WO2006050927A1

WO2006050927A1 - Method for producing a laminated glass, and laminated glass itself

Info

Publication number: WO2006050927A1
Application number: PCT/EP2005/011987
Authority: WO
Inventors: Helmut Szynka
Original assignee: Hsb Selbstbausysteme Gmbh; Helmut Szynka
Priority date: 2004-11-09
Filing date: 2005-11-09
Publication date: 2006-05-18
Also published as: DE102004054348A1

Abstract

The invention relates to a method for producing a laminated glass (1), during which at least one support glass (2) is pretreated with an adhesion promoter (4), and at least one layer made of resin (3) is subsequently applied two-dimensionally to the support glass (2). Once this is completed, a laminated glass (1) can be manufactured that has UV resistance, fulfills the requirements of a laminated safety glass and, furthermore, can be produced in a simplified and cost-effective manner. To this end, the resin (3) comprises a liquid, UV-resistant 1K polyurethane material that contains, in essence, one prepolymer based on an aliphatic isocyanate with small monomeric portions, and a temperature of up to approximately 30 °C is provided for curing the resin. In addition, the aim of the invention is to create a laminated glass (1) comprising at least one support glass (2) and at least one layer made of resin (3), which has UV-resistance, fulfills the requirements of a laminated safety glass, and which is produced in a simplified and cost-effective manner. To this end, the resin (3) is a liquid, UV-resistant 1K polyurethane material containing, in essence, one prepolymer based on an aliphatic isocyanate with small monomeric portions.

Description

Method for producing a laminated glass and laminated glass

The invention relates to a method for producing a laminated glass, in which at least one carrier glass is pretreated with a bonding agent and da¬ after the support glass at least one layer of resin is applied flat. Moreover, the invention relates to a laminated glass with at least one carrier glass with at least one layer of resin.

Laminated glass has long been known for use as safety glass, for example in the automotive industry and in building construction for window and facade cladding elements.

Safety glasses are basically subdivided into two different types, the laminated safety glass (LSG) and the single-pane safety glass (ESG). A laminated glass safety glass consists of two glass panes, which are glued together with the interposition of a plastic film or casting resin. Single-pane safety glasses (ESG), in contrast to conventional glasses, are characterized in that they chip in a defined manner in the event of a break-down. On the one hand, very small splinters can arise, which essentially have no sharp-edged areas, and on the other hand, alternative tempered safety glass can be designed in such a way that very large pieces are produced, which are much easier to handle, in contrast to the aforementioned small splinters.

It is known from the prior art to coat glass either with one- or two-component cast resin (i.e., IK or 2K casting resin). In the case of the 2K.RTM. Resin system, an addition of a hardener follows immediately before the application. The processor has a limited amount of time to process after the addition of the hardener. In the 1-component resin system, polyurethanes having reactive end groups cure without the addition of hardeners alone by the reaction with the atmospheric moisture.

EP 1 195 243 A1 discloses a safety glass which is intended to meet safety-relevant aspects and, in particular, should have a high splinter bond and a high bending strength, so that the possibility of, in particular, a mechanical see after treatment is opened. For this purpose, a safety glass for use in the interior and exterior area is provided, which consists of a sheet-like transparent carrier glass and a resin layer applied on one side of the carrier glass, wherein the carrier glass and the resin layer over the entire contact area firmly together to form an integrative component adhesively bonded together.

DE 196 35 771 A1 describes a solvent-free, thermosetting IK coating material for coating glass, in particular glass bottles, and a method for producing glass coatings in the μm range. After heat curing of the coating material at about 18O ⁰ C the formation of a high wash liquor resistance is to be achieved more quickly, which is required on the sector's Getränkefla ^¬. For this purpose, the thermosetting LC coating material having a viscosity at 60 ⁰ C of 1000-50,000 mPas, containing substantially 85- 96 wt .-% at least one Isoeyanurat- and urethane-containing isocyanate prepolymer, 4-12 wt .-% finely divided melamine with an average particle diameter of 1-30 microns and 0-3 wt .-% aids.

It is an object of the invention to provide a method of the type mentioned, with which a laminated glass can be made, which has UV resistance and meets the requirements of a laminated safety glass and also verein¬ facht and can be produced inexpensively. In addition, it is an object of the invention to provide a laminated glass which has UV resistance, meets the requirements of a laminated safety glass and is simplified and inexpensive to manufacture.

According to the invention, the object with regard to the method is achieved in that the resin is a liquid, UV-resistant LC polyurethane material which essentially comprises a prepolymer based on an aliphatic isocyanate having low monomeric proportions and wherein a temperature for curing the Resin to about 30 ⁰ C is provided.

The core idea of the invention is to use a one-component (1K) polyurethane material for coating glass instead of a two-component (2K) polyurethane material. This has the advantage that annoying mixing of the resin with the hardener, which often contains viscose components, is omitted before the application. It cures solely by the existing humidity. Since the resin is moisture-curing, it remains elastic, which may be important for the after-treatment on facades, among other things. A further, surprising advantage is that aliphatic isocyanates can be used as the resin material, which have a UV resistance in combinations according to the invention. In addition there is the further advantage that preferably zwi¬ rule about 5 ° and 30 ⁰ C can be produced and thus no additional Ener¬ strategies for curing the resin are required.

Advantageously, the resin comprises the following constituents a) a proportion of about 80-96% by weight, in particular of 81-95.7% by weight, of a solvent-based prepolymer based on an aliphatic isocyanate, b) a proportion of 2.5- 10 wt .-% 1, 2, 4 trimethylbenzene, c) a proportion of about 0.5-2.5 wt.% Polyfunctional aliphatic isocyanate, d) a proportion of about 0.5-2.5 wt. E) a proportion of about 0.5-2.5% by weight of mesitylene, T) a proportion of about 0.1-0.5% by weight of hexahydromethylphthalic anhydride, g) a proportion of about 0.1-0.5% by weight of dibutyltin dilaurate and h) a proportion of about 0.1-0.5% by weight of 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, the constituents b) h) positively influence the flowability. This combination is particularly advantageous, since the combination of these makes the resin material flowable and remains permanently elastic.

A particular advantage of the method according to the invention is also the subsequent securing and refurbishing of glasses and glass surfaces on building structures by applying the resin to already installed support glass on the building. In this case, the resin may not only be transparent, but also contain all known from the prior art color pigments.

According to the invention, the object with regard to the laminated glass is achieved by virtue of the fact that the resin is a liquid, UV-resistant LC polyurethane material which essentially comprises a prepolymer based on an aliphatic isocyanate with low monomeric proportions. The resin is of course cured in the final product.

Such a laminated glass is characterized by a resin, which after curing

UV-resistant and has a tough and tough elastic film. The surface of the resin is shiny. The resin makes the carrier glass a bundglas that meets the requirements of a safety glass. In particular, it can be used where laminated safety glass is urgently necessary due to regulations, eg for glass in the overhead area. This safety glass according to the invention is cheaper to produce than conventional laminated safety glass, since only one resin layer has to be applied to a carrier glass and the resin cures at ambient temperatures without the application of heat energy.

Conveniently, the at least one carrier glass is float glass. Float glass is a quali¬ tatively high quality and inexpensive to produce glass and is ideal as a safety glass. The safety glass can be used both outdoors and indoors.

Preferably, the at least one carrier glass comprises ornamental glass, cast glass or U-glass. Ornamental or Gusgläsern and U-glasses are glasses that have a curved structure by their casting and thus previously did not qualify as safety glasses in question, because due to the unevenness of the glasses no so-called splinters adhering. Only by very expensive methods so far could Glasses are processed to safety glass. An advantage of the method according to the invention is that a safety glass can also be produced from such glasses by simple coating, spraying or rolling, either unpigmented or pigmented.

For safety-relevant requirements, the laminated glass according to the invention can comprise a single-pane safety glass (ESB) or a partially tempered glass as a carrier glass. Thus, the advantages of the tempered safety glass or the partially tempered glass are combined with the advantages of a glass with coated resin.

The at least one carrier glass has a thickness of up to 25 mm and larger. Preferably, the at least one carrier glass has a thickness of 2-12 mm. Such a layer thickness is inexpensive to produce and is sufficient for most applications. Conveniently, the thickness of the resin layer is proportional to the thickness of the zu¬ least one carrier glass, but at least 0.2 mm thick. With a layer thickness of the resin of at least 0.2 mm, the effect of fragmentation can already be achieved. Such a toughened safety glass can easily and easily be insulated cost-effective processing and can be delivered cheaper to the customer.

For glass in safety-related areas, such as in the overhead area of buildings, a larger layer thickness of the resin is required due to safety regulations of up to 2 mm.

In addition, the laminated glass according to the invention can be used in areas that have hitherto not been possible, in particular public areas are addressed, where hitherto, an ornamental and corrugated glass could not be used or only with a large expensive additional effort.

In addition, works of art with thin glass and hand-blown glasses can also be coated with the resin according to the invention in the process according to the invention and thereby made splinter-binding. In this case, the layer thickness may also be less than or equal to 2 mm, in particular 1 to 2 mm.

Advantageously, the resin is unpigmented and thus transparent. This is advantageous if safety glass is required and nevertheless a high light transmittance is required. Alternatively, the resin may be pigmented and thus simultaneously form a decorative element. Pigmented resin is known from the prior art.

Advantageously, the resin comprises the following constituents a) a proportion of about 80-96% by weight, in particular 81-95.7% by weight, of a solvent-containing prepolymer

Basis of an aliphatic isocyanate, b) a proportion of 2.5-10 wt .-% 1, 2, 4 trimethylbenzene, c) a proportion of about 0.5-2.5 wt.% Polyfunctional aliphatic

D) a proportion of about 0.5-2.5% by weight of propylbenzene, e) a proportion of about 0.5-2.5% by weight of mesitylene, f) a proportion of about 0.1% G) a proportion of about 0.1-0.5% by weight of dibutyltin dilaurate and h) a proportion of about 0.1-0.5% by weight 3 -Isocyanatmethyl-3,5,5

Trimethylcyclohexyl. It is understood that the ^¬ and yet to explain the above-mentioned features hereinafter combinations thereof are used not only in the respectively specified combination but also in at ^¬.

The invention will be explained in more detail below with reference to an embodiment under Bezugnah ^¬ me an accompanying drawing. Eleven images document falling ball ^experiments on the laminated glass ^according to the invention. Show it:

1 shows a schematic cross section through an inventive composite glass,

FIG. 2 a holding device for falling ball tests on the composite glass according to the invention, FIG.

FIGS. 3 to 12 fracture images of ball drop tests carried out for eight different laminated glass panes.

FIG. 1 shows a laminated glass 1 according to the invention with a carrier glass 2 and a layer of resin 3 applied flatly. The carrier glass 2 is a float glass, but can also be an ornamental glass or a toughened safety glass. An adhesion promoter 4 between the support glass 2 and the layer of resin 3 provides a good bond between the resin layer 2 and the glass 3. Such a laminated glass 1 is intended for installation on structures.

According to the inventive method for producing a laminated glass, a carrier glass 2 is pretreated with an adhesion promoter 4 at least on one side. A resin 3 is applied in a liquid state to the side of the carrier glass 2 which is precoated with the adhesion promoter 4 by simple brushing, spraying or rolling. The resin prepolymer based on an aliphatic isocyanate having low monomeric proportions is solvent-containing or low-solvent , It contains no melamine. The binder base is polyurethane, which has a density according to DIN 53217 at 20 ° of 1.02 g / cm ³ in the transparent state and 1.10 g / cm ³ in a pigmented state auf¬. The viscosity at 23 ° C is 1500 mPas (colorless) or 2800 mPas (pigmented). The dynamic viscosity is measured using a Haake RS 100 rotary body tester in accordance with the TPOS Verkehrsblatt Doc. No .: B 5234 viscosity standard; Method B: dynamic viscosity has been measured. The polyurethane has a tensile strength according to DIN 53504 of 9 N / mm ² , an elongation at break according to DIN 53504 of 200% and a Shore A hardness of 90 after 7 days. The diffusion resistance is 4000 μ for H ₂ O and 750,000 μ for CO ₂ . Tures the object and processing temperatures will be generally usual ambient temperatures, usually between at least 5 ° C and a maximum of 30 ⁰ C and preferably at room temperature. Thus, no additional heat energy is necessary for processing. The permissible relative air ^humidity is at least 40 to a maximum of 90%.

The resin 3 contains, in order to positively influence the flowability, and in order to obtain elasticity, the following constituents a) contain about 80-96% by weight, in particular 81-95.7% by weight, of a solvent-containing material B) an amount of 2.5-10% by weight 1, 2, 4 trimethylbenzene, c) an amount of about 0.5-2.5% by weight polyfunctional aliphatic isocyanate, d) a proportion of about 0.5-2.5% by weight of propylbenzene, e) a proportion of about 0.5-2.5% by weight of mesitylene, f) a proportion of about 0.1- G) a proportion of about 0.1-0.5% by weight of dibutyltin dilaurate and h) an amount of about 0.1-0.5% by weight 3 -Isocyanatmethyl-3,5,5-trimethyl.

To use the laminated glass as safety glass also e.g. used in the overhead area, the Tägerglas has a glass thickness of at least 2-12 mm. The thickness of the resin layer depends on the safety regulations at least 0.2 mm to about 2.0 mm thick.

The resin 3 can be applied to existing built-glass structures and thereby isolate the glass and subsequently make a safety glass.

The laminated glass 1 according to the invention has a high splinter bond and a high bending strength due to the resin layer 3 bonded to the carrier glass 2.

The resin 3 may also have color pigments and thus give the carrier glass 2 additional decorative possibilities. Such embodiments are known for example from DE 297 24 151 Ul, DE 102 49 223 Al and EP 864 444 Al and are hereby incorporated by reference. example 1

In order to investigate the breaking strength of the laminated glass 1 according to the invention, float glass, as support glass 2, was subjected to 3 falling ball tests in accordance with DIN 52 338 with a resin coating. The test parameters were selected in accordance with the construction product: "laminated safety glass with PVB film" in accordance with BRL A Part 1.

The predetermined dimensions of the specimens were in width and length 500 mm. The specimens consisted of 5 mm and 6 mm thick float glass with a one-sided PU resin coating of about 0.5 mm thickness. Externally visible damage to the discs to be tested was not apparent. The test specimens were prepared from a batch. The samples are marked with the inscription 01 to 08.

Falling ball tests according to DIN 52 338: 1985-09 were carried out. The holding device for the sample body is shown in FIG. 2. The falling body used is a ball of Wälz¬ bearing steel of 63.5 mm diameter and a mass of 1030 g. The height of fall is specified in accordance with BRL A Part 1. Section 1.3.2 with 4 m. The disc structure is specified as a deviation from the VSG composite with 5 mm or 6 mm float glass and a one-sided PU resin coating. The resin coating was positioned reciprocally to the discharge side and to the sample bottom. The impact points should not be more than 50 mm from the center of the sample.

The test results of the ball drop tests carried out are summarized in Table 1.

2 shows a holding device 5 for the ball drop test on a laminated glass 1 according to the invention. The holding device 5 has an upper frame 6, on which the laminated glass 1 rests as a test piece having the dimensions 500 mm × 500 mm. The upper frame 5 is supported on rubber pads 7, which are 3 mm thick and 15 mm wide and have a hardness: 40 IRHD. These rubber liners 7 rest on a lower frame 8, which in turn rests on an intermediate layer of 3 mm thick rubber. Table 1

FS: Fire side

BS: bath side (tin side) top: discharge side

Layer thickness of

Resin coating: measured according to the

Diagonal intersection

2 shows the fracture pattern of the disc 1 after the ball fall in an overview. Figures 4 and 5 show fracture images of the disc 2 after the ball fall in an overview and in detail. Figures 6 and 7 show fracture images of the discs 3 and 4 in an overview. Figures 8 and 9 show fracture images of the discs 5 and 6 in an overview. Figures 10 and 11 represent fracture images of the disc 7 after the ball fall in an overview and in detail. The fracture pattern of the disc 8 after the ball fall is shown in an overview of Figure 12.

The performance of falling ball tests according to DIN 250 338 on float glass with a resin coating according to the invention has shown that the ball drop tests comply with DIN 52 338 and BRL A Part 1, Section 1.3.2. The laminated glass 1 to be tested was neither penetrated by the falling body, nor did fragments break away from the resin-coated glazing.

As explained with reference to the exemplary embodiments, the use of float glass in connection with the resin coating offers an outstanding possibility of greatly improving the fracture properties of the laminated glass. In addition, the production of float glass is comparatively inexpensive, so that overall a qualitatively high-quality safety glass is obtained, which is superior in terms of the production costs of existing glass products or laminated safety glass (VSG) and single pane safety glass (ESG). The properties of the float glasses coated according to the invention, in particular the fracture properties, such as residual load capacity, as well as the break-out behavior, essentially correspond to the properties of conventional laminated safety glass. The glass-based glass based on float glass produced by the process according to the invention is therefore suitable for use in the overhead area or in public buildings because of its outstanding breaking properties, since this glass is comparable with conventional laminated safety glass or single-pane safety glass with regard to break resistance. The use of float glass for the production of a laminated glass or the laminated safety glass, whose support glass comprises a float glass, therefore relates to an essential aspect of the invention.

The term float glass is understood to mean a flat glass which is produced in the so-called float process or else float glass process. In the float glass process, a molten glass is passed continuously from one side into an elongated bath of liquid tin on which the lighter glass floats. The glass spreads evenly like an oil film. Due to the surface tension of the tin and the liquid glass very smooth surfaces are formed. The solidified in the region of the cooler end of the bath glass is withdrawn from the bath and passes through a cooling oven. The use of corrugated glasses and machine glasses is also possible in the context of the invention.

* * * LIST OF REFERENCE NUMBERS

laminated glass

backing glass

Resin, resin layer

bonding agent

holder

Upper frame

Rubber Liner

Lower frame

liner

* * *

Claims

Patent claims

1. A method for producing a laminated glass (1), wherein at least one carrier glass (2) is pretreated with a bonding agent (4) and then on the carrier glass (2) at least one layer of resin (3) is applied flat, characterized in that the resin (3) is a liquid, UV-resistant LC polyurethane material which essentially comprises an aliphatic isocyanate-based prepolymer having low monomeric proportions and a temperature of from about 30 ^° C. for curing the resin.

2. The method according to claim 1, characterized in that the resin comprises (3) the following components a) a proportion of about 80-96 wt .-%, in particular of 81-95.7 wt .-%, ei¬ nes b) a proportion of 2.5-10% by weight 1, 2, 4 trimethylbenzene, c) a proportion of about 0.5-2.5% by weight polyfunctional aliphatic isocyanate , d) a proportion of about 0.5-2.5% by weight of propylbenzene, e) a proportion of about 0.5-2.5% by weight of mesitylene, f) a proportion of about 0.1-0 G) a proportion of about 0.1-0.5% by weight of dibutyltin dilaurate and h) an amount of about 0.1-0.5% by weight of 3-isocyanato-methylidene 3,5,5-trimethylcyclohexyl isocyanate, wherein the constituents b) -h) have a positive influence on the flowability.

3. laminated glass (1) with at least one carrier glass (2) and at least one layer of resin (3), characterized in that the resin (3) is a liquid, UV-resistant 1K polyurethane material, which is substantially a prepoly Mer ¬ based on an aliphatic isocyanate with low monomeric proportions.

4. Laminated glass (1) with at least one carrier glass (2) and at least one layer of resin (3), characterized in that the resin (3) is a cured, UV-resistant 1K polyurethane material which substantially one Prepolymer based on an aliphatic isocyanate having low monomer content comprises.

5. Laminated glass (1) according to claim 3 or 4, characterized in that the at least one carrier glass (2) comprises float glass.

6. laminated glass (1) according to at least one of claims 3 to 5, characterized in that the at least one carrier glass (2) ornamental glass or U glass comprises.

7. Laminated glass (1) according to at least one of claims 3 to 6, characterized gekenn¬ characterized in that the at least one carrier glass (2) single-pane safety glass (ESG) or teilvorgespanntes glass comprises.

8. laminated glass (1) according to at least one of claims 3 to 7, characterized in that the at least one carrier glass (2) has a thickness of 2 to 12 mm.

9. laminated glass (1) according to at least one of claims 3 to 8, characterized in that the thickness of the resin layer (3) is proportional to the thickness of at least one carrier glass (2) and at least 0.2 mm thick.

10. Laminated glass (1) according to at least one of claims 3 to 9, characterized in that the resin is unpigmented.

11. Laminated glass (1) according to at least one of claims 3 to 10, characterized in that the resin is pigmented.

12. laminated glass (1) according to at least one of claims 3 to 11, characterized in that the resin (3) comprises the following constituents a) a proportion of about 80-96 wt .-%, in particular 81-95.7 wt. % of a solvent-containing prepolymer based on an aliphatic isocyanate, b) a proportion of 2.5-10% by weight of 1,2,4-trimethylbenzene, c) a proportion of about 0.5-2.5% by weight. % polyfunctional aliphatic isocyanate, d) a proportion of about 0.5-2.5% by weight of propylbenzene, e) a proportion of about 0.5-2.5% by weight of mesitylene, f) a proportion of about 0.1-0, 5% by weight of hexahydromethylphthalic anhydride, g) about 0.1-0.5% by weight of dibutyltin dilaurate and h) about 0.1-0.5% by weight of 3-isocyanato-methyl-3 , 5,5-trimethylcyclohexyl isocyanate.

* * *