WO2000009619A1

WO2000009619A1 - Adhesive for the production of composite glass

Info

Publication number: WO2000009619A1
Application number: PCT/EP1999/005832
Authority: WO
Inventors: Michael Schwamb; Jörg HERASIMTSCHUK
Original assignee: Chemetall Gmbh
Priority date: 1998-08-13
Filing date: 1999-08-10
Publication date: 2000-02-24
Also published as: JP2002522620A; EP1117745A1; DE19836695A1

Abstract

The invention relates to an adhesive for the production of composite glass, consisting of reactive acrylate and methacrylate monomers, acrylate and methacrylate-functional oligomers, filling materials, adhesion promoters, photoinitiators and optionally non-reactive acrylate and methacrylate homopolymers and copolymers, softeners, tackifying additives and stabilizers and exhibiting a viscosity ranging from 5 to 300 Pa*s and a flow point ranging from 5 to 800 Pa at 23 °C. The invention also relates to the production of the adhesive according to the invention and the use of said adhesive.

Description

Kl phπt-nff TU T T-fprst-pl 1 ting of laminated glass

description

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

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

Laminated glass is used, for example, as laminated glass with safety and / or soundproofing properties, for the protection of surfaces by gluing with a glass pane or in the manufacture of solar modules. A widely used process for the production of laminated glass works in such a way that an obliquely placed pane of glass consisting of two, spaced apart, cleaned glass plates is filled with a low-viscosity casting resin. The cavity located between the two glass sheets is sealed to the outside with, for example, a double-sided adhesive tape, which is located between the two glass sheets. This edge seal can also consist of a butyl cord that contains a hard core made of a thermoplastic polymer, such as polypropylene.

After filling, tipping the filled double disc horizontally, venting and closing the filling opening with a thermoplastic material, e.g. again with a hot melt adhesive or with a butyl cord, the cast resin layer between the glass sheets is cured. In the case of a one-component system, curing can be carried out by UV light or thermally and in the case of a multi-component system by storage at room temperature or by supplying heat.

The liquid casting resins commonly used in this process have viscosities <500 mPa * s (23 ° C) and mostly consist of acrylates, which e.g. Urethane acrylate oligomers as chain crosslinkers and multifunctional standard reactive thinners based on acrylate, e.g. Triethylene glycol diacrylate. The casting resins can be transparent, colored or cloudy. After curing, the cast resin layer usually has a layer thickness of 1 to 3 mm.

The casting resins described have the disadvantage, owing to the low viscosity, in the event of inadequate wetting of the glass surface by the edge seal described (adhesive tape or butyl cord), or in the event of even slight damage to the same by infiltration the edge seal can easily run out of the filled double pane before curing. It is also important to ensure that the sealing material for the pouring resin filler opening is compatible with the edge seal and the casting resin used, since if it is not compatible there is again a risk of leakage and discoloration of the casting resin may occur.

Another disadvantage of the casting resins used up to now is their volume shrinkage of approx. 10 to 17% by volume during curing. As a result, stresses are generated in the cast resin layer in the hardened laminated glass, which in extreme cases can lead to the detachment of the cast resin layer from the glass (delamination).

The process for producing laminated glass with a casting resin is also subject to restrictions or disadvantages. The adhesive tape or the butyl cord is glued on manually, which is very time-consuming. Cast resin layers with a thickness of <0.9 mm cannot be produced - due to the need to quickly fill and vent the glass sheet composite, the process is limited to the use of low-viscosity resins; for venting, a tilting from the vertical to the horizontal is necessary, which requires manual control; with larger pane dimensions there are greater differences in layer thickness and the casting resin has to cure in a stationary manner. The layer thickness differences of the hardened cast resin layer can be due to the low viscosity of the cast resin with a nominal layer thickness of 1.0 mm in the range of 0.2 to 0.8 mm.

DE 19535935 A1 describes a radiation-curable, multi-layer coating which, among other things, consists of a coating composition which comprises 40 to 90% by weight urethane acrylate, 0 to 22% by weight polyether acrylate, 10 to 50% by weight reactive thinner, 0 to 10% by weight. % Photoinitiator, 0 to 30% by weight of pigments and 0 to 30% by weight of others contains common fillers. This coating is used, among other things, for coating glass. The coating is not intended as an adhesive for the production of laminated glass.

The invention is therefore based on the object to overcome the disadvantages of the prior art and to create an adhesive for the production of laminated glass, which is in the finished laminated glass instead of the casting resin between the glass sheets, which has a high viscosity and which uses a new one , automated process for the edge seal-free production of laminated glass allowed.

The object is achieved by the pasty and non-liquid adhesive specified in claim 1. Claims 2 to 5 further develop the specified adhesive. Claims 6 to 7 specify a method for producing the adhesive according to the invention. Claims 8 to 9 specify the use of the adhesive according to the invention in processes for the production of laminated glass.

The adhesive mainly consists of reactive acrylate and methacrylate monomers, which form a copolymer during curing, which in turn can have a cross-linked structure. The adhesive also contains acrylate and methacrylate functional oligomers (such as urethane acrylates, polyester acrylates), fillers, bonding agents and initiators. It can also contain non-reactive acrylate and methacrylate homopolymers and copolymers, plasticizers, tackifying additives and stabilizers.

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

a) reactive acrylate or methacrylate monomers 50 - 90 b) acrylate or methacrylate-functional oligomers 5 - 40 c) non-reactive acrylate or methacrylate homo- and copolymers 0 - 15 d) fillers 2 - 30 e) plasticizers 0 - 15 f) adhesion promoters 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 50 - 70 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

Monofunctional and multifunctional, preferably monofunctional, esters of acrylic and methacrylic acid are used as reactive acrylate and methacrylate monomers. The alcohol components of the esters used can be a functional group-substituted or unsubstituted alkyl group, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, their isomers and higher homologs, 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 from 5 to 20 and

Dimethylaminoethyl. Acrylic and methacrylic acid itself, the amides of these acids and acrylonitrile can also be used as reactive monomers. It can too Mixtures of the reactive acrylate and methacrylate monomers can 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, they are preferably used difunctionally. Mixtures of the oligomers can also be used.

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

Urethane acrylates are made up of isocyanates (e.g. tolylene, tetramethylxylene, hexamethylene, isophorone, cyclohexylmethane, trimethylhexamethyl, xylene or diphenylmethane diisocyanates) and polyols and functionalized with hydroxyacrylates (e.g. hydroxyethyl acrylate) or hydroxymethacrylates (e.g. hydroxy) methyl methacrylates (e.g. hydroxy) methyl acrylates.

The polyols can be polyester polyols or polyether polyols. Polyester polyols can be prepared 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, trimethylol propane, pentaerythritol or ethylene glycols, such as Diethylene glycol). Polyester polyols can also be obtained by reacting a hydroxycarboxylic acid (e.g. starting from caprolactone) with itself. Polyether polyols can be made from ethylene oxide or propylene oxide.

Polyester acrylates are polyester polyols described above which are functionalized with acrylic acid or with methacrylic acid. The silicone acrylates known per se used here are based on those functionalized with acrylate

Polydimethylsiloxanes of different molecular weights.

Non-reactive acrylate and methacrylate homo- and copolymers are homo- and copolymers of acrylic acid, methacrylic acid and the esters of these acids described above. The adhesive can also contain mixtures of the homopolymers and copolymers mentioned. The adhesive can also be produced without non-reactive acrylate or methacrylate homo- and copolymers.

Fillers can be reinforcing and non-reinforcing. Fumed or precipitated silicas, which are surface-treated or preferably hydrophilic, and cellulose derivatives, such as cellulose acetate, acetobutyrate, acetopropionate, methyl cellulose and hydroxypropyl methyl cellulose, can be used as fillers. The adhesive can also contain mixtures of the fillers mentioned.

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, esters of trimellitic acid, such as tri (2-ethylhexyl) and triisononyl trimellitate, esters of citric acid, such as acetyltributyl and acetyltriethyl citrate, and esters of dicarboxylic acids, such as di-2-ethylhexyl adipate and dibutyl sebaca. The adhesive can also contain mixtures of the plasticizers mentioned. The adhesive can also be made without a plasticizer.

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-trialkoxysilyl, mercapoxysilane, iso-butoxysilane, iso-butoxysilane, iso-butoxysilane trialkoxysilane, and from the group of silicic acid esters, such as

Tetraalkyl orthosilicate. The adhesive can also contain mixtures of the adhesion promoters mentioned.

Compounds from the group of the benzoin ethers, the benzil ketals, the α-dialkoxyacetophenones, the α-hydroxyalkylphenones, the α-aminoalkylphenones, the acylphosphine oxides, the benzophenones or the thioxantones or mixtures thereof can be used as photoinitiators.

Tackifying additives can be selected from the group of natural and synthetic, also 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 contain mixtures of the tackifying additives mentioned. The adhesive can also be made without any tackifying additives.

Stabilizers can be antioxidants such as phenols (e.g. 4-methoxyphenol) or hindered phenols (e.g. 2,6-di-tert-butyl-4-methylphenol) or mixtures of various antioxidants. The adhesive can also be made without stabilizers.

The adhesive has a higher viscosity and is preferably thixotropic. The viscosity range at 23 ° C is 5 to 300 Pa * s, the thixotropy being set higher as the viscosity decreases. The adhesive has a yield point at 23 ° C. in the range from 5 to 800 Pa, preferably in a range from 20 to 80 Pa.

The adhesive according to the invention is produced by mixing the ingredients in a suitable unit. If high shear forces to destroy Agglomerates are necessary, the aggregate can

Be a planetary dissolver with a high-speed dissolver disc. If high shear forces are not required during mixing, the unit can be a wing mixer or a turbulence mixer. Whether high or low shear forces are required depends on the ingredients used. For example, a dissolver disc is absolutely necessary to incorporate pyrogenic silica into a medium-viscosity liquid. If the viscosity is low, the use of a pearl mill may be necessary. By adding fillers, the viscosity increases significantly. The use of vacuum may be necessary during the mixing process.

The mixing temperature at the start of the mixing process is at room temperature (15 to 25 ° C) and can increase to 70 ° C depending on the consistency of the mixture and the energy input of the mixing unit used. When using low-boiling monomers, such as e.g. Methyl methacrylate, cooling is necessary.

If the adhesive contains one or more organic dyes (e.g. azo dyes or phthalocyanine metal complexes) and / or inorganic colored nanoparticles as additional ingredients, the laminated glass made from this adhesive is colored.

If the adhesive contains inorganic pigments (e.g. titanium dioxide) as additional ingredients, the laminated glass made from this adhesive is clouded. If colored inorganic pigments are used, the turbidity is colored accordingly.

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

1. cleaning and drying of the glass sheets, 2. application of a pasty adhesive to the inside of the first, horizontally lying glass sheet, 3. Placing the second glass sheet on the

Adhesive layer,

4. Pressing the sandwich arrangement and

5. Harden the adhesive layer.

This method can e.g. be structured as follows:

Cleaning with commercially available glass cleaners and drying 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 sheets must be absolutely dry, free of grease and free of detergent residues. Checking for cleanliness is an advantage. This can be done visually with the help of fluorescent tubes. When the glass sheets are cut to size beforehand, water-soluble or residue-free drying cutting oils are advantageously used.

The cleaned first glass sheet is positioned horizontally. The adhesive is applied to the inner surface of the glass sheet, which is preferably carried out automatically. The glass sheet is passed under the adhesive application device or the adhesive application device is preferably passed over the glass sheet. The precisely metered amount of adhesive is applied. In general, when applying the adhesive, an exact edge distance, which has to be determined beforehand by experiments, must be observed so that no adhesive can run off the pane edges.

The adhesive can be applied in the form of a closed film from a slot die that is perpendicular to the transport direction of the glass sheet.

Alternatively, the adhesive can be applied with a corresponding nozzle arrangement in the form of caterpillar-shaped adhesive strands that run parallel to the direction of transport of the glass sheet. The second glass sheet is placed congruently on the adhesive layer so that one

Sandwich arrangement consisting of glass-adhesive-glass forms. This method step is preferably also carried out automatically.

This sandwich arrangement is then pressed. This is done by applying moderate pressure to the outer surface of the second, top glass sheet, applying the pressure along a line that coincides with the outer surface of the second glass sheet and is generally transverse from one side of the second glass sheet to the other the same extends. This pressure line is moved from one end of the sandwich arrangement to the other. The corresponding counter pressure on the lower glass sheet is e.g. exercised by the document. The pressure to be applied is 0.5 to 16 bar. The pressure is preferably exerted on the upper second glass plate with one or more pressure rollers. The pressure on both glass sheets is particularly preferably exerted by one or more pairs of pressure rollers, the sandwich arrangement being moved through the adjustable intermediate space of a pair of pressure rollers.

Any air that may still be present escapes when pressing in front of the advancing pressure line. When a bead of adhesive is applied, the air escapes through the channels between the beads of adhesive. The result is an air bubble-free bond between the first glass sheet, adhesive and second glass sheet. The caterpillar-shaped adhesive application in particular has a positive effect on the escape of air.

Finally the adhesive is cured. This is done by irradiating with UV light, preferably generated with so-called blacklight tubes. The UV light source is to be arranged in such a way that the adhesive is irradiated with an area power of 10 to 100 W / m ² , preferably 15 to 40 W / m ² . After curing, the adhesive tray has a layer thickness of 0.2 to 5 mm, preferably 0.5 to 2 mm.

The entire arrangement of two glass sheets and adhesive is preferably conveyed automatically between and during the said process stages.

The adhesive according to the invention is also suitable for producing laminated glass with more than two glass sheets. The corresponding process steps are repeated. If a laminated glass is produced with the adhesive, the glass sheet of which is a thin-film solar module, a composite voltaic module is obtained.

Due to the rheological properties of the adhesive according to the invention, it is only possible to produce laminated glass by means of an automated process.

Of particular advantage is the possibility of using the adhesive according to the invention to produce a laminated glass that is free of edge seals. Without edge sealing, less stresses are generated when the adhesive hardens than when hardening cast resin in a laminated glass with edge sealing.

Another advantage is the less than 10% lower volume shrinkage of the adhesive according to the invention during curing in comparison with conventional casting resin. Due to the high viscosity of the adhesive and the uniform pressing of the sandwich arrangement, a uniform layer thickness is achieved after curing. This also reduces stresses in the laminated glass, which advantageously reduces the risk of damage due to the adhesive layer becoming detached from the glass.

Another advantage is the faster curing of the adhesive according to the invention compared to UV-curing casting resins. The subject matter of the invention is illustrated by the following examples. Unless otherwise noted, the percentages are percentages by weight:

Examples 1 to 3: Production of the adhesive

Example 1:

In a planetary dissolver, the reactive acrylate monomers were 215.3 g (35.9%) 2-ethylhexyl acrylate, 48 g (8.0%) polypropylene glycol monomethacrylate with a degree of polymerization 6 (bisomer PPM6E from Inspec) and 90 g (15%) acrylic acid and as an adhesion promoter, 3 g (0.5%) of vinyl trimethoxysilane (Dynasilan VTMO from Sivento) were mixed with 3.6 g (0.6%) of the photoinitiator l-hydroxycyclohexylphenyl ketone (Irgacure 184 from Ciba Specialty Chemicals) within 5 minutes. This was followed by dissolving 60 g (10%) of the filler cellulose acetobutyrate (CAB 381-0.5 from Eastman) over a period of 40 minutes. Thereafter, 144 g (24%) of an aliphatic urethane acrylate (Genomer 4258 from Rahn) were mixed in as the acrylate-functional oligomer within 15 minutes, and 36 g (6.0%) of highly disperse silica (CAB-O-SIL LM 150 from the company) were mixed in over 20 minutes Cabot) as a further filler and then a vacuum of 200 mbar is applied for 15 minutes. An adhesive was obtained with a viscosity of 41 Pa * s (23 ° C) and a yield point of 20 Pa (23 ° C).

Example 2:

1200 g (30.0%) 2-ethylhexyl acrylate, 400 g (10.0%) polypropylene glycol monoacrylate with degree of polymerization 6 were used as reactive acrylate monomers in a mixer from Molteni equipped with a butterfly stirrer and dissolver disc (Bisomer PPA6 from Inspec) and 600 g (15.0%) acrylic acid and as an adhesion promoter 16 g (0.4%) of the organofunctional silane 3-mercapto propyltrimethoxysilane

(Dynasilan MTMO from ^' Sivento) and 24 g (0.6%) of the photoinitiator l-hydroxycyclohexylphenyl ketone (Irgacure 184 from Ciba Specialty Chemicals) mixed together within 10 minutes, then 320 g (8.0%) of the for 40 minutes Filler cellulose acetobutyrate (CAB 381-0.5 from Eastman) dissolved, then 1200 g (30.0%) of an aliphatic urethane acrylate (Genomer 4258 from Rahn) added as an acrylate-functional oligomer and mixed for 15 minutes. Thereafter, 240 g (6.0%) of a highly disperse silica (Aerosil 200 from Degussa) were incorporated as a further filler for 20 minutes. Finally, a vacuum of 100 mbar was applied for 30 minutes. The viscosity of the adhesive obtained was 20 Pa * s (23 ° C) and the yield point 107 Pa (23 ° C).

Example 3:

In a mixer from Molteni equipped with a butterfly stirrer and dissolver disc, 1200 g (30.0%) of 2-ethylhexyl acrylate, 400 g (10.0%) were used as reactive acrylate monomers.

Polypropylene glycol monoacrylate with degree of polymerization 6 (bisomer PPA6 from Inspec) and 600 g (15.0%) acrylic acid and as an adhesion promoter 16 g (0.4%) of the organofunctional silane 3-mercaptopropyltrimethoxysilane (Dynasilan MTMO from Sivento) and 24 g ( 0.6%) of the photoinitiator l-hydroxycyclohexylphenyl ketone (Irgacure 184 from Ciba Specialty Chemicals) mixed with one another within 5 minutes, then 240 g (6.0%) of the filler cellulose acetobutyrate (CAB 381-2 from Eastman) were dissolved over 60 minutes , then 1280 g (32.0%) of an aliphatic urethane acrylate (Craynor CN 965 from Cray Valley) are added as an acrylate-functional oligomer and mixed for 15 minutes. After that 240 g (6.0%) of a highly disperse silica (CAB-O-SIL M5 from Cabot) were incorporated as a further filler for 20 minutes. Finally, a vacuum of 50 mbar was applied for 30 minutes. The viscosity of the adhesive obtained was 15 Pa * s (23 ° C) and the yield point 50 Pa (23 ° C).

Examples 4 to 7: Use of the adhesive, production of laminated glasses

Example 4: Production of a laminated glass

200 g of the adhesive from Example 3 were placed "sausage-like" on a cleaned, horizontally lying glass sheet measuring 400 x 300 x 3.85 mm along the 300 mm long edge of the pane. The adhesive was then removed in the longitudinal direction with a notched trowel and the amount of adhesive applied was weighed out. The adhesive applied was 91 g. A second, cleaned glass sheet with identical dimensions was placed congruently on the adhesive beads produced, so that there were air channels next to the bead-shaped adhesive strands. This sandwich arrangement was pressed with a hand roller (diameter 100 mm). For this purpose, the hand roller was moved in the longitudinal direction from one side of the sandwich arrangement to the other under a moderate pressure exerted by hand, the air still remaining between the two glass sheets escaping through the channels in front of the pressure line, the channels closing and an air bubble-free bond the two glass sheets with the adhesive layer in between. The adhesive was then cured for 7 minutes under a UV sky from Torgauer Maschinenbau (Philips tubes type TL-D 36W / 08). The area power of the UV radiation was 23 W / m ² (measured at the level of the glass surface). The thickness of the air-bubble-free laminated glass obtained was then determined using a Micrometer screw measured. It was 8.42 mm, which corresponds to an adhesive layer thickness of 0.72 mm.

Example 5: Production of a laminated glass

157 g of the adhesive from Example 2 were placed on a cleaned, horizontally lying glass sheet measuring 500 x 150 x 3.85 mm. The adhesive was distributed using a notched trowel and channels were drawn into the adhesive in the longitudinal direction of the glass sheet, so that the adhesive was caterpillar-shaped on the glass sheet. After a rest period of 1 minute, a second, cleaned glass sheet with identical dimensions was placed on top of it so that there were air channels next to the caterpillar-shaped strands of adhesive. This sandwich arrangement was passed through the 9.8 mm gap of a rubberized pair of rollers (diameter of the rollers 35 mm) and was pressed without air bubbles. The curing was carried out as in Example 4. The thickness of the air-bubble-free laminated glass obtained was 9.73 mm, which corresponds to an adhesive layer thickness of 2.03 mm.

Example 6: Production of a laminated glass

3250 g of the adhesive produced in Example 3 were placed on a cleaned, horizontally lying glass sheet measuring 1500 x 1000 x 3.85 mm. The adhesive was distributed using a notched trowel and channels were drawn into the adhesive in the longitudinal direction of the glass sheet, so that the adhesive was caterpillar-shaped on the glass sheet. A second, cleaned glass plate with identical dimensions was placed on top of it. This sandwich arrangement was made free of air bubbles with two rubberized pressure rollers (diameter 50 mm) arranged one behind the other at a distance of 200 mm, which were guided and pressed on by hand as in Example 4 pressed. The curing was carried out as in Example 4. The thickness of the air-bubble-free laminated glass obtained was 9.74 mm, which corresponds to an adhesive layer thickness of 2.04 mm.

Example 7: Production of a laminated glass

147 g of the adhesive produced in Example 3 were placed on a cleaned, horizontally lying glass sheet measuring 500 × 350 × 5.85 mm. The adhesive was distributed using a notched trowel and channels were drawn into the adhesive in the longitudinal direction of the glass sheet, so that the adhesive was caterpillar-shaped on the glass sheet. A second, cleaned glass plate with identical dimensions was placed on top of it. This sandwich arrangement was pressed in the same way as in Example 4 using a hand roller without air bubbles. 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 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 sheet measuring 150 x 150 x 3.85 mm, 30 g of adhesive was applied as a blob in the middle of the glass sheet and a second, cleaned glass sheet with identical dimensions was placed congruently on it. This sandwich arrangement was pressed on a surface press, which was set at 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 sky from Torgauer Maschinenbau with Philips tubes type TL-D 36W / 08. The area power of the UV radiation was 23 W / m ² (measured at the level of the glass surface). The temperature on the glass panel facing away from the UV light was measured with a temperature sensor PT 100 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 in succession for the adhesives from Examples 1 to 3.

The results are shown in Table 1.

Comparative Example A: Production of a laminated glass with an 1-component casting resin that cures with UV light and determination of the curing time

On a cleaned, horizontally lying glass sheet measuring 1500 x 1000 x 3.85 mm, a 2 mm thick, 6 mm wide, double-sided adhesive, foamed closed-cell acrylate tape (Acrylic Foam Tape Type 4912 from 3M) was wrapped all around in the edge area of the The glass panel is placed in such a way that there is still a gap of approx. 50 mm width (filler opening for the casting resin) between the ends of the strip. Then a second, cleaned glass sheet was placed congruently, so that there was a sealed space with an approximately 50 mm wide opening. The glass sheets were then pressed with moderate hand pressure to create intimate contact and wetting between the adhesive tape and the glass sheets. This composite was placed at an angle, ie at an angle of 70-80 °, on a filling / tilting table from Torgauer Maschinenbau and with the help of a metering pump from Torgauer Maschinenbau and one Stainless steel flat nozzle filled with 3003 g of a 1-component, UV-light-curing casting resin based on acrylate (Naftolan UV 11 from Chemetall). The filling opening was then closed with an ethylene-vinyl acetate hot-melt adhesive (hot-melt adhesive 22 from Chemetall) and the sandwich arrangement by UV irradiation with Blacklight tubes, type TL-D 36W / 08 from Philips, under a UV sky from Torgauer Maschinenbau cured within 15 minutes and in the course of these 15 minutes the temperature was measured with a temperature sensor PT 100 on the glass surface facing away from UV light and recorded with a y / t chart recorder.

The results are shown in Table 1.

Comparative Example B: Production of a laminated glass with a multi-component casting resin and determination of the curing time

Analogous to Comparative Example A, a composite was produced from 2 glass sheets and adhesive tape. A multi-component system based on acrylate was used as the pouring resin. 3364.2 g of the "Naftolan S700M" acrylate resin from Chemetall were added as the first component with 33.6 g of the hardener "Catalyst Solution 66" from Chemetall (organic peroxide containing tert-butyl perbenzoate) as the second component and 67.2 g of the adhesion promoter "catalyst solution 91" from Chemetall (consisting of silanes) as the 3rd component mixed using a magnetic stirrer. 3300 g of this casting resin were filled into the inclined composite of glass panels and adhesive tape via a stainless steel filling nozzle. The filling opening was closed as in Comparative Example A and the sandwich arrangement was stored in a horizontal position on a curing table with a flat plate from Torgauer Maschinenbau at room temperature. The casting resin cured in a period of 2 hours, the Temperature on the glass surface was measured with a temperature sensor type PT 100 and registered with a y / t recorder.

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 from Examples 1 to 3 require much shorter curing times than known casting resin systems, which also means shorter irradiation times and thus a faster and less expensive manufacturing process. Example 9: Comparison of the layer thicknesses of laminated glasses with the adhesive according to the invention and of laminated glasses with conventional casting resin

The in Example 6, Comparative Example A and

Comparative example B produced laminated glasses were divided into a 100 mm measuring grid to measure the layer thickness, resulting in 10 x 15 measuring points. The layer thickness of the laminated glass was measured using a vortex current measuring device (Multi NCDT series 300 from Micro-Epsilon) and an iron plate (150 * 150 * 3.85 mm) on which the laminated glass rested. The results are shown 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:

9.82 9.68 9.72 9.69 9.72 9.72 9.69 9.71 9.74 9.74 9.75 9.82 9.80 9.75 9.87

9.78 9.61 9.62 9.61 9.64 9.63 9.72 9.74 9.63 9.64 9.65 9.74 9.74 9.70 9.82

9.69 9.58 9.58 9.58 9.61 9.64 9.75 9.81 9.61 9.66 9.62 9.68 9.74 9.71 9.81

9.71 9.59 9.61 9.62 9.65 9.69 9.82 9.87 9.66 9.66 9.69 9.77 9.75 9.80 9.82

9.70 9.65 9.70 9.72 9.77 9.75 9.88 9.91 9.75 9.76 9.81 9.89 9.84 9.76 9.83

9.71 9.69 9.77 9.78 9.84 9.84 9.80 9.89 9.83 9.84 9.87 9.91 9.89 9.77 9.86

9.71 9.65 9.74 9.74 9.78 9.80 9.70 9.78 9.76 9.81 9.81 9.91 9.78 9.75 9.78

9.69 9.64 9.71 9.70 9.72 9.75 9.82 9.69 9.72 9.75 9.74 9.78 9.74 9.68 9.75

9.69 9.77 9.72 9.72 9.71 9.74 9.75 9.74 9.71 9.75 9.70 9.76 9.70 9J1 9.82

9.71 9.74 9.71 9.71 9.75 9.74 9.69 9.83 9.74 9.69 9.66 9.71 9.74 9.69 9.72

Laminated glass from comparative example! L A:

9.76 9.76 9.76 9.78 9.77 9.76 9.78 9.76 9.76 9.80 9.76 9.77 9.75 9.74 9.74

9.71 9.74 9.71 9.76 9.75 9.71 9.75 9.75 9.74 9.74 9.76 9.74 9.65 9.63 9.74

9.65 9.68 9.70 9.66 9.69 9.70 9.66 9.70 9.74 9.72 9.72 9.74 9.68 9.62 9.71

9.62 9.64 9.71 9.68 9.78 9.75 9.70 9.72 9J7 9.75 9.75 9.72 9.65 9.63 9.74

9.57 9.66 9.76 9.87 9.84 9.77 9.88 9.89 9.88 9.84 9.83 9.86 9.80 9.74 9.75

9.61 9.72 9.83 9.97 9.95 9.99 10.0 10.0 9.99 9.95 9.98 9.99 9.91 9.87 9.78

9.61 9.69 9.78 9.95 9.92 9.84 9.92 9.94 9.88 10.0 9.81 9.98 9.93 9.84 9.80

9.59 9.63 9.76 9.87 9.83 9.75 9.84 9.81 9.78 9.84 9.78 9.86 9.81 9.78 9.75

9.58 9.63 9.70 9.81 9.74 9.71 9.78 9.74 9.66 9.80 9.70 9.77 9.76 9.72 9.74

9.58 9.55 9.61 9.66 9.63 9.62 9.68 9.63 9.63 9.68 9.64 9.69 9.66 9.72 9.69

Laminated glass from comparative example B:

9.80 9.77 9.92 9.72 9.77 9.95 9.93 9.92 9.91 9.88 9.87 9.89 9.88 9.89 9.82

9.72 9.78 10.0 9.70 9.65 9.86 9.86 9.88 10.0 10.0 9.98 9.94 9.92 9.98 9.86

9.66 9.63 9.91 9.77 9.62 9.79 9.81 9.90 9.92 9.91 9.83 9.78 9.77 9.72 9.80

9.57 9.54 9.81 9.82 9.68 9.74 9.71 9.81 9.82 9.75 9.69 9.65 9.62 9.62 9.75

9.66 9.66 9.83 9.88 9.77 9.77 9.73 9.77 9.80 9.76 9.71 9.70 9.62 9.62 9.69

9.72 9.78 9.99 9.82 9.75 9.72 9.78 9.85 9.91 9.84 9.83 9.84 9.74 9.65 9.69

9.70 9.76 10.0 9.74 9.71 9.70 9.69 9.82 9.97 9.98 9.95 9.89 9.89 9.70 9.78

9.65 9.68 9.89 9.72 9.68 9.68 9.75 9.95 9.89 9.97 9.95 9.93 9.89 9.69 9.72

9.66 9.77 9.81 9.71 9.80 9.82 9.79 9.88 9.86 9.95 9.91 9.84 9.88 9.80 9.74

9.66 9.78 9.71 9.80 9.78 9.73 9.75 9.79 9.74 9.77 9.69 9.76 9.81 9.72 9.72

Statistical evaluation of the layer thickness:

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

Example 10: Comparison of the stresses in a laminated glass manufactured according to Example 6 and a laminated glass manufactured according to Comparative Example A.

In order to make the stresses in the laminated glass caused by the adhesive or casting resin layer visible, sections of the size 40 x 100 mm were cut out 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 tension tester with polarized light. From both Laminated glass sections were taken in this way. Fig.l. shows the recordings schematically. In the case of the laminated glass produced in Example 6 using the adhesive according to the invention, significantly fewer stresses can be seen in the glass than in the laminated glass produced using conventional casting resin from Comparative Example A.

Claims

1. Adhesive for the production of laminated glass with a viscosity of 5 to 300 Pa * s (23 ° C) and a yield point of 5 to 800 Pa (23 ° C), containing the following ingredients (data in percent by weight, sum of the ingredients used = 100 %):

a) reactive acrylate or methacrylate monomers 50 - 90 b) acrylate or methacrylate functional oligomers 5 - 40 c) non-reactive acrylate or methacrylate homo- and copolymers 0 - 15 d) fillers 2 - 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 (information in percent by weight, sum of ingredients used = 100%):

a) reactive acrylate or methacrylate ^monomers' 50-70 b) acrylate or methacrylate-functional oligomers 20 - 40 c) non-reactive acrylate or methacrylate homo- and copolymers 0 - 15 d) fillers 5-25 e) plasticisers 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 in that the flow limit of the adhesive is 20 to 80 Pa (23 ° C).

4. Adhesive according to one of claims 1 to 3, containing, as further ingredients, one or more organic dyes and / or inorganic colored nanoparticles for coloring the laminated glass.

5. Adhesive according to one of claims 1 to 4, containing, as further ingredients, inorganic pigments for clouding the laminated glass.

6. A method for producing the adhesive according to claims 1 to 5, characterized in that the ingredients are mixed with a planetary dissolver, a wing mixer 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 are mixed under vacuum or under a protective gas.

8. Use of the adhesive according to one of claims 1 to 5 in a method for producing laminated glass, in which the glass sheets are cleaned and dried, the adhesive is applied to the inside of the first, horizontally lying glass sheet, the second glass sheet congruent on the

Adhesive layer is placed, the sandwich arrangement obtained is pressed and the adhesive layer is cured by UV radiation.

9. Use of the adhesive according to one of claims 1 to 5 in a process for the production of edge seal-free laminated glass.