Laminated glass and primer used for its production

Compositions: coating or plastic – Coating or plastic compositions – Heavy metal compound containing

Reexamination Certificate

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C106S287130, C106S287190

Reexamination Certificate

active

06419734

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a laminated glass (glazing) comprising at least one layer (sheet) of transparent glass and at least one transparent layer (sheet) of ionomer resin, where one of these layers is at least partly coated with a primer, and the primer used to make the glazing.
2. Discussion of the Background
Laminated glasses are frequently used in the building industry and in the transportation industry as glass having “protection security” characteristics and for reducing the probabilities of breakage and accidents by shock. One conventional example of laminated glass particularly resistant to shock, is a laminated glass containing at least one layer of glass and at least one layer of polycarbonate. However, those glasses have significant problems in adhering the polycarbonate onto the glass or cracking (due to the difference between thermal expansion coefficients) when the glass and the polycarbonates are directly connected. One method to remedy those problems, has been to insert between the glass and the polycarbonate at least one layer of polyurethane. However, the use of such material considerably increases the cost of the product.
Another less expensive laminated glass used in the same type of applications contains a layer of glass and a transparent layer of ionomer resin. Such a laminated glass has been described in the patents EP-191,088, U.S. Pat. Nos. 4,619,873, 4,732,944, 4,906,703 and EP-483,087. In order to increase the adhesion between the glass and the layer of ionomer resin, it is known to prime the glass' surface with a coupling agent, such as a silane, organic amine (aliphatic amine, ethanolamine . . . ) or diisocyanate, before applying the layer of ionomer resin. However, these coupling agents can sometimes be insufficient to provide adequate adhesion between the glass and ionomer resin, with delamination possibly occurring during processing such as cutting operations of the obtained laminated glazing. Thus, there is a need to further increase the adhesion between the ionomer resin layers and the substrates, notably the glass substrates, which are associated with them in the laminated glazings.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide an improved laminated glazing, having good properties of chock resistance, good optical properties and an accrued resistance to delamination.
A further object of the present invention is to provide such a laminated glazing which is also economical.
These and other objects of the present invention have been satisfied by the discussion of a laminated glazing having at least one layer of glass and at least one transparent layer of ionomer resin adhered thereto, wherein the layer of ionomer resin is adhered to another layer of the glazing at at least a portion of the surfaces in contact with one another, wherein the adhesion is performed with the use of at least one metal chelate, and a primer comprising such a metal chelate for use in the laminated glazing.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the present invention, the expression “ionomer resin” means a resin that can be extruded and that contains ethylene/carboxylic acid or alpha olefin/carboxylic acid copolymers, those polymers being crosslinked by ionic reaction. This type of resin has been previously described in patents EP-483,087, EP-191,088, U.S. Pat. Nos. 4,619,973, 4,732,944 and 4,906,703, the relevant portions of which are hereby incorporated by reference. As a preferred ionomer resin, one can use resins based on ionically crosslinked copolymers obtained by combination of ethylene, styrene, or propylene monomers with monomers of acrylic acid, methacrylic acid or maleic anhydride. The one or more ionomer resins used in the laminated glazing according to the invention are preferably made of (meth)acrylic acid (where “(meth)acrylic” refers to either methacrylic or acrylic)/ethylene (or alpha olefin) copolymer(s), crosslinked by ionic reaction. The ionomer resins available commercially usually contain the previously mentioned acidic copolymers, partially neutralized or not, or metallic or amino salts of the mentioned acidic copolymers (one can notably find zinc or sodium ionomers).
The ionomer resin layers can be prepared by conventional means such as by casting or extrusion. Several glazing structures according to the invention are possible such as the structures described in patents EP-0,191,088 or EP-0,483,087 which are hereby incorporated by reference. The glazing according to the present invention can therefore contain one or several glass layers, each glass layer being optionally coated with one or several thin layers which affect optical or energy properties of the glazing, such as the transmission of energy or light. The glazing also contains one or several ionomer resin layers and, optionally, one or several layers of one or several other plastic materials conventionally used in laminated glass, such as polyurethane, polycarbonate, polymethylmethacrylate or another acrylic plastic or polyvinylbutyral. The ionomer resins adhere more or less well to the other plastic materials that can be used to make the laminated glazing, and if desired or needed, can be co-extruded with the mentioned materials. Preferably, each layer of the ionomer resin of the glazing according to the present invention is placed between two glass layers or two plastic layers or between one glass layer and one plastic layer.
The chelate used according to the invention to improve the adhesion between the layer of ionomer resin and at least one adjacent layer, notably a glass layer or another plastic layer, can intervene in different forms in the laminated glazing. In particular it can be part of a primer used to coat at least a portion of at least one face of the ionomer resin layer and/or at least a portion of at least one adjacent layer, notably a glass layer (provided or not with thin layers which affect optical or energy properties), before assembling of the two layers. It can also be incorporated in the composition of one of the layers, notably into a layer of the ionomer resin, in order to make it self-adhesive.
The metal chelate used according to the present invention can be any metal chelate, for example a titanium, zirconium, chromium chelate, and is preferably a titanium chelate. The substituents (or ligands) of that chelate are generally groups having an alkoxy functionality linked to the chelate central metal atom. Preferably at least one of the substituents has at least one additional second atom having one or more pairs of free electrons, such as a nitrogen, oxygen or sulfur atom. Preferred substituents for the present metal chelate include: triethanolamine, acetylacetonate, octyleneglycol, isopropoxyl and butoxyl . . . Most preferably, the present chelate used is a metal chelate having at least one (most preferably two) acetylacetonate group(s) and having at least one (most preferably two) alkoxy group(s) (notably C
1
-C
4
alkoxy group(s), such as propoxyl or butoxyl). Most preferred chelates include diisopropoxy-bis[acetylacetonate] titanium or isopropoxy butoxy-bis[acetylacetonate] titanium (those products being simply designated by “titanium acetylacetonate”).
The use of the present chelate to improve the adhesion between the layer(s) of ionomer resin and at least one of the adjacent layers within the laminated glazing allows the laminated glazing to have an increased resistance to delamination over time. This resistance is particularly advantageous in instances where the laminated glazing is of large dimensions and is meant to be sawed. Any delamination during the sawing is thus eliminated in the glazing according to the present invention.
The resistance to delamination of glazing according to the invention due to the improved adhesion between the resin layer(s) and the adjacent layer(s) is notably characterized by a value of at least 3 Pummel units, when the glazing is submitted to the Pummel test, described below in the Exam

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