film made of a single polymer, it has already been some time since begun to produce so-called composite films, ie films with a multilayer structure. In order to achieve the essential characteristics of a packaging film, such as tear resistance, taste neutrality and barrier properties, various methods are used for joining the individual film components into a composite film.

For example, multilayer systems with separate barrier layers are constructed by combining polyvinylidene chloride (PVDC), ethylene vinyl alcohol (EVOH), and / or aluminum films with polyethylene films, polyester films, and / or polyvinyl chloride films. These multilayer systems can be constructed either by coextrusion or by bonding separately prepared films.

In another method, packaging films, e.g. based on polyethylene terephthalate or biaxially oriented polypropylene, coated with an aluminum and / or silicon oxide layer (in vacuo). Another known method uses the surface refinement of the flexible packaging films by coating the films with solvent or water-based polyvinylidene chloride solutions or dispersions. Coating agents and adhesives based on PVDC or EVOH often have insufficient adhesive strength on polyolefin films. Composites of polyolefin films with such adhesives can already be separated by hand. If necessary, a primer must therefore be applied in an upstream process step in order to effect a good adhesion of the surface coating or of the adhesive to the substrate film.

These known processes for the production of packaging / composite materials with good barrier properties are generally very expensive and costly. The use of metal layers either by vapor deposition of metal or by laminating of metal foils leads in practice again and again to defects by a large number of fine holes in the metal layer, which significantly affect the otherwise good barrier effect of the metal layer. In the search for simpler methods, adhesives have been developed which, in addition to the required adhesive effect, additionally have barrier effects against oxygen, aroma substances and water vapor.

EP 0906944 A2 discloses solvent-free polyurethane adhesives which have barrier properties to oxygen and moisture. These polyurethane adhesives are obtainable by reacting a linear diol with a linear polyester to form a crystalline hydroxyl-terminated polyester which is reacted with a liquid diisocyanate at an NCO / OH ratio of between about 1 and about 1.1. The polyurethane adhesives thus obtained are used as laminating adhesives. The disadvantage is that these types of coating agents often do not have the desired flexibility. Another disadvantage is that long reaction times are required to achieve high barrier properties.

WO 02/26908 describes laminating adhesive compositions based on polymeric binders, in particular based on one- or two-component polyurethane adhesives, which contain fillers with platelet-like crystallite structure with aspect ratios> 100 in the binder matrix. The fillers are for example dispersed in the hydroxyl-containing component of the 2-component adhesive. The laminating adhesives show a significant reduction in the oxygen transmission rate. For some applications, however, the pot life may be too short.

The object of the present invention is to improve the processing and use properties of binders having barrier properties. A further object of the invention was the provision of binders with barrier properties, in particular with respect to CO ₂ , O ₂ , N ₂ , water vapor and flavorings, at low temperatures, ie at 20 ⁰ C to 100 ⁰ C, preferably 25 to 80 ° C, particularly preferably 3O ⁰ C to 6O ⁰ C, are applicable and have a good initial adhesion. The binders should be particularly suitable as laminating adhesives for food packaging. 06835

When using the binder as a sealant or filler shrinkage during the curing process should be as low as possible. When used for example for coating or as an adhesive, adhesion to surfaces which are difficult to wet is to be improved.

Another object is the provision of adhesives, sealants and fillers that can be processed quickly.

The solution of the problem according to the invention can be found in the claims. It consists essentially of a binder with barrier properties, containing

A) at least one in the range of 18 ° C to 100 ⁰ C, preferably 2O ⁰ C to 80 ⁰ C, flowable compound having at least one radiation-curable reactive functional group as component (A);

B) at least one compound having at least one radiation-curable reactive functional group and at least one COOH group as component (B); and

C) at least one nanoscale filler as component (C), which is preferably selected from the group: oxides, nitrides, halides, sulfides, carbides, tellurides, selenides of the second to fourth main group, the transition elements, the lanthanides and / or from the group the polyorganosiloxanes.

The binder according to the invention has barrier properties to CO ₂ , O ₂ , N ₂ , water vapor and aroma substances. The preferred use as a sealant or adhesive reduces the number of production steps involved in making composite materials having barrier properties since the usual additional coatings with polyvinylidene chloride and / or ethylene vinyl alcohol layers or vapor deposition with aluminum layers are no longer required. Due to the absence of a metal layer, the composite materials are more sorted and thus easier to dispose of. In particular, the absence of a metal layer makes it possible to produce transparent film composites with barrier properties. The binders of the invention have at 60 ° C a viscosity of 50mPa.s to 52,000 mPa.s (measured by Brookfield, digital viscometer RVT DV-II ₁ spindle 27) and are therefore at low temperatures, ie in a range of 40 ^0th C to 120 ⁰ C ₁ easy to apply and quickly have a good initial adhesion. Temperature-sensitive substrates, for example polyolefin films, can thus be reliably bonded without damaging the substrate.

The binder according to the invention is radiation-curable and is used in a preferred embodiment as dual your system. The binders should then be anhydrous. Dual your systems are characterized by the fact that they are both radiation-curable and curable by a second, independent curing mechanism. The binders according to the invention can preferably be used as 1-component (I K) systems, so that the provision of additional components, in particular hardeners, can be dispensed with.

The adhesives, sealants and fillers which comprise the binder according to the invention have little to no migration-capable constituents. This eliminates the usual waiting times until complete curing after application of the adhesive, sealant or filler.

In the context of the present invention, binders are to be understood as meaning substances which can join the same or different substrates or can themselves adhere firmly to them.

The terms "curing", "curing" or similar terms in the context of the present text refer to polyreactions as they may occur within individual components of the composition considered in each case in connection with the term. The polyreaction can be a free radical, anionic or cationic polymerization, polycondensation or polyaddition, in which a reactive functional group can react with a suitable further functional group to increase the molecular weight of the molecule carrying it. Usually, crosslinking reactions also take place at the same time. P2005 / 006835

The term "radiation-curable" in the context of the present invention means the initiation of a polyreaction under the influence of radiation. Radiation is to be understood here as meaning any type of radiation which causes irreversible crosslinking in the crosslinkable binder layer to be irradiated. Particularly suitable are UV, electron beams, visible light, but also IR radiation.

For example, an irradiation-curable reactive functional group is a group having a carbon-carbon double bond.

Unless indicated otherwise, molecular weight data relating to polymeric compounds are based on the number-average molecular weight (M _n ). Unless indicated otherwise, all molecular weight data refer to values obtainable by gel permeation chromatography (GPC).

Component (A) used are monomeric, oligomeric and polymeric compounds, provided that they have at least one radiation-curable reactive functional group. Preferably, component (A) in the range of 18 ° C to 100 ⁰ C, preferably 2O ⁰ C to 80 ⁰ C, flowable.

Such compounds which can be used as component (A) are selected from the group: polyacrylic and / or polymethacrylic acid alkyl, cycloalkyl or aryl esters, methacrylic acid and / or acrylic acid homopolymers and / or copolymers, unsaturated polyesters, Polyethers, polycarbonates, polyacetals, polyurethanes, polyolefins, vinyl polymers or rubber polymers such as nitrile or styrene / butadiene rubber.

For the invention as component (A) usable compounds are, for example, in CG. Roffey in "Photogeneration of Reactive Species for UV Curing", John Wiley & Sons, 1997, at pages 182 (vinyl derivatives), 482-485 (unsaturated polyesters), 487-502 (polyester, polyether, epoxy, Polyurethane and melamine acrylates), 504-508 (radiation-crosslinkable organopolysiloxane polymers) and R. Holmann and P. Oldring in "UV and EB Curing Formulation for Printing Inks, Coatings and Paints", published by SIFA (Selective Industrial Training Associates Limited , London, UK), 2nd edition, 1988, at pages 23-26 (epoxy acrylates), 27-35 (urethane acrylates), 36-39 T / EP2005 / 006835

(Polyester acrylates), 39-41 (polyether acrylates), 41 (vinyl polymers), 42-43 (unsaturated polyesters).

Preferably used as component (A) are compounds from the group: (meth) acrylic acid homopolymers and / or copolymers, polyester (meth) acrylates, epoxy (meth) acrylates or polyurethane (meth) acrylates. The term "(meth) acrylate" is intended here to mean a shortened notation for "acrylate and / or meth acrylate".

Comonomers of (meth) acrylic acid containing as comonomer styrene, methylstyrene and / or other alkylstyrenes and / or alpha-olefins are preferred. Particularly suitable components (A) are di- and / or higher-functional acrylate or methacrylate esters. Such acrylate or methacrylate esters preferably comprise esters of acrylic acid or methacrylic acid with aromatic, aliphatic or cycloaliphatic polyols or acrylate esters of polyether alcohols. Suitable compounds are in CG. Roffey "Photogeneration of Reactive Species for UV Curing" at pages 537-560, and R. Holman and P. Oldring "U.V. and E.B. Curing Formulation for Printing Inks, Coatings and Paints" at pages 52-59.

Compounds which are particularly preferred as component (A) include (meth) acrylate esters of aliphatic polyols having from 2 to about 40 carbon atoms.

Such compounds are preferably selected from the group: neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and (meth) acrylate esters of sorbitol and other sugar alcohols. The (meth) acrylate esters of aliphatic or cycloaliphatic diols can be modified with an aliphatic ester or an alkylene oxide. The aliphatic ester-modified acrylates include, for example, neopentyl glycol hydroxypivalate di (meth) acrylate, caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylates, and the like. The alkylene oxide-modified acrylate compounds include, for example, ethylene oxide-modified neopentyl glycol di (meth) acrylates,

Propylene oxide-modified neopentyl glycol di (meth) acrylates, ethylene oxide-modified 5 006835

8th

1,6-hexanediol di (meth) acrylates or propylene oxide-modified 1,6-

Hexanediol di (meth) acrylates or mixtures of two or more thereof. It is also possible to use acrylates or methacrylates which contain aromatic groups. These include corresponding bisphenol A compounds, for example diacrylates or dimethacrylates of adducts of bisphenol A with alkylene oxides, e.g. Adducts of bisphenol A with ethylene oxide and / or propylene oxide. Acrylate monomers based on polyether polyols include, for example, neopentyl glycol-modified (meth) acrylates, trimethylolpropane di (meth) acrylates, polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates, and the like. Tri- and higher-functional acrylate monomers include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- and tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurates or trimethylolpropane tetra (meth) acrylate or mixtures of two or more thereof. Among the di-, tri- or higher-functional acrylate monomers which can be used according to the invention as component (A) are di-, tri- and tetrapropylene glycol diacrylate, neopentyl glycol propoxylate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane monethoxytri (meth) acrylate and pentaerythritol triacrylate preferred.

(Meth) acrylate esters based on urethane-containing polyols can be prepared by reacting a polyol with a di- or higher-functional isocyanate to form OH-terminated polyurethane prepolymers, which are esterified with (meth) acrylic acid to give the corresponding diesters.

In a particularly preferred embodiment, compounds having the general formula (I) are used as component (A):

H ₂ C = CR ¹ -C (= O) -O- (R ⁷ -O) _n R ⁸ (I) with: R ¹ = H ₁ CH ₃ ;

R ⁷ = straight-chain or branched alkylene group of C ₂ to C 10 -o; R ⁸ = straight-chain or branched alkylene group of C 1 to C ₅ ; n = 1 to 25. 5 006835

Preferred compounds of the general formula (I) are methoxyethyl acrylate, ethoxymethyl methacrylate, methoxyethoxyethyl methacrylate, ethoxyethoxyethyl acrylate, butyldiethylene glycol methacrylate, ethoxylated nonylphenol acrylate, ethoxylated lauryl alcohol methacrylate, alkoxylated tetrahydrofurfuryl acrylate, methoxypolyethylene glycol monoacrylate.

Component (A) is more preferably selected from the group: hydrofunctional ethylhexyl methacrylate, octyl / decyl acrylate, ethoxylated trimethylolpropane triacrylate, modified aromatic or aliphatic epoxy acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth ) acrylate, pentaerythritol tetra (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, caprolactone-modified neopentyl glycol hydroxy-pivalate di (meth) acrylates, ethylene oxide-modified neopentyl glycol di (meth) acrylates, propylene oxide-modified neopentyl glycol di (meth) acrylates, ethylene oxide-modified 1 , 6-hexanediol di (meth) acrylates, propylene oxide-modified 1,6-hexanediol di (meth) acrylates, polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, T ris [(meth) acryloxyethyl] isocyanurate,

Caprolactone-modified tris [(meth) acryloxyethyl] isocyanurates, di-, tri- and tetrapropylene glycol diacrylate, neopentyl glycol propoxylate di (meth) acrylate, trimethylolpropane monethoxytri (meth) acrylate, amine-modified polyether acrylates.

The molar mass of the compound (A) is in the range of 100 to 15,000 g / mol, preferably 100 to 10,000 g / mol and more preferably 100 to 8,000 g / mol.

The compound (A) is involved in the radiation-curable binder according to the invention

Barrier properties account for from 5 to 60% by weight, preferably from 5 to 45% by weight.

%, particularly preferably 5 to 30 wt .-%.

Acrylated carboxylic acid-terminated polyesters, carboxylic acid-modified polybutadienes and acid-modified (meth) acrylates based on polyether polyols are preferably used as component (B). The latter are obtainable by reacting polyether polyols, such as ethylene glycol or propylene glycol, with aromatic or aliphatic dicarboxylic acids, such as adipic acid or phthalic acid, and (meth) acrylic acid.

In particular, the components (B) used are products which are disclosed in WO 01/16244 A1 and whose entire content is expressly included in the present patent application.

Preferred commercially available compounds which are used as component (B), from Cognis under the trade name PHOTOMER ^® 5429 F ₁ 5432, 4173, 4149, 3038 or 4017, from BASF under the trade name Laromer PE 44F, PE 55F , PE 56F, 8800, 8981, 9004, available from Cray Valley under the trade name Craynor 203, 293, 294 E, UVP 210, UVP 220 or the trade name Synocure AC 1007, from Rahn under the trade name Genomer 6043, 6050, available from UCB under the trade name Ebecryl 436, 438, 584, 586, 588.

The molar mass of the compound (B) is in the range of 100 to 15,000 g / mol, preferably 100 to 10,000 g / mol, and more preferably 100 to 8,000 g / mol.

The compound (B) is involved in the radiation-curable binder according to the invention

Barrier properties account for from 5 to 70% by weight, preferably from 10 to 60% by weight.

%, particularly preferably 20 to 40 wt .-%.

As component (C), the binder according to the invention contains a nanoscale filler which is preferably selected from the group: oxides, nitrides, halides, sulfides, carbides, tellurides, selenides of the second to fourth main group, the transition elements, the lanthanides and / or from Group of polyorganosiloxanes.

Nanoscale fillers are also referred to as nanodisperse fillers or "nanoparticles", since the smallest particles forming a rigid unit in the dispersion have an expansion of not more than 1000 nanometers in the number-weighted average of all particles in at least one direction that can be chosen for each particle (nm), preferably not more than 500 nm, and more preferably not more than 100 nm. 5 006835

11

The nanoparticles have, for example, a spherical, rod-like, platelet-like structure or represent mixtures of different structures. The nanoparticles contained in the nanoscale filler preferably have in the number-weighted average sizes in the range of 1 to 40 nm, more preferably between 3 and 30 nm. The particle size is preferably determined by the UPA method (Ultrafine Particle Analyzer), for example according to the laser scattered light method ("Laser Light Back Scattering"). In order to prevent or avoid agglomeration or coalescence of the nanoparticles, they can usually be surface-modified or surface-coated. Such a method for producing agglomerate-free nanoparticles is given in columns 8 to 10 using the example of iron oxide particles in DE-A-19614136. Some possibilities for superficial coating of such nanoparticles to avoid agglomeration are given in DE-A-19726282. In a preferred embodiment of the invention nanoscale fillers are used whose smallest in the dispersion, a rigid unit-forming constituents in two mutually perpendicular, arbitrary directions each have an extension of at least ten times the size of the components in the direction with the smallest extension of the component exhibit. The thickness of these particles is preferably less than 10 nm. The nanoscale filler is selected from the group: oxides, nitrides, halides, sulfides, carbides, tellurides, selenides of the second to fourth main group, the transition elements or the lanthanides, in particular oxides, hydroxides, Nitrides, halides, carbides or mixed oxide / hydroxide / halide compounds of aluminum, silicon, zirconium, titanium, tin, zinc, iron or the (alkaline) alkali metals. These are essentially clays, for example aluminas, boehmite, bayerite, gibbsite, diaspore and the like. Suitable are phyllosilicates such as bentonite, montmorillonite, hydrotalcite, hectorite, kaolinite, boehmite, mica, vermiculite or mixtures thereof. Particular preference is given to using phyllosilicates, such as magnesium silicate or aluminum silicate, and montmorillonite, saponite, beidellite, nontronite, hectorite, stevensite, vermiculite, halloysite or their synthetic analogs. Of the modifications cristobalite, quartz and tridynite of the silica, quartz modification is preferred. Furthermore, magnesium oxide, aluminum oxide, magnesium fluoride,

Cadmium sulfide, zinc sulfide, cadmium selenide and the like. Ä. Suitable as nanoscale packing.

In a particularly preferred embodiment of the invention is component

(C) amorphous silica.

As a method of measuring the nanoparticles, in particular the amorphous

Silica particles, the neutron small angle scattering (SANS small angle neutron scattering) is used. This measuring method is the

Expert familiar and needs no further explanation. At the SANS

Measurement contains a particle size distribution curve in which the

Volume fraction of particles of appropriate size (diameter) is plotted over the particle diameter. The mean particle size in the sense of the invention is defined as the peak of such a SANS distribution curve, that is to say the largest volume fraction with particles of corresponding diameter. The average particle size is preferably between 6 and 40 nm, more preferably between 8 and 30 nm, particularly preferably between 10 and 25 nm

Silica particles are preferably substantially spherical.

The proportion of the nanoscale filler used as component (C) in the binder of the invention is 5 wt .-% to 50 wt .-%, preferably

20 to 45 wt .-% and particularly preferably 30 to 40 wt .-%.

In a particularly preferred embodiment, the nanoscale filler is dispersed in a flowable phase, wherein the flowable phase is polymerizable

Contains monomers, oligomers and / or polymers. The flowable phase can consist of a mixture of components (A), (B) and (D), preferably the flowable phase is formed from component (A). Particularly preferred is the as

Dispersant used flowable phase anhydrous, so it contains only small traces of water.

Process for the preparation of such dispersions and silicon dioxide

Dispersions themselves are disclosed in EP-A1-1236765, the entire contents of which are incorporated in the present patent application.

Commercially available dispersions of components (A) and (C) are available from Hanse Chemie under the tradename Nanocryl®. Applicable products are preferably Nanocryl® XP21 / 0746, XP21 / 0768, XP 21/0396, XP 21/1045 or XP 21/1515.

In a further preferred embodiment, the inventive

Binder at least one silicon-organic compound as component (D).

From the group of usable as component (D) silicon-organic

Compounds as component (D1) at least one three-dimensionally crosslinkable polyorganosiloxane, which after crosslinking a middle

Particle diameter in the range of 70 nm to 1000 nm used.

Such polyorganosiloxanes are described in EP-B1-0407834 on page 3, line 43 to page 4, line 19.

In a preferred embodiment, component (D) as component (D2) is a reaction product, preferably an esterification or transesterification product

Acrylic acid and / or methacrylic acid or derivatives thereof with a silane (s) which is characterized by the general formula (II):

Y-A-Si ((Z) ") (T) 3." (II) with

Y = epoxide, -OH, -COOH, -SH ₁ -NH ₂ , NHR "group;

R "= linear or branched, saturated or unsaturated C 1 -C ₈ -alkyl; C ₅ -

C ₈ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₂ aralkyl; Oxyalkylene with up to 4

C atoms, preferably - (CH ₂ -CH ₂ -O) ₁₁₁ -H and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; A-

Si ((Z) _n ) (X) ₃ _-n ; one substituted with alkyl, cycloalkyl or aryl groups

Siloxane residue having from about 1 to about 20 Si atoms; A = a linear or branched, saturated or unsaturated alkylene group with

1 to 12 C atoms, preferably a linear or branched alkylene group having 1 to 4 C atoms;

Z = C 1 -C ₈ -alkyl group, preferably C 1 -C ₄ -alkyl group; T = -NH ₂ ; -NH-CO-R ⁵ , -OOC-R ⁵ ; -ON = C (R ⁵ ) ₂ or OR ⁶ ; R ⁵ = a linear or branched, saturated or unsaturated C ₁ -C ₁₈ -

Alkyl radical, preferably a methyl, ethyl-propyl or iso-propyl radical; R ⁶ = R ⁵ , preferably a methyl, ethyl, propyl or isopropyl radical; or a

Oxyalkyenrest with up to 4 C-atoms, preferably - (CH ₂ -CH ₂ -O) ₁₁₁ -H 5 006835

14

and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; a C ₅ -C ₈ cycloalkyl group; a C ₆ -C ₁₀ aryl or a C ₇ -C ₂ aralkyl; m = 1 to 40, preferably 1 to 20, particularly preferably 1 to 10; n = 0, 1 or 2.

Examples of compounds of the formula (II) are H ₂ N-CH ₂ -Si (O-CH ₂ -CHs) ₃ , HO-CH ₂ -Si (OCHs) ₃ , HO- (CH ₂ ) ₃ -O-CH ₂ -Si (O-CH ₃₎ _3, HO-CH ₂ -CH ₂ -O- CH ₂ -Si (OCH) _3, (HO-C ₂ H ₄₎ ₂ N-CH ₂ -Si (O-CH ₃₎ ₃ , HO- (C ₂ H ₄ -O) ₃ -C ₂ H ₄ -N (CH 3) -CH ₂ -Si (O-CHs) ₃ , H ₂ N-CH ₂ -C ₆ H ₄ -CH ₂ - NH-CH ₂ -Si (O-CH ₃ ) S, HS-CH ₂ -Si (O-CHs) ₃ , H ₂ N- (CHz) ₃ -NH-CH ₂ -Si (OCHs) ₃ , H ₂ N -CH ₂ -CH ₂ -NH-CH ₂ -Si (O-CHs) ₃ , HN - ((CH ₂ ) ₃ -Si (O-CH ₂ -CH ₃ ) ₃ ) ₂ , or CH ₃ - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -Si (O-CH ₃ ) ₃ , H ₂ N- (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) ₃ , H ₂ N-CH (CH ₃ ) -CH ₂ - Si (O-CH ₃ ) _S , H ₂ N- (CH ₂ ) S-Si (O-CH ₃ ) ₃ , H ₂ N-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -Si (O -CH ₃ ) ₃ , (HO-C ₂ H ₄ ) ₂ N- (CH ₂ ) ₃ -Si (O-CH ₃ ) ₃ , HO- (C ₂ H ₄ -O) ₃ -C ₂ H ₄ -N (CH ₃ ) - (CH ₂ ) ₃ -Si (OC ₄ H ₉ ) ₃ , H ₂ N-CH ₂ -C ₆ H ₄ -CH ₂ -CH ₂ -Si (O-CH ₃ ) S, H ₂ N - (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -Si (O-CH ₃ ) ₃₎ H ₂ N-CH ₂ -CH ₂ --NH- (CH ₂ ) ₂ -Si (OCHs) s, H ₂ N- (CH ₂ ) ₂ -NH- (CH ₂ ) s -Si (O-CH ₃ ) ₃ , H ₂ N-CH (C ₂ Hs) -CH ₂ -Si (O-CH ₃ ) s, H ₂ N-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -Si (OC ₂ Hs) ₃ , (HO-C ₂ H ₄ ) ₂ N- (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) 3, H ₂ N-CH ₂ -C ₂ H ₄ -CH ₂ -CH ₂ -Si (OC ₂ H ₅ ) S, H ₂ N- (CH ₂ ) S-NH- (CH ₂ ) S- Si (OC ₂ Hs) ₃ , H ₂ N-CH ₂ -CH ₂ -NH- (CH ₂ ) ₂ -Si (OC ₂ H ₅ ) ₃ , H ₂ N- (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -Si (OC ₂ H ₅ ) 3, as well as mixtures of two or more thereof.

In the context of the present invention, as silane (s) of the general formula (II), preference is given to 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxyphenylsilane and 3-aminopropyldiethoxyethylsilane, in particular 3-aminopropyltrimethoxysilane or bis (3-triethoxysilylpropyl) amine , or mixtures thereof, used. Commercially available silanes (e) are offered by Dynamit Nobel under the name DYNASYLAN®. These are alkoxysilane derivatives having two or three alkoxy radicals and one or two alkyl radicals to which functional groups may additionally be bonded, for example amino, mercapto, methacryloxy or a nitrile group or a halogen radical such as chlorine. Especially preferred as component (D2) is 3-methacryloxypropyltrimethoxysilane and / or allyltriethoxysilane. Component (D2) can be used alone or in admixture with component (D1). In a further preferred embodiment, component (D) as component (D3) is a urethane group-containing silane having an isocyanate content <1% by weight of NCO, preferably <0.5% by weight of NCO and particularly preferably 0.1% by weight of NCO , Component (D3) can be used alone or in mixture with component (D1) and / or component (D2). Such urethane group-containing silanes are obtainable by reacting polyisocyanates (c) with silanes (e) of the general formula (II).

Component (D1), (D2) and / or (D3) are at 0.3 wt .-% to 20 wt .-%, preferably 0.4 wt .-% to 15 wt .-% and particularly preferably to 0, 5% by weight.

From the group of silicon-organic compounds which can be used as component (D), urethane group-containing silanes with at least one radiation-curable reactive group are used as component (D4) in a particularly preferred embodiment.

Component (D4) is prepared by containing at least one polyisocyanate (c) with at least one compound (d) which contains both at least one NCO-reactive functional group and at least one radiation-curable reactive functional group and at least one Silane (e) of the formula (II) is implemented. Such methods are known to the person skilled in the art. For the purposes of the invention, unsymmetrical diisocyanates and / or polyurethane prepolymers with free NGO groups are preferably selected from the group of polyisocyanates (c).

Unsymmetrical diisocyanates have isocyanate groups in the molecule which differ in their reactivity. Preferred unsymmetrical diisocyanates are 2,4-diphenylmethane diisocyanate (MDI), the isomers of tolylene diisocyanate (TDI), 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (IPDI). Information on the broad spectrum of suitable polyol and isocyanate components and processes for the preparation of polyurethane prepolymers can be found by the person skilled in the literature on polyurethane prepolymers, for example EP 0 150444, EP 0 590 398 or WO 99/24486. 35

16

A low-monomer polyurethane prepolymer is preferably used as the polyisocyanate (c), whereby in the context of the present invention a low concentration of the monomeric, in particular aromatic, diisocyanates in the PU prepolymer with free NCO groups is to be understood as "low in monomer". The concentration of these so-called "residual monomers" is below one, preferably between 0 and 0.5 wt .-%, particularly preferably between 0 and 0.2 wt .-%, based on the composition of the PU prepolymer having free NCO groups.

Low-monomer PU prepolymers with free NCO groups are known, for example, from DE 4136490, WO 01/40342 and WO-97/46603 and expressly the subject of this invention.

The functional group reactive with an NCO group is a group having an active hydrogen atom which can be determined by the Zerewittinoff test and bonded to an N, O or S atom. These include, in particular, the hydrogen atoms of water, carboxy, amino, imino, hydroxy, and thiol groups.

Preference is given to using a (meth) acrylate of the general formula (III) as compound (d) which contains both at least one NCO-reactive functional group and at least one radiation-curable reactive functional group:

H ₂ C = CR ¹ -C (= O) -OR ² -Y (III) with:

Y = an NCO-reactive group, preferably OH, COOH ₁ SH, NH ₂ , NHR ³ ;

R ¹ = H ₁ CH ₃ ;

2

R = saturated or unsaturated linear or branched alkylene group having 2 to 21 carbon atoms, optionally substituted with functional groups, for example with a phenoxy or acetoxy group; preferably 2 to 6 carbon atoms, in particular an ethylene, propylene, isopropylene, n-butylene, isobutylene group, or a C 2 -C 4 -alkylene oxide group, preferably an ethylene oxide and / or propylene oxide group, in particular preferably an ethylene oxide group having 2 to 10 ethylene oxide units and / or a propylene oxide group having 1 to 7 propylene oxide units; R ³ = linear or branched, saturated or unsaturated C 1 -C -alkyl radical; C ₅ - Cs cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₂ -aralkyl.

The preparation of such (meth) acrylates of the general formula (III) is known to the person skilled in the art.

Hydroxy (meth) acrylates (Y = OH) are preferably used as (meth) acrylates of the general formula (III), for example: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate and polypropylene glycol methacrylate, glycerol mono (meth) acrylate, 1,3-glycerol di (meth) acrylate, 3-phenoxy-2-hydroxypropyl

(meth) acrylate, 3-toluenyloxy-2-hydroxypropyl (meth) acrylate, 3-acetoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3 - [(2-methyl-1-oxo-2-propenyl) oxy ] propyl ester of 4-hydroxybenzoic acid, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate. The hydroxy acrylates or methacrylates are used individually or in a mixture.

The amounts of the polyisocyanate (c) and (meth) acrylate of the general formula (III) can be selected in a wide range. Thus, the ratio of the NCO group of the polyisocyanate (c) to the NCO group-reactive group Y of the (meth) acrylate of the general formula (III) can be between 0.6: 1 to 20: 1. The ratio NCO: Y is preferably 1, 2: 1 to 10: 1. The molar mass of the reaction product of polyisocyanate (c) with compound (d), which contains both at least one NCO-reactive functional group and at least one radiation-curable reactive functional group, is between 100 g / mol and 10,000 g / mol , preferably between 110 g / mol and 6000 g / mol and more preferably between 120 g / mol and 4000 g / mol. The NCO value of the reaction product of polyisocyanate (c) with compound (d), which contains at least one with NCO Groups containing reactive functional group and at least one radiation-curable reactive functional group is between 2 wt .-% and 30 wt .-%, preferably between 5 wt .-% and 25 wt .-% (determined according to Spiegelberger).

For the preparation of component (D4) it is possible to use both mixtures of polyisocyanates (c) and / or mixtures of silane (s). The reaction of the polyisocyanate component (c) with the silane (e) is carried out in a molar NCO / Y ratio of 1: 0.01 to 1, preferably 1: 0.05 to 0.7 and particularly preferably 1: 0, 1 to 0.4.

The reaction product of the polyisocyanate component (c) and the silane (e) has an NCO value of 1-30%, preferably 10-28%, particularly preferably 15-25%, determined according to Spiegelberger and has a molar mass of 100 g / mol to 1000 g / mol. Processes for the preparation of such reaction products and the reaction products themselves are disclosed in DE-A1-10162642.

For the preparation of component (D4), the at least one polyisocyanate (c) which contains at least one compound (d) which contains both at least one functional group reactive with NGO groups and at least one radiation-curable reactive functional group and at least one Silane (s) in a so-called "one-pot reaction" reacted with each other. However, the reaction can also be carried out in stages, that is, in a first stage, (c) is reacted with (d) or (e) and in a second stage, (e) or (d) with the corresponding reaction product from the first stage on implemented.

At the end of the reaction, component (D4) has a content of free monomeric polyisocyanate of <0.05% by weight, based on the total weight of component (D4).

In order to mix component D stably with the binder according to the invention, it should not contain any groups reactive with the other constituents under storage conditions. In particular, it should be free from isocyanate groups. The functional group - Si (T) 3. _n according to formula (II) of the silicon-organic compound used as component (D3) and (D4) serves to build up an inorganic network of Si-O-Si units.

When using the binder according to the invention as a 1-component (1 K) adhesive component (D3) and (D4) is preferably sensitive to hydrolysis, that is, in the presence of water or humidity, the Si-T bond with release of corresponding cleavage products and simultaneous crosslinking decomposes. Corresponding to the group T in formula (II) arise in the running as a polycondensation reaction crosslinking as cleavage products, for example, amines, acid amides, oximes or alcohols. The course of Si-O-Si network formation can be z. B. by Karl Fischer titration (determination of water consumption in the hydrolysis) are examined.

Component (C) is preferably capable of network formation, in particular Si-O-Si network formation by polycondensation is preferred.

In a preferred embodiment of the invention, a reaction on the surface of component (C) with component (D) in the presence of a metal compound of the formula (IV): MR ⁹ _X (IV) as component (E).

The metal M of this compound is selected from those elements of the main and subgroups of the periodic table which may formally exist in the oxidation state 3 or 4. It preferably means Ge, Sn, Pb, Ti, Zr, B or Al. Depending on valence, x = 3 or 4.

The group R ⁹ , which may be the same or different, is selected from halogen, alkoxy, alkoxycarbonyl and hydroxyl. Since many metal compounds having the formal oxidation state 3 or 4 may also be present as complexes with a multiplicity of ligands, the binder may instead or in addition, however, also contain compounds in which part or all of the groups R ^{9 of} the formula (IV) are replaced by one or more ligands L which are more strongly bonded to the metal M than the group R ⁹ . Compounds of this type are described, for example, in DE 10044216 A1 (page 4, lines 1 to 31). 5 006835

20

Suitable metal compounds are also known as "coupling agents" and are one or more metal centers such as Si, Ti, Zr or Al bonded to functional organic groups.

Corresponding titanium, zirconium or aluminum compounds are described, for example, in DE 4128743 C2 on pages 7 and 8, where r = 0 applies to the Zr and Ti compounds.

Preference is given to using as component (E) tetrabutyl titanate, tin (II) octanoate, dibutyltin dilaurate, tetraethoxysilane or methyltrimethoxysilane. Further preferred metal compounds (IV) which can be used as component (E) are described in EP 1342742 A1 on page 5, lines 28 to 52, and are included in the subject matter of the present invention.

Commercially available are titanates from the company Kenrich Petrochemicals, Inc. Available under the name "KR" or "LICA" substances. Similar to the silanes mentioned above, these reagents are compounds with alkoxy radicals and optionally additionally substituted by functional groups radicals which are bonded to the metal center via oxygen. The functional groups are, for example, amino, mercapto or hydroxyl groups.

Suitable zirconate compounds are, for example, the compounds obtainable as "KZ" or "LZ" reagents from Kenrich Petrochemicals, Inc., where appropriate with amino or mercapto groups.

Component (E) is used in the binder according to the invention to 0 to 12 wt .-%, preferably 0.5 wt .-% to 10 wt .-% and particularly preferably from 1 wt .-% to 5 wt .-%, based on the total amount of the components used. The reaction takes place in particular under the action of water, d. H. In particular, after application as an adhesive, moisture can penetrate into the adhesive and then ensure chemical crosslinking between the components C and D and, if necessary, E.

The triggering of the poly-reaction of the radiation-curable groups can be effected by UV, electron beams, visible light, but also IR radiation. In the case of electron or UV irradiation, the desired product properties are set via the radiation dose, with IR radiation via the product temperature and the residence time. The course of the photochemical curing can IR 005/006835

21

be examined spectroscopically (intensity and relation of the C = C and C = O bands).

Within the scope of the invention, irradiation with UV light or with electron beams is preferred.

In the event that the radiation-curable binder according to the invention with barrier properties is to be polymerized under UV irradiation, the binder composition contains at least one photoinitiator (F). Preferably, a photoinitiator (F) is used, which upon irradiation with light of a wavelength of about 215 to about 480 nm is capable of initiating a free-radical polymerization of olefinically unsaturated double bonds. In the context of the present invention, all customary photoinitiators which are compatible with the binder according to the invention are suitable for use as photoinitiator (F). H. at least largely homogeneous mixtures result.

For example, these are all Norrish-Type I fragmenting substances. Examples include benzophenone, camphorquinone, Quantacure (manufacturer: International Bio-Synthetics), Kayacure MBP (manufactured by Nippon Kayaku), Esacure BO (manufactured by Fratelli Lamberti), Trigonal 14 (manufacturer: Akzo), photoinitiators of the Irgacure ^® - or Darocur ^® - series (Ciba), for example, Darocur ^® 1173, and / or Fi-4 (Herstel¬ ler: Eastman). Particularly suitable are including Irgacure ^® 651, Irgacure ^® 369, Irgacure ^® 184, Irgacure ^® 907, Irgacure ^® 784, Irgacure 500, Irgacure 1000, Darocur MBF, Irgacure 1300, Darocur 4265, Darocur TPO, Irgacure 819 and 918 DW, Irgacure 2022 or Irgacure ^® 2959 or mixtures of two or more thereof. Also suitable are phosphine oxide compounds (Lucirin TPO, manufacturer: BASF AG), which can also be used in admixture with one or more of the above-mentioned photoinitiators.

The binder of the invention having barrier properties contains the photoinitiator (F) in an amount of 0 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total amount the binder composition.

Optionally, the binder according to the invention may contain additives (G) which account for up to about 50% by weight of the total binder. 06835

22

can have. The additives (G) which can be used in the context of the present invention include, for example, plasticizers, catalysts, stabilizers, dispersants, antioxidants, dyes, fillers and agents for influencing the flowability of the dispersion of component (C) in component (A), (B) or (D) or in a mixture of these components.

The binder according to the invention having barrier properties preferably contains

I) 5 to 80 wt .-%, preferably up to 60 wt .-%, in particular up to 45 wt .-%, particularly preferably 5 to 30 wt .-% at least one in the range of 18 ° C to 100 ⁰ C, preferably 20 ⁰ C to 80 ⁰ C, flowable compound having at least one radiation-curable reactive functional group as component (A);

II) 1 to 70 wt .-%, preferably about 5 wt .-%, in particular 10 to 60 wt .-%, more preferably 30 to 40 wt .-% of at least one compound having at least one curable by irradiation reactive functional group and at least a COOH group as component (B);

III) 5 to 50 wt .-%, preferably 20 to 45 wt .-%, particularly preferably 30 to 40 wt .-%, at least one nanoscale filler as component (C), which is preferably selected from the group: oxides, nitrides , Halides, sulfides, carbides, tellurides, selenides of the second to fourth main group, the transition elements, the lanthanides and / or from the group of polyorganosiloxanes.

IV) 0 to 50 wt .-%, preferably, 0.3 to 40 wt .-%, more preferably 0.5 to 30 wt .-% of at least one silicon-organic compound as a component

(D),

V) 0 to 12 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-% of a metal compound of the formula (IV)

MR _x ⁹ (V) with M = Ge, Sn, Pb, Ti ₁ Zr, B, Al,

X = 3 or 4, R ⁹ = halogen, hydroxyl, alkoxy, alkoxycarboxyl group, where the radical R may be identical or different, as component (E), EP2005 / 006835

23

VI) O to 15 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-% of a photoinitiator as component (F),

VII) O to 50% by weight of additives as component (G) ₁ selected from the group of plasticizers, catalysts, stabilizers, dispersants, antioxidants, dyes, fillers, and agents for influencing the flowability of the dispersion of component (C) in component ( A), (B) or (D) or in a mixture of these components, wherein the sum of said components gives 100 wt .-%.

In a particular embodiment of the invention, the binder contains barrier properties

10 to 50 wt .-%, particularly preferably 15 to 40 wt .-%, of the organosilicon compound as component (D4), wherein component (D4) is obtainable by reacting

(i) a monomer-poor polyurethane prepolymer having free NCO groups as polyisocyanate (a), wherein the low-monomer polyurethane prepolymer is an addition product of at least one polyisocyanate of the group IPDI, MDI or TDI and at least one polyol having a molar mass of 150 g / mol to 2000 g / mol; and at least

(ii) a hydroxyacrylate selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,

Hydroxyhexyl (meth) acrylate, and at least (iii) a compound of the formula: YA-Si ((Z) n) (T) ₃ . _n (II) where Y = an NCO-reactive group, preferably one

-OH, -COOH, -SH, -NH ₂ , NHR "- group;

R ^"= a linear or branched, saturated or unsaturated Ci-Ciβ alkyl; C ₅ -C ₈ cycloalkyl, C ₆ -C ₀ aryl, _{_C7-Ci2} aralkyl; oxyalkylene radical having up to 4 carbon Atoms, preferably - (CH ₂ -CH ₂ -O) _m -H and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; A-Si ((Z) _n ) (X) ₃ _-n ; alkyl, cycloalkyl or aryl substituted siloxane group having from about 1 to about 20 Si atoms; 06835

24

A = a linear or branched, saturated or unsaturated alkylene group having 1 to 12 C atoms, preferably a linear or branched alkylene group having 1 to 4 C atoms

Z = C 1 -C ₈ -alkyl group, preferably C 1 -C ₄ -alkyl group;

T = -NH ₂ ; -NH-CO-R ⁵ ; -OOC-R ^5; -ON = C (R ⁵ ) ₂ or OR ⁶ ;

R ⁵ = a linear or branched, saturated or unsaturated C ₁ -C ₁₈ -alkyl radical, preferably a methyl, ethyl-propyl or iso-propyl radical;

R ⁶ = R ⁵ , preferably a methyl, ethyl, propyl or isopropyl radical; or an oxyalkylene radical having up to 4 carbon atoms, preferably - (CH ₂ -CH ₂ -O) _m -H and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; a C ₅ -C ₈ cycloalkyl group; a C ₆ -C ₁₀ - aryl or C ₇ -C ₂ aralkyl; m = 1 to 40, preferably 1 to 20, particularly preferably 1 to 10; n = 0, 1 or 2.

The monomer-poor polyurethane prepolymer of step (i) contains less than 0.5% by weight, preferably less than 0.3 and especially preferably less than 0.1% by weight, of free monomeric polyisocyanate of the group IPDI, MDI or TDI, based on the total amount of PU prepolymer. The isocyanate groups present should react during the reaction of the components i, ii, iii to D4. In a further preferred embodiment of the invention, the components (D1), (D2) and / or (D3) to 0.3 wt .-% to 20 wt .-%, preferably 0.4 wt .-% to 15 wt. % and in particular preferably 0.5 to 10 wt .-%, based on the total composition of components (I) to

(VII).

The radiation-curable binder according to the invention with barrier properties can, depending on the required field of application, still up to 60 wt .-% of inert

Contain solvents.

In principle, all organic solvents known to the person skilled in the art are used as solvents

Solvents usable, in particular esters, ketones, halogenated

Hydrocarbons, alkanes, alkenes and aromatic hydrocarbons.

Examples of such solvents are methylene chloride, trichlorethylene, toluene, xylene,

Butyl acetate, amyl acetate, isobutyl acetate, methyl isobutyl ketone, methoxybutyl acetate,

Cyclohexane, cyclohexanone, dichlorobenzene, diethyl ketone, di-isobutyl ketone, dioxane, 35

25

Ethyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl acetate, 2-ethylhexyl acetate, glycol diacetate, heptane, hexane, isobutyl acetate, isooctane, isopropyl acetate, methyl ethyl ketone, tetrahydrofuran or tetrachlorethylene or mixtures of two or more of said solvents.

The preparation of the radiation-curable binder according to the invention having barrier properties can be carried out by customary techniques known to the person skilled in the art in the context of the preparation of polymeric mixtures.

The curing of the binder leads to block-resistant, ie non-adhesive and in particular scratch-resistant coatings, fillers or sealants with flexible. Properties or surface-adhesive adhesives. The radiation-curable binders according to the invention having barrier properties can therefore be used as coating agents, fillers, sealants or adhesives and are characterized as adhesive seals or fillers with barrier properties to CO ₂ , O ₂ , N ₂ , gas mixtures, for example from CO ₂ and N ₂ , water vapor and flavors.

In principle, the radiation-curable binder according to the invention having barrier properties can be used for filling, sealing, coating and bonding a wide variety of materials. The materials include, for example, wood, metal, glass, vegetable fibers, stone, paper, cellulose hydrate, plastics such as polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl acetate olefins, polyamides, or metal foils, for example Aluminum, lead or copper.

The radiation curable binder of the present invention having barrier properties can be applied to the substrate by any suitable method, for example, spraying, knife coating, 3-4 roll applicators in the case of using a solventless binder, or 2 roll coaters in the case of using a solventborne binder. 06835

26

The radiation-curable binder according to the invention with barrier properties is suitable for coating substrates of glass, metal, plastic, paper, ceramic, etc. by dipping, pouring, brushing, spraying, electrostatic spraying, electrodeposition coating, etc. The binders are in particular for the coating optical, Optoelectrical or electronic article suitable and for coating containers for fuels and heating fuels.

With the radiation-curable binder according to the invention, adhesives having barrier properties are provided, which are preferably suitable for the production of film composites. By a content of less than 0.05 wt .-% of monomeric polyisocyanate, the binder is particularly suitable for flexible film composites, which are used in food packaging.

Another object of the present invention is therefore also a process for the production of film composites of at least two identical or different plastic films, which are obtainable by the partial or full surface bonding of films, using the radiation-curable binder according to the invention with barrier properties.

The order of the binder on the films to be bonded can be done with commonly used for such purposes machines, for example, with conventional laminating. Particularly suitable is the application of the binder in the liquid state to a film to be bonded to a laminate, for example a film made of plastic or metal. The viscosity of the binder is selected to have a viscosity of about 500 mPas, in particular 1,000 mPas to about 5,000 mPas (measured with Brookfield Digital Viscometer RVT DV-II, spindle 27) at typical processing temperatures. Temperatures typical Verarbeitungs¬ are, for example, about 25 ° C to about 75 ⁰ C in the manufacture of flexible packaging films (flexible packaging), about 70 to about 90 ° C in the lamination of glossy films and about 80 to about 130 ° C for applications in the textile industry.

The coated with the inventive solvent-containing radiation-curable binder with barrier properties film is first in the drying channel at 40 bis 120 ⁰ C dried, then with at least one further film, optionally under pressure, laminated and then irradiated. In the inventive solvent-free

Binder eliminates the drying step.

The radiation-curable binder according to the invention having barrier properties is obtained by the irradiation and the crosslinking reaction associated therewith

Molecular weight, thus has more cohesion and has a sticky

Surface. If the irradiation takes place by means of UV light, the binder used according to the invention contains at least one photoinitiator as component (F).

The described method can be repeated several times, so that

Foil composites can be made, which consist of more than two bonded

Layers exist.

The process according to the invention can be carried out under a protective gas atmosphere, ie in

However, it is also advantageously under a normal atmosphere, as typically in the

Production halls prevails, easy to carry out.

Another object of the invention is a composite film prepared by the process according to the invention using the binder according to the invention. The composite film is particularly suitable as a barrier film for packaging food. In the practice of food packaging, barrier films are used when the oxygen permeability Q (O ₂ ) <100 cm ³ / (m ² × day × bar) and the water vapor permeability Q (H ₂ O) <10 g / (m ² × day) ) at 23 ⁰ C and 85% rel. Moisture is (Delventhal, Verpackungs-Rundschau 3/1991, page 19-23).

06835

28

Examples of laminating adhesive:

It will

18.75 g (component A) of a difunctional aromatic polyurethane acrylate having a molecular weight of about 5000 g / mol (Akzo Nobel Actilane

170), 76.5 g (component B of a carboxylic acid-modified acrylate derivative (Cognis

Photomer 4173),

51, 0 g finely dispersed SiO ₂ mixed and homogenized. 1, 5 g (component D) of allyltrimethoxysilane are then added and mixed. 2.25 g of a commercially available photoinitiator (Ciba Irgacure 819) are added and homogenized. A liquid laminating adhesive is obtained.

Comparative test

An analogous adhesive mixture without SiO 2 is prepared, the amount of component C being replaced by equal proportions of component B.

Kaschierversuche

The adhesive is applied to an Oa film at about 80 ^° C. The coating weight of the adhesive was 2 g / m ^{2 in} each case. Subsequently, a second film is laminated. The following were laminated: a) 2 oriented polypropylene (OPP) films (ExxonMobil MB 400) b) polyester film (PET) (Mitsubishi RNK) with polyethylene film (Nordenia PE K088).

This was followed by irradiation with UV rays with a 120 W mercury lamp (UV dose = 70 mJ / cm ² ). This results in a clear and stable bond. The barrier behavior against water vapor is good. 005/006835

29

Oxygen permeability measurements:

Tests according to DIN 53380, data in mean values from 3 measurements.

• Bonded with trial adhesive: OPP // OPP composite: 157 cm ³ / m ³ .24h.atm PET // PE compound: 17 crτv7m ³ .24h.atm

• Bonded with comparative experiment: OPP // OPP composite: 596 cm ³ / m ³ .24h.atm PET // PE compound: 77 cm ³ / m ³ .24h.atm

The oxygen permeability with the adhesive according to the invention is improved.

Claims

claims

1. Binder with barrier properties, containing

A) at least one in the range of 18 ° C to 100 ⁰ C ₁ preferably 2O ⁰ C to 80 ⁰ C, flowable compound having at least one radiation-curable reactive functional group as component (A);

2. A binder according to claim 1, characterized in that it has at 60 ° C has a viscosity of 50 mPa.s to 52 000 mPa.s (measured according to Brookfield, Digital Viscometer RVT DV-II, spindle 27).

3. A binder according to claim 1, characterized in that the viscosity at the processing temperature between 500 mPas to 5000 mPas.

4. A binder according to claim 1 to 3, characterized in that component (A) is selected from the group: polyacrylic and / or polymethacrylic acid alkyl, cycloalkyl or aryl esters, methacrylic acid and / or acrylic acid homo- and / or Copolymers, unsaturated polyesters, polyethers, polycarbonates, polyacetals, polyurethanes, polyolefins, vinyl polymers or rubber polymers such as nitrile or styrene / butadiene rubber.

5. A binder according to any one of claims 1 to 4, characterized in that as component (A) compounds from the group: (meth) acrylic acid homopolymers and / or copolymers, polyester (meth) acrylic, epoxy (meth) acrylates or polyurethane (meth) acrylates. P2005 / 006835

31

6. A binder according to claim 1 to 3, characterized in that as component (A) esters of acrylic acid or methacrylic acid with aromatic, aliphatic, cycloaliphatic, polyols or polyether alcohols, in particular (meth) acrylate esters of aliphatic polyols having 2 to about 40 carbon atoms are selected ,

7. A binder according to claim 6, characterized in that as component (A) compounds having the general formula (I) are used:

H ₂ C = CR ¹ -C (OO) -O- (R ⁷ -O) _n R ⁸ (I) with:

R ¹ = H, CH ₃ ;

R ⁷ = straight-chain or branched alkylene group of C ₂ to C ₁₀ ; R ⁸ = straight-chain or branched alkylene group of C 1 to C ₅ ; n = 1 to 25.

8. A binder according to claim 7, characterized in that component (A) is methoxyethyl acrylate, ethoxymethyl methacrylate, methoxyethoxyethyl methacrylate, ethoxyethoxyethyl acrylate, butyldiethylene glycol methacrylate, ethoxylated nonylphenol acrylate, ethoxylated lauryl alcohol methacrylate, alkoxylated tetrahydrofurfuryl acrylate, or methoxypolyethylene glycol monoacrylate.

9. A binder according to claim 6 or 7, characterized in that component (A) is selected from the group hydrofunctional Ethylhexylmethacrylat, octyl / decyl acrylate, ethoxylated trimethylolpropane triacrylate, modified aromatic or aliphatic epoxy acrylates, Neopentylglykoldi (meth) acrylate, 1, 6 Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, neopentyl glycol hydroxy-pivalate di (meth) acrylate, caprolactone-modified neopentyl glycol hydroxypivalate di (meth) acrylates, ethylene oxide-modified neopentyl glycol di (meth) acrylates, propylene oxide -modified neopentyl glycol di (meth) acrylates, ethylene oxide-modified 1,6-hexanediol di (meth) acrylates or propylene oxide-modified 1,6-hexanediol di (meth) acrylates, polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates, pentaerythritol tri- and tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone-modified tris [(meth) acryloxyethyl] isocyanurates or trimethylolpropane (meth) acrylate, di-, tri- and tetrapropylene glycol diacrylate, neopentyl glycol propoxylate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane monethoxytri (meth) acrylate and pentaerythritol triacrylate, amine-modified polyether acrylates.

10. A binder according to claim 1 to 3, characterized in that component (B) is selected from the group: built on polyether acid-modified (meth) acrylates, acrylated carboxylic acid-terminated polyester, acid-modified polybutadienes or mixtures thereof of said compounds.

11. A binder according to claim 1, characterized in that component (C) is amorphous silica.

12. A binder according to any one of claims 1 to 11, characterized in that as component (D) at least one silicon-organic compound is contained.

13. A binder according to claim 12, characterized in that component (D) as component (D1) at least one three-dimensionally crosslinkable polyorganosiloxane, which after crosslinking has an average particle diameter in the range of 70 nm to 1000 nm, is.

14. Binder according to claim 12, characterized in that as component (D) a reaction product (D2) is used, preferably a Ver or transesterification product of acrylic acid and / or methacrylic acid or derivatives thereof with a silane (e), wherein the silane (e) is characterized by the general formula (II): With

Y = epoxide, -OH, -COOH, -SH, -NH ₂ , NHR "- group;

R ^" = linear or branched, saturated or unsaturated C 1 -C ₈ -alkyl, C 1 -C 6 -cycloalkyl, C ₆ -C 10 -aryl, C ₇ -C ₁₂ -aralkyl radical; oxyalkylene radical having up to 4 C atoms, being preferred - (CH ₂ -CH ₂ -O) _m -H and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; A-Si ((Z) _n ) (X) ₃ -n; Alkyl, cycloalkyl or aryl groups substituted siloxane radical having from about 1 to about 20 Si atoms; siloxane radical having from about 1 to about 20 Si atoms;

A = a linear or branched, saturated or unsaturated alkylene group having 1 to 12 C atoms, preferably a linear or branched alkylene group having 1 to 4 C atoms;

Z = Ci-Ci ₈ alkyl group, preferably CrGt alkyl group;

T = -NH ₂ ; -NH-CO-R ⁵ , -OOC-R ⁵ ; -ON = C (R ⁵ ) ₂ or OR ⁶ ;

R ⁵ = a linear or branched, saturated or unsaturated C ₁ -C ₈ -alkyl radical, preferably a methyl, ethyl, propyl or isopropyl radical;

R ⁶ = R ⁵ , preferably a methyl, ethyl, propyl or isopropyl radical; or an oxyalkylene radical having up to 4 carbon atoms, preferably - (CH ₂ -CH ₂ -O) _m -H and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; a C ₅ -C ₈ cycloalkyl group; a C ₆ -C ₀ - aryl or C ₇ -C ₂ aralkyl; m = 1 to 40, preferably 1 to 20, particularly preferably 1 to 10; n = 0, 1 or 2.

15. Binder according to claim 14, characterized in that the silane (e) of the general formula (II) is selected from the group: 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxyphenylsilane and 3-aminopropyldiethoxyethylsilane, in particular 3 -Aminopropyltrimethoxysilane or bis (3-triethoxysilylpropyl) amine, or mixtures thereof.

16. A binder according to claim 14, characterized in that component (D2) is 3-methacryloxypropyltrimethoxysilane and / or allyltriethoxysilane.

17. A binder according to claim 12, characterized in that as component (D) a urethane group-containing silane (D3) having an isocyanate content <1 wt .-% NCO, preferably <0.5 wt .-% NCO and particularly preferably <0.1 % By weight of NGOs.

18. A binder according to claim 12, characterized in that component (D) as component (D4) is a urethane group-containing silane having at least one curable by irradiation reactive group.

19. Binder with barrier properties, containing

I. 5 to 80 wt .-%, preferably 5 to 45 wt .-% at least one in the range of 18 ° C to 100 ⁰ C, preferably 20 ⁰ C to 80 ⁰ C, flowable compound having at least one curable by irradiation reactive functional Group as component (A);

II. 1 to 70 wt .-%, preferably 10 to 60 wt .-% of at least one compound having at least one radiation-curable reactive functional group and at least one COOH group as component (B);

III. 5 to 50 wt .-%, preferably 20 to 45 wt .-%, particularly preferably 30 to 40 wt .-%, at least one nanoscale filler as component (C), which is preferably selected from the group: oxides, nitrides, halides , Sulfides, carbides, tellurides, selenides of the second to fourth main group, the transition elements, the lanthanides and / or from the group of polyorganosiloxanes.

IV. 0 to 50 wt .-%, preferably, 0.3 to 40 wt .-%, particularly preferably 0.5 to 30 wt .-% of at least one silicon-organic compound as component (D),

V. 0 to 12 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-% of a metal compound of the formula (IV)

MR _x ⁹ (IV) with M = Ge ₁ Sn ₁ Pb ₁ Ti, Zr ₁ B ₁ Al ₁

X = 3 or 4,

R ⁹ = halogen, hydroxyl, alkoxy, alkoxycarboxyl group, wherein the

R may be the same or different, as component (E),

VI. 0 to 15 wt .-%, preferably 0.5 to 10 wt .-%, particularly preferably 1 to 5 wt .-% of a photoinitiator as component (F). ₁

VII. 0 to 50 wt .-% of additives as component (G) ₁ selected from the group of plasticizers, catalysts, stabilizers, dispersants, antioxidants, dyes, fillers, and means for influencing the flowability of the dispersion of component (C) in component ( A) ₁ (B) or (D) or in a mixture of these components, wherein the sum of said components gives 100 wt .-%.

20. A binder according to claim 19, containing as component (D)

10 to 50 wt .-%, particularly preferably 15 to 40 wt .-%, an organosilicon compound (D4), wherein component (D4) is obtainable by reacting

(i) a monomer-poor polyurethane prepolymer having free NGO groups as polyisocyanate (a), wherein the low-monomer polyurethane prepolymer is an addition product of at least one polyisocyanate of the group IPDI, MDI or TDI and at least one polyol having a molar mass of 150 g / mol to 2000 g / mol; and at least (ii) a hydroxyacrylate selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,

Hydroxyhexyl (meth) acrylate, and at least (iii) a compound of the formula: YA-SK (Z) _n ) (T) ₃ -H (II) where Y = an NCO-reactive group, preferably one

-OH ₁ -COOH ₁ -SH ₁ -NH ₂ , NHR "- group;

R ^"= a linear or branched, saturated or unsaturated alkyl CrCiβ C _δ -Cs-cycloalkyl, C ₆ -C ₀ aryl, _{_C7-Ci2} aralkyl; oxyalkylene radical having up to 4 carbon atoms, preferably - (CH ₂ -CH ₂ -O) ₁₁₁ -H and / or (CH ₂ - CH _(CH3) -O) _m -H; A-Si ((Z) _n ) (X) ₃ _-n ; one with alkyl, cycloalkyl or

Aryl-substituted siloxane radical having from about 1 to about 20 Si

atoms; A = a linear or branched, saturated or unsaturated

Alkylene group having 1 to 12 carbon atoms, preferably a linear or branched alkylene group having 1 to 4 carbon atoms Z = Ci-Ci ₈ alkyl group, preferably Ci-C ₄ alkyl group; T = -NH ₂ ; -NH-CO-R ⁵ ; -OOC-R ^5; -ON = C (R ⁵ ) ₂ or OR ⁶ ; R ⁵ = a linear or branched, saturated or unsaturated C ₁ -C ₈ -

Oxyalkyenrest with up to 4 C-atoms, preferably - (CH ₂ -CH ₂ -O) _1T1-H and / or (CH ₂ -CH (CH ₃ ) -O) _m -H; a C ₅ -C ₈ cycloalkyl group; a C ₆ -C ₁₀ -

Aryl radical or a C ₇ -C ₁₂ aralkyl radical; m = 1 to 40, preferably 1 to 20, particularly preferably 1 to 10; n = 0, 1 or 2.

21. Binder according to claim 20, characterized in that the low-monomer polyurethane prepolymer less than 0.5 wt .-%, preferably less than 0.3 and particularly preferably less than 0.1 wt .-% free polyisocyanate of the group IPDI, MDI or TDI, based on the total amount of PU prepolymer contains.

22. Use of the binder according to one of claims 1 to 21 as a radiation-curable binder in coating compositions, fillers, sealants or adhesives.

23. Use of the binder according to claim 22 for the production of film composites.

24. A process for the production of film composites from at least two identical or different plastic films, characterized in that one uses a binder according to one of claims 1 to 21.

25. film composite obtainable by the process according to claim 24.

26. Film composite according to claim 25, characterized in that it has barrier properties to CO2, O ₂ , N ₂ , water vapor and flavorings.

27.Use of a film composite according to claim 25 or 26 for packaging food.