DE19836695A1 - Adhesive for production of laminated glass, e.g. safety glass, contains acrylic monomers, acrylate-functional oligomers, coupling agent and photoinitiator, optionally with inert polymer and other additives - Google Patents

Abstract

An adhesive for the production of laminated glass contains (meth)acrylate monomers, (meth)acrylate-functional oligomers, coupling agent and photoinitiator, and optionally also unreactive (meth)acrylate homo- and co-polymers, fillers, tackifiers and stabilizers. An adhesive for the production of laminated glass has a viscosity of 5-300 Pa.s and a liquid limit of 5-800 Pa and contains (a) 5-90 wt.% (meth)acrylate monomers, (b) 5-60 wt.% (meth)acrylate-functional oligomers, (c) 0-15 wt.% unreactive (meth)acrylate homo- and co-polymers, (d) 0-30 wt.% fillers, (e) 0-15 wt.% plasticizers, (f) 0.3-3 wt.% coupling agent, (g) 0.1-3 wt.% photoinitiator, (h) 0-5 wt.% tackifiers and (i) 0-2 wt.% stabilizers. An Independent claim is also included for a process for the production of this adhesive by mixing the components at 15-70 deg C in a planetary dissolver, a blade mixer and/or a turbulent mixer.

Description

The present invention relates to a new adhesive for the production of laminated glass.

Laminated glass consists of at least two sheets of glass and an intermediate layer that connects the glass panels connects. The glass panels can be used in any combination can be selected from inorganic glasses such as float glass, White glass, toughened safety glass, partially toughened Glass, colored glass, coated glass, mirrored Glass, thin-film solar modules, and made of organic glasses, such as polycarbonate (PC) or polymethyl methacrylate glass (PMMA).

Laminated glass is used e.g. B. as laminated glass with Safety and / or soundproofing properties when Protection of surfaces by gluing with a Glass pane or in the manufacture of solar modules.

A widely used method of making Laminated glass works in such a way that an oblique erected, from two, at a certain distance existing, cleaned glass panels Disc pack filled with a low-viscosity casting resin will. Here is the one between the two glass panels located cavity to the outside with z. B. a double-sided tape, which is between the two Glass panels located, sealed. This edge seal can also with a butyl cord that has a hard core made of one thermoplastic polymer such as B. polypropylene, contains, exist.

After filling, tilt the filled double pane in the horizontal, venting and sealing the Filling opening with a thermoplastic material, e.g. B. again with a hot melt adhesive or with a Butyl cord, the curing takes place between the Cast resin layer located on the glass panels. the In the case of a one-component system, curing can be caused by UV Light or thermal and with a multi-component system by storage at room temperature or by supplying heat take place.

Those commonly used in this procedure liquid casting resins have viscosities <500 mPa.s and usually consist of acrylates, which z. B. urethane acrylate Oligomers as chain crosslinkers and multifunctional ones Standard reactive thinners based on acrylate, such as B. Triethylene glycol diacrylate. The casting resins can transparent, colored or cloudy. the Cast resin layer usually has after hardening a layer thickness of 1 to 3 mm.

The casting resins described have due to the low Viscosity has the disadvantage with insufficient wetting of the Glass surface through the edge sealing described (Tape or butyl cord) or even just minor damage to the same due to infiltration the edge seal slightly out of the filled double disc to run out. Also is to make sure that the sealing material for the Cast resin filling opening compatible with edge sealing and to the casting resin used, as it is incompatible again there is a risk of leakage and additionally Discoloration of the casting resin can occur.

Another disadvantage of the casting resins used hitherto is their volume shrinkage of approx. 10 to 17 vol% during the Curing. This will result in the hardened laminated glass Stresses generated in the cast resin layer, which in the Extreme case of detachment of the cast resin layer from the glass (Delamination) can lead.

Also the process of making laminated glass with a casting resin is subject to limitations or disadvantages. This is how the adhesive tape or the Butyl cord manually, which is very time consuming. Cast resin layers with a thickness <0.9 mm cannot getting produced; due to the need for the fast filling and venting of the glass panel composite is the process based on the use of low-viscosity resins limited; for venting is tipping from the Vertical to horizontal necessary, what a manual control required; with larger ones Disc dimensions result in stronger Layer thickness differences, and the casting resin must be stationary Harden. The layer thickness differences of the hardened Cast resin layer can be due to the low Viscosity of the casting resin with a nominal layer thickness of 1.0 mm range from 0.2 to 0.8 mm.

The invention is therefore based on the object that To overcome disadvantages of the prior art and to Manufacture of laminated glass to create an adhesive which is in the finished laminated glass instead of the cast resin located between the glass sheets, which has a high viscosity and the use of a new, automated Process for the production of edge sealing-free Laminated glass allowed.

The object is given by the one in claim 1 Solved adhesive. Claims 2 to 5 form the specified adhesive further. The claims 6 to 7 give a method for producing the invention Adhesive. Claims 8 to 9 give the use of the adhesive according to the invention in processes for Manufacture of laminated glass.

The adhesive mainly consists of reactive acrylate and methacrylate monomers that form upon curing Copolymer form, which in turn has a crosslinked structure may have. The adhesive also contains acrylate and methacrylate-functional oligomers (such as Urethane acrylates, polyester acrylates), adhesion promoters and Initiators. He can still use non-reactive acrylate and Methacrylate homo- and copolymers, fillers, plasticizers, contain tackifying additives and stabilizers.

The adhesive has the following composition (data in% by weight):

a) reactive acrylate or methacrylate monomers 5-90 b) acrylate- or methacrylate-functional oligomers 5-60 c) non-reactive acrylate or methacrylate homo- and copolymers 0-15 d) fillers 0-30 e) plasticizers 0-15 f) adhesion promoter 0.3-3 g) photoinitiators 0.1-3 h) tackifying additives 0-5 i) stabilizers 0-2

A preferred form of the adhesive has the following composition:

a) reactive acrylate or methacrylate monomers 30-60 b) acrylate- or methacrylate-functional oligomers 20-40 c) non-reactive acrylate or methacrylate homo- and copolymers 0-15 d) fillers 5-25 e) plasticizers 0-15 f) adhesion promoter 0.5-3 g) photoinitiators 0.1-2 h) tackifying additives 0-5 i) stabilizers 0-2

Are used as reactive acrylate and methacrylate monomers monofunctional and multifunctional, preferred monofunctional, esters of acrylic or methacrylic acid used. The alcohol components used in the esters can be substituted by functional groups or unsubstituted alkyl group, such as methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, pentyl, hexyl, their Isomers and higher homologues, such as 2-ethylhexyl, Phenoxyethyl, hydroxyethyl, 2-hydroxypropyl, Caprolactone hydroxyethyl, polyethylene glycols with a Degree of polymerization from 5 to 20, polypropylene glycols with a degree of polymerization of 5 to 20 and Dimethylaminoethyl. As reactive monomers can also the acrylic and methacrylic acids themselves, the amides of these Acids and acrylonitrile are used. It can too Mixtures of the reactive acrylate and methacrylate monomers be used.

Examples of acrylate and methacrylate functional Oligomers are epoxy acrylates, urethane acrylates, Polyester acrylates and silicone acrylates. The oligomers can be mono- or higher functional, preferably they will used difunctionally. Mixtures of the Oligomers are used.

Epoxy acrylates are based on each with acrylic or Methacrylic acid terminated bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, their oligomers or Novolak glycidyl ether.

Urethane acrylates are made up of isocyanates (e.g. Toluene, tetramethylxylene, hexamethylene, isophorone, Cyclohexylmethane, trimethylhexamethyl, xylene or Diphenylmethane diisocyanate) and polyols and functionalized with hydroxyacrylates (e.g. Hydroxyethyl acrylate) or hydroxymethacrylates (e.g. Hydroxyethyl methacrylate).

The polyols can be polyester polyols or Polyether polyols. Polyester polyols can be made are made from a dicarboxylic acid (e.g. adipic acid, Phthalic acid or its anhydrides) and a diol (e.g. 1,6- Hexanediol, 1,2-propanediol, neopentyl glycol, 1,2,3- Propanetriol, trimethylolpropane, pentaerythritol or Ethylene glycols such as diethylene glycol). Polyester polyols can also be achieved by reacting a hydroxycarboxylic acid (e.g. starting from caprolactone) can be obtained with itself. Polyether polyols can be made from ethylene oxide or propylene oxide getting produced.

Polyester acrylates are the polyester polyols described above, functionalized with acrylic acid or with methacrylic acid are.

The silicone acrylates used here, which are known per se are based on functionalized with acrylate Polydimethylsiloxanes of different molecular weights.

Non-reactive acrylate and methacrylate homo- and copolymers are homo- and copolymers of acrylic acid, the Methacrylic acid and the above-described esters thereof Acids. The adhesive can also be mixtures of the above Contain homo- and copolymers. The glue can too without non-reactive acrylate or methacrylate homo- and Copolymers are produced.

Fillers can be reinforcing and non-reinforcing. Fumed or precipitated silicas, which are preferably hydrophilic or surface treated, and cellulose derivatives, such as cellulose acetate, -acetobutyrate, -acetopropionate, methyl cellulose and Hydroxypropylmethylcellulose, can be used. Of the Adhesive can also be mixtures of the fillers mentioned contain. The adhesive can also be used without fillers getting produced.

Examples of plasticizers are esters of phthalic acid, such as Di-2-ethylhexyl, diisodecyl, diisobutyl, dicyclohexyl, and dimethyl phthalate, esters of phosphoric acid, such as 2- Ethylhexyl-diphenyl-, tri (2-ethylhexyl) - and tricresyl phosphate, ester of trimellitic acid, such as tri (2-ethylhexyl) - and triisononyl trimellitate, esters of citric acid, such as Acetyl tributyl and acetyl triethyl citrate, and esters of Dicarboxylic acids such as di-2-ethylhexyl adipate and Dibutyl sebacate. The adhesive can also be mixtures of the contain plasticizers mentioned. The glue can too are made without plasticizers.

Adhesion promoters can be selected from the group of organofunctional silanes such as 3-glycidyloxypropyl trialkoxysilane, 3-aminopropyl-trialkoxysilane, N-aminoethyl- 3-aminopropyl-trialkoxysilane, 3-methacryloxypropyl trialkoxysilane, vinyl trialkoxysilane, iso- Butyltrialkoxysilane, mercaptopropyl-trialkoxysilane, and off the group of silicic acid esters, such as Tetraalkyl orthosilicate. The adhesive can also be mixtures of the mentioned adhesion promoters included.

As photoinitiators, compounds from the Group of benzoin ethers, benzil ketals, α- Dialkoxyacetophenones, the α-hydroxyalkylphenones, the α- Aminoalkylphenones, the acylphosphine oxides, the benzophenones or the thioxantones or mixtures thereof are used will.

Tackifying additives can be selected from Group of natural and synthetic, even afterwards modified, resins. Serve as resins Hydrocarbon resins, rosin and its derivatives, Polyterpenes and their derivatives, coumarone-indene resins, Phenolic resins, polybutenes, hydrogenated polybutenes, Polyisobutenes and hydrogenated polyisobutenes. The adhesive can also include mixtures of the tackifying additives mentioned contain. The glue can also be used without tackifying Additives are made.

Stabilizers can include antioxidants such as phenols (e.g. 4- Methoxyphenol) or sterically hindered phenols (e.g. 2,6- Di-tert-butyl-4-methylphenol) or mixtures of various antioxidants. The glue can too can be produced without stabilizers.

The adhesive is more viscous and preferably thixotropic set. The viscosity range is 5 to 300 Pa.s. the thixotropy increases with decreasing viscosity is set. The adhesive has a yield point in the Range from 5 to 800 Pa, preferably in a range from 20 to 80 Pa.

The adhesive of the invention is made by mixing the Ingredients produced in a suitable aggregate. If high shear forces are used to destroy Agglomerates are necessary, the aggregate can be a Planetary dissolver with fast rotating dissolver disc be. If high shear forces are not required when mixing the unit can be a paddle mixer or a Be turbulence mixer. Whether high or low shear forces needed depends on the ingredients used away. So is z. B. to incorporate fumed silica a dissolver disk in a medium viscosity liquid indispensable. At low viscosities, the Use of a bead mill may be necessary. By mixing the viscosity of fillers increases significantly. At the Mixing process can use vacuum or inert gas to be necessary.

The mixing temperature is at the start of mixing Room temperature (15 to 25 ° C) and may depend on the consistency of the mixture and the energy input of the used mixing unit up to 70 ° C. at Use of low-boiling monomers, such as. B. Methyl methacrylate, cooling may be necessary.

If the adhesive contains an additional ingredient or more organic dyes (e.g. azo dyes or Phthalocyanine metal complexes) and / or inorganic colored Nanoparticles, that's what is made from this adhesive Laminated glass colored.

The glue contains additional ingredients inorganic pigments (e.g. titanium dioxide), that's off Laminated glass made with this adhesive tarnished. Will If colored inorganic pigments are used, the cloudiness is the result appropriately colored.

The adhesive according to the invention can be used in a process for the production of laminated glass in which only five process steps are necessary:

• 1.Cleaning and drying the glass panels,
• 2. Application of a liquid adhesive to the inside the first, horizontally lying glass panel,
• 3. congruent placement of the second glass panel on the Adhesive layer,
• 4. Compression of the sandwich arrangement and
• 5. Curing of the adhesive layer.

This method can e.g. B. be designed as follows:
The cleaning with commercially available glass cleaners and the drying of the glass panels is done in a manner known per se. This can preferably be done automatically in a washing machine. After washing, the glass panels must be absolutely dry, free of grease and free of cleaning agent residues. A check for cleanliness is an advantage. This can be done visually with the help of fluorescent tubes. When cutting the glass sheets beforehand, it is advantageous to work with water-soluble cutting oils or with cutting oils that dry without leaving any residue.

The cleaned first glass panel becomes horizontal positioned. On the inside of the above The adhesive is applied to the glass panel. Preferably will the glass panel automatically under the Adhesive applicator passed through, wherein the precisely dosed adhesive application takes place. In general, the Adhesive application an exact one for the respective structure Edge distance to be determined beforehand through experiments to be adhered to so that there is no glue on the edges of the pane can expire.

The adhesive can be applied from a perpendicular to the Transport direction of the glass sheet upright slot nozzle in the form of a closed film.

Alternatively, the adhesive can be applied with a corresponding nozzle arrangement in the form of caterpillar-shaped Strands of adhesive that are parallel to the transport direction of the Glass panel run, take place.

The second sheet of glass is placed on top of the adhesive layer stored congruently so that a Sandwich arrangement, consisting of glass-adhesive-glass, forms. This process step is also preferred carried out automatically.

This sandwich arrangement is then pressed. In addition will put moderate pressure on the outer surface of the second, overhead glass panel exerted, with the pressure is applied along a line that joins the outer Surface of the second glass sheet collapses and is in the general transversely from one side of the second Glass plate extends to the other side of the same. These Print line is from one end of the sandwich to the moved others. The corresponding counter pressure on the lower Glass panel is z. B. exercised through the pad. Of the the pressure to be exerted is 0.5 to 16 bar. Is preferred the pressure with one or more pressure rollers on the upper one second glass plate exercised. The is particularly preferred Print on both glass panels by one or more Pressure roller pairs exerted, the sandwich arrangement through the adjustable space of a Print roller pair is moved.

Any air still present escapes during pressing before the advancing print line. With a caterpillar-shaped When the adhesive is applied, the air escapes through the between the Adhesive beads existing channels. There arises a Air bubble-free bond of the first glass sheet, adhesive and second glass panel. In particular the caterpillar-shaped one Adhesive application has a positive effect on the escape of the Air out.

Eventually the adhesive is cured. this happens by exposure to UV light. After hardening it shows the adhesive layer has a thickness of 0.2 to 5 mm, preferably 0.5 to 2 mm.

The entire arrangement of two glass panels is preferred and glue between and during the aforesaid Process stages automatically funded.

The adhesive according to the invention is also suitable for Manufacture laminated glass with more than two sheets of glass. In addition the corresponding procedural steps are repeated. If a laminated glass is produced with the adhesive, its a glass panel is a thin-film solar module, one obtains a composite voltaic module.

The option to use the adhesive according to the invention an edge seal-free Manufacture laminated glass. Without edge sealing, the curing of the adhesive is less than they harden cast resin in a laminated glass occur with edge sealing.

Another advantage is the less than 10% Volume shrinkage of the adhesive according to the invention during the hardening in comparison with ordinary casting resin. Due to the high viscosity of the adhesive and the uniform compression of the sandwich arrangement is achieved an even layer thickness after curing. Even this reduces stresses in the laminated glass, which advantageously the risk of damage from detachment the adhesive layer is diminished from the glass.

The one that is also advantageous compared to UV-curing Casting resins faster curing of the invention Adhesive.

The object of the invention will be based on the following Examples explained in more detail. The percentages are so far not otherwise noted, weight percent:

Example 1 to 3 Manufacture of the adhesive example 1

In a planet dissolver were considered reactive Acrylate Monomers 215.3 g (35.9%) 2-ethylhexyl acrylate, 48 g (8.0%) polypropylene glycol monomethacrylate with the Degree of polymerization 6 (bisomer PPM6E from Inspec) and 90 g (15%) acrylic acid and as an adhesion promoter 3 g (0.5%) Vinyltrimethoxysilane (Dynasilan VTMO from Sivento) within 5 minutes with 3.6 g (0.6%) of the photo Initiator 1-Hydroxycyclohexylphenylketon (Irgacure 184 der Company Ciba Specialty Chemicals) mixed. Afterward the dissolution took place over a period of 40 minutes of 60 g (10%) of the filler cellulose acetobutyrate (CAB 381-0.5 from Eastman). Thereafter, within 15 Minutes as acrylate-functional oligomer 144 g (24%) of an aliphatic urethane acrylate (Genomer 4258 of From Rahn) and 36 g (6.0%) for 20 minutes highly disperse silica (CAB-O-SIL LM 150 from the company Cabot) incorporated as a further filler and then 15 Minutes a vacuum of 200 mbar was applied. Was received an adhesive with a viscosity of 41 Pa.s and a Yield point of 20 Pa.

Example 2

In one with butterfly stirrer and dissolver disc equipped mixers from Molteni were used as reactive acrylate monomers 1200 g (30.0%) 2- Ethylhexyl acrylate, 400 g (10.0%) Polypropylene glycol monoacrylate with a degree of polymerization of 6 (Bisomer PPA6 from Inspec) and 600 g (15.0%) Acrylic acid and as an adhesion promoter 16 g (0.4%) des organofunctional silane 3-mercaptopropyltrimethoxysilane (Dynasilan MTMO from Sivento) and 24 g (0.6%) des Photoinitiator 1-Hydroxycyclohexylphenylketone (Irgacure 184 from Ciba Specialty Chemicals) within 10 Mixed together for minutes, then for 40 minutes 320 g (8.0%) of the filler cellulose acetobutyrate (CAB 381-0.5 of the Eastman company), then as Acrylate Functional Oligomer 1200 g (30.0%) of one aliphatic urethane acrylate (Genomer 4258 from the company Rahn) was added and mixed for 15 minutes. After that were 240 g (6.0%) of a further filler during 20 minutes highly disperse silica (Aerosil 200 from Degussa) incorporated. Finally a vacuum was applied for 30 minutes of 100 mbar applied. The viscosity of the obtained The adhesive was 20 Pa.s and the yield point was 107 Pa.

Example 3

In one with butterfly stirrer and dissolver disc equipped mixers from Molteni were used as reactive acrylate monomers 1200 g (30.0%) 2- Ethylhexyl acrylate, 400 g (10.0%) Polypropylene glycol monoacrylate with a degree of polymerization of 6 (Bisomer PPA6 from Inspec) and 600 g (15.0%) Acrylic acid and as an adhesion promoter 16 g (0.4%) des organofunctional silane 3-mercaptopropyltrimethoxysilane (Dynasilan MTMO from Sivento) and 24 g (0.6%) des Photoinitiator 1-Hydroxycyclohexylphenylketone (Irgacure 184 from Ciba Specialty Chemicals) within 5 Mixed together for minutes, then for 60 minutes 240 g (6.0%) of the filler cellulose acetobutyrate (CAB 381-2 of the Eastman company), then as Acrylate Functional Oligomer 1280 g (32.0%) of one aliphatic urethane acrylates (Craynor CN 965 from Cray Valley) and mixed for 15 minutes. Thereafter were used as a further filler 240 g (6.0%) for 20 minutes a highly disperse silica (CAB-O-SIL M5 from the company Cabot) incorporated. Eventually it was on for 30 minutes A vacuum of 50 mbar is applied. The viscosity of the obtained Adhesive was 15 Pa.s and the yield point 50 Pa.

Examples 4 to 7 Use of the glue, manufacture of laminated glasses Example 4 Production of a laminated glass

On a cleaned, horizontally lying glass panel of the Dimensions 400 × 300 × 3.85 mm were along the 300 mm long pane edge 200 g of the adhesive from Example 3 "Wurstig" launched. Then with a Notched trowel peeled off the adhesive lengthways and the amount of adhesive applied is balanced. It happened an adhesive application of 91 g. On the resulting A second, cleaned glass sheet was made with adhesive beads identical dimensions placed congruently so that each next to the caterpillar-shaped adhesive strands Air ducts were located. This sandwich arrangement was made with a hand roller (diameter 100 mm) pressed. This was done the hand roller under a moderate, hand-exercised Print lengthways from one side of the Sandwich arrangement moved to the other, with the still between the two glass panels through the Canals before the print line escaped, the canals closed and an air bubble-free composite of the two Glass panels with the adhesive layer in between originated. The adhesive was then for 7 min under a UV sky from Torgauer Maschinenbau hardened. Subsequently, the thickness of the obtained, bubble-free laminated glass with a micrometer screw measured. It was 8.42 mm, which is one Adhesive layer thickness of 0.72 mm.

Example 5 Production of a laminated glass

On a cleaned, horizontally lying glass panel of the Dimensions 500 × 150 × 3.85 mm were 157 g of the Adhesive from Example 2 given. With help of a Notched trowel, the glue was spread and there were channels in the adhesive in the longitudinal direction of the glass sheet pulled so that the adhesive bead-shaped on the Glass panel. After a rest period of 1 minute it was on it a second, cleaned glass panel with identical ones Dimensions placed congruently so that each air ducts next to the caterpillar-shaped adhesive strands found. This sandwich arrangement was through the 9.8 mm large gap of a pair of rubberized rollers (diameter of the Rollers 35 mm) and pressed in the process without air bubbles. The curing was carried out as in Example 4. the Thickness of the obtained air bubble-free laminated glass was 9.73 mm, which corresponds to an adhesive layer thickness of 2.03 mm is equivalent to.

Example 6 Production of a laminated glass

On a cleaned, horizontally lying glass panel of the Dimensions 1500 × 1000 × 3.85 mm, 3250 g of the in Example 3 prepared adhesive given. With help A notched trowel was used to spread the glue and it were in the longitudinal direction of the glass sheet channels in the Adhesive pulled so that the adhesive bead-shaped on the glass panel. A second, cleaned one was then added Glass panel with identical dimensions congruent hung up. This sandwich arrangement was made with two im Distance of 200 mm arranged one behind the other rubberized Pressure rollers (diameter 50 mm), which are analogous to Example 4 of Hand guided and pressed on, free of air bubbles pressed. The curing was as in Example 4 carried out. The thickness of the obtained, air-bubble-free Laminated glass was 9.74mm, which is one Corresponds to an adhesive layer thickness of 2.04 mm.

Example 7 Production of a laminated glass

147 g of the adhesive prepared in Example 3 were placed on a cleaned, horizontally lying glass panel measuring 500 × 350 × 5.85 mm. The adhesive was spread with the aid of a notched trowel and channels were drawn into the adhesive in the longitudinal direction of the glass sheet, so that the adhesive lay on the glass sheet in a bead-like manner. A second, cleaned glass panel with identical dimensions was placed congruently on top. This sandwich arrangement was pressed free of air bubbles using a hand roller in the same way as in Example 4. The curing was carried out as in Example 4. The thickness of the air bubble-free laminated glass obtained was 12.52 mm, which corresponds to an adhesive layer thickness of 0.82 mm.

Example 8 and Comparative Examples A and B Determination of the curing times Example 8

The curing times required for the respective adhesive from Examples 1 to 3 (and thus the required irradiation times) were determined as follows:
On a cleaned, horizontally lying glass panel measuring 150 × 150 × 3.85 mm, 30 g of adhesive were applied as a blob in the middle of the glass panel and a second, cleaned glass panel with identical dimensions was placed congruently on it. This sandwich arrangement was pressed on a surface press, which was set to a distance of 9.8 mm, with a pressure of 3 bar for 1 minute. This sandwich arrangement (adhesive layer thickness before curing = 2.1 mm) was then placed under a UV canopy from Torgauer Maschinenbau with Philips TL-D 36W / 08 tubes and the temperature on the glass panel facing away from the UV light was measured using a PT 100 temperature sensor measured in the course of the irradiation time and recorded with a y / t recorder. The time until the maximum temperature was reached was defined as the curing time and measured successively for the adhesives from Examples 1 to 3.

The results are shown in Table 1.

Comparative example A. Manufacture of a laminated glass with a 1-component casting resin that cures with UV light and determining the curing time

On a cleaned, horizontally lying glass panel of the Dimensions 1500 × 1000 × 3.85 mm was one side a 2 mm thick, 6 mm wide, double-sided adhesive, foamed closed-cell acrylic tape (acrylic foam tape type 4912 from 3M) all around the edge of the glass panel so laid that there is still a gap between the ends of the tape approx. 50 mm wide (filling opening for the casting resin) remained. Thereupon was a second, cleaned glass panel stored congruently so that a sealed There was a gap with an opening approx. 50 mm wide. the Glass panels were then made with moderate, by hand exerted, pressure compressed to ensure intimate contact and thus wetting between the adhesive tape and the glass panels to create. This composite was oblique, i.e. H. in one Angle of 70-80 °, on a filling / tilting table from the company Torgauer Maschinenbau and with the help of a Dosing pump from Torgauer Maschinenbau and one Stainless steel flat nozzle over the filling opening with 3003 g of a 1-component casting resin that cures with UV light Acrylate base (Naftolan UV 11 from Chemetall) filled. The filling opening was then with a Ethylene vinyl acetate hot melt adhesive (hot melt adhesive 22 of the Chemetall) closed and the sandwich arrangement by UV irradiation with Blacklight tubes, type TL-D 36W / 08 from Philips, under a UV canopy from Torgauer Mechanical engineering cured within 15 minutes and at the same time the temperature over the course of these 15 minutes with a Temperature sensor PT 100 on the one facing away from the UV light Glass surface measured and with a y / t recorder registered.

The results are shown in Table 1.

Comparative example B Manufacture of a laminated glass with a multi-component casting resin and determination of the Curing time

Analogously to comparative example A, a composite from 2 Glass panels and adhesive tape made. As to be filled Cast resin became a multi-component system based on acrylate used. For this purpose, 3364.2 g of the acrylate resin "Naftolan S700M "from Chemetall as 1st component with 33.6 g of des Hardener "catalyst solution 66" from Chemetall (organic peroxide containing tert-butyl perbenzoate) as 2nd component and 67.2 g of the adhesion promoter "Catalyst solution 91" from Chemetall (consisting of Silanes) as the 3rd component using a magnetic stirrer mixed. From this casting resin 3300 g were over a Stainless steel filling nozzle in the inclined assembly filled from glass panels and tape. The filling opening was closed analogously to Comparative Example A and the Sandwich arrangement in a horizontal position on one Curing table with flat plate from Torgauer Mechanical engineering stored at room temperature. The casting resin cured in a period of 2 hours, with the Temperature on the glass surface with a Temperature sensor type PT 100 measured and with a y / t- Was registered.

The results are shown in Table 1.

Table 1

Curing times for the adhesives from Comparative Examples A and B and for the adhesives according to the invention from Examples 1 to 3 (determined in Example 8)

It can be seen that the adhesives according to the invention consist of Examples 1 to 3 compared to known ones Cast resin systems have much shorter curing times need what also shorter irradiation times and thus a faster and cheaper manufacturing process contains.

Example 9 Comparison of the layer thicknesses of laminated glass with adhesive according to the invention and with laminated glasses conventional casting resin

The in Example 6, Comparative Example A and Comparative Example B produced laminated glasses were used for Measurement of the layer thickness in a 100 mm measuring grid divided, which resulted in 10 × 15 measuring points. the Layer thickness of the laminated glass was with a Eddy current measuring device (Multi NCDT series 300 from Micro- Epsilon) and an iron plate (150.150.3.85 mm) that the laminated glass was in contact with, measured. The results are listed in Table 2.

Table 2

Layer thicknesses in mm (individual measuring points) of laminated glasses produced according to Example 6 and Comparative Examples A and B

Laminated glass from example 6

Laminated glass from Comparative Example A

Laminated glass from Comparative Example B

Statistical evaluation of the layer thickness

The evaluation shows that with the new adhesive according to the invention laminated glasses with more uniform layer thicknesses can be produced.

Example 10 Comparison of the stresses in a post Example 6 produced laminated glass and one according to Comparative Example A produced laminated glass

In order to make the stresses in the laminated glass caused by the adhesive or cast resin layer visible, sections of 40 × 100 mm were cut from the laminated glasses from Example 6 and Comparative Example A and the stresses in the glass were made visible as color changes in a glass stress tester with polarized light. A picture was taken of both laminated glass sections in this way. Fig. 1 shows the recordings schematically. In the laminated glass produced with the adhesive according to the invention from Example 6, significantly fewer stresses can be seen in the glass than in the laminated glass produced with conventional casting resin from Comparative Example A.

Claims (9)

1. Adhesive for the production of laminated glass with a viscosity of 5 to 300 Pa.s and a flow limit of 5 to 800 Pa, containing the following ingredients (data in percent by weight, sum of the ingredients used = 100%):
a) reactive acrylate or methacrylate monomers 5-90 b) acrylate- or methacrylate-functional oligomers 5-60 c) non-reactive acrylate or methacrylate homo- and copolymers 0-15 d) fillers 0-30 e) plasticizers 0-15 f) adhesion promoter 0.3-3 g) photoinitiators 0.1-3 h) tackifying additives 0-5 i) stabilizers 0-2 2. Adhesive according to claim 1, containing the following ingredients (data in percent by weight, sum of ingredients used = 100%):
a) reactive acrylate or methacrylate monomers 30-60 b) acrylate- or methacrylate-functional oligomers 20-40 c) non-reactive acrylate or methacrylate homo- and copolymers 0-15 d) fillers 5-25 e) plasticizers 0-15 f) adhesion promoter 0.5-3 g) photoinitiators 0.1-2 h) tackifying additives 0-5 i) stabilizers 0-2 3. Adhesive according to one of claims 1 to 2, characterized characterized in that the yield point of the adhesive 20 to 80 Pa. 4. Adhesive according to one of claims 1 to 3, containing one or more organic ingredients as additional ingredients Dyes and / or inorganic colored nanoparticles for Coloring of the laminated glass. 5. Adhesive according to one of claims 1 to 4, containing inorganic pigments are used as additional ingredients Clouding of the laminated glass. 6. Process for the preparation of the adhesive according to the Claims 1 to 5, characterized in that the Ingredients with a planetary dissolver, a Mixing blades and / or a turbulence mixer and the mixing temperature is between 15 and 70 ° C. 7. The method according to claim 6, characterized in that the ingredients under vacuum or under protective gas be mixed. 8. Use of the adhesive according to one of claims 1 to 5 in a process for the production of laminated glass, in which
the glass panels are cleaned and dried,
the adhesive is applied to the inside of the first, horizontally lying glass panel,
the second glass panel is placed congruently on the adhesive layer,
the sandwich arrangement obtained is pressed and
the adhesive layer is cured by UV radiation. 9. Use of the adhesive according to any one of claims 1 to 5 in a process for the production of Edge seal-free laminated glass.