One component glass primer including oxazoladine

(54) Title: MONOCOMPONENT LONG OPEN TIME PREMIER COMPOSITION, METHOD FOR CONNECTING A GLASS PANEL TO A VEHICLE STRUCTURE AND CONNECTED STRUCTURE (30) Unionist Priority: 24/04/2007 us 60 / 913,700 (73) ): dow global Technologies inc.

(72) Inventor (s): arcangelo bighetti, dirkschwoeppe (74) Attorney (s): Antonio Maurício Pedras Arnaud (86) International Order: pct US2008054273 of 02/19/2008 (87) International Publication: W0 2008 / i34iiode06 / n / 2008 (57) Abstract: OPEN MONOCOMPONENT primer composition, METHOD FOR CONNECTING A GLASS PANEL TO A VEHICLE STRUCTURE AND CONNECTED STRUCTURE. The present invention relates to improved long open monocomponent primer compositions for bonding substrates, methods and articles made from them. Primer compositions include an ingredient including an oxazolidine ring or derivative or analog thereof.

PI08044ÍI9-6

MONOCOMPONENT LONG-TERM PRIMER COMPOSITION, METHOD FOR CONNECTING A GLASS PANEL TO A VEHICLE STRUCTURE AND CONNECTED STRUCTURE.

Field of invention

This invention relates to a primer, and more particularly to a primer to connect one or more seals to a non-porous substrate, such as to connect a glass panel to a motor vehicle.

Background of the invention

In the field of glass bonding, there is a need for a primer that can be used under a range of conditions. A desired function of the primer is to treat the glass surface to ensure a tenacious bond between the glass and the sealant (eg, adhesive). In an application, adhesive or other sealant will be applied shortly after the primer has been applied. In other applications, the adhesive or other sealant is applied after a considerable period of time has passed. It is important in all of these applications that the primer is functional at the time when the adhesive or sealant is applied. It is common to refer to the functional life of the primer as its open time. This generally refers to the time between application of the primer and the time when an adhesive or other sealant can no longer be applied to the primer and used optimally for bonding. That is, for an application involving the installation of glass in a motor vehicle, if the primer cures too fast and becomes intractable for additional work, then a window iristalizer will not have enough time to install and properly position the glass within the vehicle frame. . For the present purposes of bonding glass (particularly in automotive applications), an optimal bond generally requires that the failure mode of the adhesive or other sealant to the primer be predominantly cohesive and, more specifically, substantially totally cohesive.

Examples of literature relating to primer materials in this field include patent application publications

US n^the US20010041782A1, 20030100676A1; US patents n^the5.010.202, 4.874.805, 4.396.681, 4.367.313, 6.875.470;

EP patent No. 1217049A1; publication of JP patent applications n^the JP2003-336008, JP2003-128988, JP2002-309182 and

JP2002-309163, all of which are expressly incorporated herein by reference. Two-component primers may be used and many are known to exhibit both long open and short open properties. However, two-component primers generally require additional work and handling steps.

US patent No. 6,133,398, incorporated by reference, describes a one-component adhesive composition including a polyurethane prepolymer, which may employ a compound containing at least a portion of oxazolidine. Summary of the invention

The present invention is generally directed to a single component long open primer composition comprising a base primer composition (preferably dispersed or dissolved in a volatile solvent) including (a) a prepolymer with isocyanate functionality (prepolymer (a)) derived from reaction product of an aliphatic polyisocyanate and a polyol, and which is partially reacted with an amino group of a secondary aminosilane, the aminosilane includes two or three methoxy groups linked to silicon, two or three ethoxy groups linked to silicon, or a combination thereof; (b) a prepolymer with isocyanate functionality (prepolymer (b)) with an isocyanate content greater than about 1%, which is the reaction product of an aromatic polyisocyanate and a polyol of M_n> 300 (eg, a reaction product of an aromatic diisocyanate and a polyether triol); and an ingredient including an oxazolidine ring or derivative or analog thereof, the primer exhibiting an open time of at least about 1 week, more preferably at least about 1 month, and even more preferably at least about 3 months or more .

The primer composition may also include one or a combination of (1) a first adduct of (i) an aliphatic isocyanate and (ii) a mercaptosilane, an aminosilane (eg, a secondary aminosilane) or both (e.g. ., particularly a silane having two or three such methoxy and / or ethoxy groups attached to the Si atom); or (2) an adhesion promoter, such as one including a second adduct of (i) an aromatic polyisocyanate and (ii) a mercaptosilane, an amino silane (e.g., a secondary aminosilane) or both (e.g. ., particularly a silane having two or three of these methoxy and / or ethoxy groups attached to the Si atom). For example, for use in the adhesion promoter, a possible aromatic polyisocyanate includes a thiophosphate, a phosphate, a thiophosphane moiety, or any combination thereof. Specifically, it could be a tris thiophosphate (isocyanatophenyl).

The compositions may additionally include a dye or a pigment (e.g., carbon black). The ingredients are dispersed and / or dissolved in a suitable solvent, and may optionally include a suitable catalyst.

The ingredient including an oxazolidine ring, or derivative or analog thereof, includes a bisoxazolidine and is present in an amount of about 2 to about 8% w / w of the overall composition. For example, it may include a carbamic acid, 1,6-hexanediyl bis-, bis- (2 (2- (1-methylethyl) -3-oxazolidinyl) ethyl) ester, and will be present in an amount of about 4 to about 6% by weight of the overall composition.

It is possible that the composition will employ the second adduct in an amount ranging from about 0 to about 20% by weight of the overall composition, such as from about 2 to about 10% by weight of the overall composition, or even more specifically from about 4 to about 8% by weight of the overall composition. The composition may additionally include any or any combination of a (meth) acrylic film former in an amount of less than about 10% by weight of the overall composition; a load; a stabilizer such as diethyl malonate; or an acid such as phosphoric acid.

The invention also contemplates methods for using the composition here, which includes the steps of applying the primer compositions to a first substrate; wait at least about 20 seconds, 1 minute, 3 minutes or more; apply an adhesive over the primer composition and attach a second substrate to the adhesive. For example, a method for attaching a glass panel to a vehicle structure, may include the steps of (a) applying the primer here substantially along the periphery of one side of a glass panel; (b) superimposing a fillet of an adhesive onto the primer composition; and (c) installing the glass panel by contacting the adhesive with a vehicle frame defining an opening for receiving the glass panel. Steps (a) and (b) can be separated by a period longer than 20 seconds and shorter than 3 months at room temperature; for a period longer than 1 day at room temperature or for a period longer than a week or a month at room temperature. The invention also contemplates bonded structures resulting from the other structures that include primers described here.

Detailed description of the invention

Unless stated otherwise (e.g., as a weight ratio), as used here, all parts by weight are based on 100 parts by weight of the described composition. In the case of the resulting composition, this means that the weights are based on 100 parts by weight of the resulting overall composition. It will be appreciated that concentrates or dilutions of the amounts disclosed here may also be employed. In general, the relative proportions of the ingredients disclosed here will remain the same. Hence, for example, if the teachings require 30 parts by weight of Compounds A and 10 parts by Component B, the skilled person will recognize that such teachings also constitute a teaching of the use of Component A and Component B at a weight ratio of 3: 1.

In one aspect, the present invention is directed to a base primer composition including (a) a prepolymer with isocyanate functionality (prepolymer (a)) derived from the reaction of an aliphatic polyisocyanate and a polyol, and which is at least partially reacted with a secondary amino group of a secondary aminosilane, where the aminosilane includes two or three methoxy groups linked to silicon, two or three ethoxy groups linked to silicon, or a combination thereof; (b) an isocyanate-functional prepolymer (prepolymer (b)) with an isocyanate content greater than about 1% and (c) at least one solvent for (a) and (b); and an ingredient including an oxazolidine ring or derivative or analog thereof.

In another aspect, the present invention provides an improved one-component, open long-time primer composition that includes a base primer composition in combination with: an ingredient having an ingredient including an oxazolidine ring or derivative or analog thereof; a first adduct of (i) an aliphatic isocyanate and (ii) a mercaptosilane, an amino silane (eg, a secondary aminosilane) or both (eg, particularly a silane having two or three of these methoxy groups and / or ethoxy bonded to the Si atom); and an adhesion promoter, including a second adduct of (i) an aromatic polyisocyanate and (ii) a mercaptosilane, an amino-silane (eg, a secondary aminosilane) or both (eg, particularly a silane having two or three of these methoxy and / or ethoxy groups attached to the Si atom). The composition desirably further includes a dye or pigment (for example, carbon black) and a solvent. In one approach, the combination of materials above is employed in a base primer composition that includes at least one isocyanate prepolymer that includes a silicon (e.g., it is at least partially silylated, with an amine-functional silane).

The ingredient including an oxazolidine ring or derivative or analogue of this invention may be any suitable ingredient and desirably may be one that hydrolyzes upon exposure to moisture to give reactive hydroxyl and amine functionalities to react with isocyanates present. In a specific illustration, it includes a bisoxazolidine. However, it is possible that it includes an isoxazolidine. In addition, oxazolidine derivatives or analogues may be employed, such as that including an oxazolidinone moiety, oxazolidinedione moiety, or a combination of these. In a particular aspect of the present invention, a preferred azole will be based on a bisoxazolidine, having functionality of at least 2, and more specifically a functionality of 4. Desirably, the ingredient will have a flash point greater than about 50 ° C, e.g., about 60 or even 75 ° C or higher, and may additionally have an equivalent NH / OH weight of about 80 or higher . For example, it is possible that the ingredient is an aliphatic polyamine alcohol based on a bisoxazolidine urethane. An illustrative oxazolidone-containing compound is carbamic acid, 1,6-hexanediyl bis-, bis- (2- (2- (1-methylethyl) 3-oxazolidinyl) ethyl) ester. Examples of commercially available ingredients useful here include Incozol 4 or Incozol LV, commercially available from Industrial Cupiymers Ltd., or Hardener OZ, commercially available from Bayer MaterialScience. The ingredient including an oxazolidine ring or derivative or analog thereof will generally be present in an amount ranging from about 1 to about 10% by weight of the total composition, more particularly about 2 to about 8% by weight of the total composition. Optionally, the ingredient including an oxazolidine ring or derivative or analog thereof is provided as a coated or encapsulated particle or droplet, e.g., in accordance with the teachings of US Patent No. 6,133,398 (incorporated by reference).

commercially

Desmodur® N100

The prepolymer with isocyanate functionality (b) with an isocyanate content greater than about 1% is usually the reaction product of a polyol having a functionality of more than about 2 and a molecular weight (M_n) greater than about 300 and an isocyanate, and more preferably an aromatic polyisocyanate. In a specific aspect, the preferred isocyanate will be a diisocyanate, such as a diisocyanate having a functionality of at least 2 (e.g., tri-functional). For example, the diisocyanate may be an aromatic diisocyanate, such as one selected from TDI and MDI, or a combination of these, such as one that includes approximately 97% 4,4'-diphenylmethane diisocyanate and 3% 2,4-diisocyanate '-diphenylmethane. A commercially available example of such an isocyanate is MDI Isonate® M125, commercially available from The Dow Chemical Company.

Although other polyols can be selected, a particularly preferred one will be a triol, and particularly one having a hydroxyl number of at least 200. an example of such a polyol is commercially available from The Dow Chemical Company, under the name VORANOL^mR CP260.

first adduct will typically be a reaction product of (I) an aliphatic isocyanate and (II) a mercaptosilane, an amino silane (eg, a secondary aminosilane) or both (eg, particularly a silane having two or plus methoxy and / or ethoxy groups attached to the Si atom). A specific preferred diisocyanate is an aliphatic isocyanate, and particularly a trifunctional aliphatic polyisocyanate, such as based on a hexamethylene diisocyanate (HDI) (an example of which is under the trade name MaterialScience). Although other mercaptosilanes can be selected, a particularly preferred one will be a trimethoxysilane mercaptopropyl (eg, one as commercially available from Bayer available as Dynasilan MTMO from Degusssa or as

Silquest^MRGeneral Electric's A-189. The molecular weight of mercaptosilane is desirably less than about 2000, more specifically less than about 900, and even more preferably less than about 500 (e.g., about 200 or even about 80). The third prepolymer, if present, will generally be present in an amount ranging from about 0 to about 20% by weight of the total composition, more particularly about 1 to about 10% by weight of the total composition, and even more particularly about from 2 to about 4% by weight of the total composition.

The second adduct typically functions as an adhesion promoter, which is usually a reaction product of an organofunctional silane and an isocyanate. More specifically, as will be explained, the adhesion promoter makes use of an adhesion promoter that includes at least one aromatic polyisocyanate which, more particularly, includes phosphorus.

In one embodiment, an ingredient of the second adduct may include an amino-silane and, more particularly, a secondary amino-silane. One at least two silyl groups attached to each attractive silane includes with three methoxy silane groups an amino group one of the secondary hindered groups or any combination thereof. An example of such a commercially available amino silane is bis- (trimethoxysilylpropyl) -amine, such as Silquest A1170, from GE Advanced Materials-Silicones. Additional information on silane materials suitable for use here is found in US Patent No. 4,374,237, incorporated herein by reference. Other examples of silanes include, without limitation (individually or in combination with bis- (trimethoxysilylpropyl) -amine), include silanes having a hydroxy functionality, a functional mercapto, or both, such as 3-aminopropyltrimethyloxysilane, 3aminopropyltriethyloxysilane, 3-aminopropyltrismethoxyethoxysilane, 3 -aminopropyl-methyl-dietoxyethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-butyl-39 aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl-methyl-dimethoxysilane, (N-cyclohexylaminomethyl) methyldi-ethoxysilane, (N-cyclohexylaminomethyl) methyltriethoxysilane, (N-phenylaminomethyl) methyl-methoxyethylmethyl, (4-phenylamethylmethyl) amino-3,3-dimethylbutyltrimethoxysilane, or any combination thereof.

The second adduct also includes as one of its ingredients an aromatic isocyanate, and particularly trifunctional. In a preferred embodiment, it includes at least one match.

an isocyanate particularly isocyanate isocyanate 6,974,500,

An example of including is hereby incorporated by reference, one such

The generally described in the US patent is not represented by the following formula 1:

<img file="BRPI0804499A2_D0001.tif" />

NCO

Pittsburgh, Pa. (Which may

Formula 1

A possible isocyanate is tris (p-isocyanate) thiophosphan. A particularly preferred isocyanate is a thiophosphate with an isocyanate group such as a solution of tris thiophosphate (p-isocyanate-phenyl) in ethyl acetate sold under the trade name DESMODUR RFE and commercially available from Bayer Corporation, Other examples of possible isocyanates are employed individually or in combination with tris thiophosphate (p-isocyanate-phenyl) include trifunctional isocyanates, which may be aromatic or aliphatic (eg, an aliphatic polyisocyanate based on HDI, and possibly having an isocyanate content of about 15 to about 25 percent). Examples of suitable trifunctional isocyanates include those commercially available under the designations Desmodur N 100, Desmodur N 3300, or Tolonate HDT.

In general, the second adduct is prepared by mixing silane with the isocyanate, particularly in an amount of about 1 mole of isocyanate to about 1 to about 3 moles of silane (eg, amino-silane, mercapto silane, or combination thereof), and more specifically about one mole of isocyanate with about 2.3 moles of silane (e.g., amino-silane, mercapto-silane, or a combination of these).

A particular approach to making the second adduct is to at least partially react an aromatic polyisocyanate having a functionality greater than about 2 with a silane (eg, amino-silane (such as a silane with secondary amino functionality), silane mercapto , or a combination thereof with silane including a plurality of silicon-linked alkoxy groups, two or three silicon-linked ethoxy groups, a combination of these or the like).

In general, the present compositions are based on combining the ingredients with a base primer that includes at least a first prepolymer (a) derived from the reaction of at least one polyisocyanate and at least one polyol, and particularly one that will have a free isocyanate content . In a more particular aspect, the base primer includes a prepolymer with isocyanate functionality derived from the reaction of an aliphatic polyisocyanate and a polyol. In a highly specific embodiment, the base primer includes an isocyanate prepolymer derived from the reaction of an aliphatic and a polyol, and is at least reacted with an amino group of a particularly, an aminosilane (eg, a secondary aminosilane), the aminosilane includes a plurality of silicon-linked alkoxy groups (e.g., two or three silicon-linked methoxy groups, two or three silicon-linked ethoxy groups, a combination of these or the like); and a second prepolymer (b), described herein, and preferably with at least one partially silane polyisocyanate functionality, and solvent for the two prepolymers. An example of commercially available primers that can be used in accordance with this teaching includes, without limitation, Betaprime^MR 5500.

Without wishing to be bound by any theory, it is believed that the present compositions advantageously employ a particular molecular structure by which at least a portion of the molecule includes silicon (e.g., it is silane), and a portion of the molecule includes functionality , such as an isocyanate feature, that is able to bind to a base primer such as through a molecular reticulate of the base primer and the combination of an aliphatic isocyanate prepolymer with an aromatic isocyanate prepolymer. Such prepolymers may form part of a base primer composition.

The isocyanates useful here may be selected from diisocyanates, triisocyanates, or any combination of these. Suitable isocyanates may include an aliphatic, cycloaliphatic, heterocyclic isocyanate, aromatic isocyanate, combination of these. Particular examples may include an isocyanate selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-diphenyl methylene diisocyanate (MDI) or any combination thereof, and even more particularly an isophorone diisocyanate (IPDI) , methylene diphenyl (MDI), toluene diisocyanate (TDI), or any combination thereof. As noted, polymeric derivatives of any of the isocyanates here are also contemplated. Preferably, the polyisocyanates used have an average isocyanate functionality of at least 2.0 and an equivalent weight of at least about 80. Preferably, the isocyanate functionality of the polyisocyanate is at least 2.0, more preferably at least about 2.2, and most preferably at least about 2.4; and is preferably not greater than araliphatic, or any selected from 4,4'-diisocyanate about 4.0, more preferably not greater than about 3.5, and most preferably not greater than about 3.0. Higher functionality may also be used, but it may cause excessive crosslinking, and the result is an adhesive that is too viscous for easy handling and application, and may cause the cured primer to be too brittle. Preferably, the equivalent weight of the polyisocyanate is at least about 100, more preferably at least about 110, and the

<td>more preferably at</td><td>any less</td><td>fence</td><td>in</td><td> 120;</td><td>and is</td>

<td>preferably not greater</td><td>what</td><td>fence</td><td>in</td><td> 300,</td><td>more</td>

<td>preferably not greater</td><td colspan="2">what about</td><td> 250,</td><td colspan="2">It is the most</td>

preferably not greater than about 200.

Exemplary isocyanate-reactive compounds may be an organic compound having at least two isocyanate-reactive moieties, such as a compound containing an active hydrogen moiety or an iminofunctional compound. For the purposes of this invention, a portion containing active hydrogen refers to a portion containing a hydrogen atom which, due to its position in the molecule, exhibits significant activity according to the Zerewitnoff test described by Wohler in the Journal of the American Chemical Society, Vol. 49, p. 3181 (1927). Illustrative of such active hydrogen plots are -COOH, -OH, -NH₂, -NH-, -CONH₂, -SH, and -CONH-.

Preferred active hydrogen-containing compounds include polyols, polyamines, polymeraptanes, and polyacids. Suitable polyols may include, for example, polyether polyols, polyester polyols, poly (alkylene carbonate) polyols, hydroxyl-containing polyethers, polymeric polyols, and mixtures thereof. Polyether polyols may include, for example, one or more diols, triols or tetrols based on polyoxyethylene, polyoxypropylene, polyoxybutylene, and / or polytetramethylene ether. In general, polyether polyols are prepared by polymerizing alkylene oxides in the presence of an initiator compound containing active hydrogen. Most preferred, however, are polyols capped with alkylene oxide.

Preferably, the isocyanate-reactive compound has a functionality of at least preferably at least preferably preferably more plus and is more plus less about 1.5, about 1.8, and at least about 2.0;

not greater than about 4.0, preferably not greater than about 3.5, and preferably

Preferably, no greater than about 3.0. the equivalent weight of the reactive compound

<td>with isocyanate</td><td>it's from</td><td>fur</td><td>least about 200,</td><td>more</td>

<td>preferably</td><td>fur</td><td>any less</td><td>about 500, and it's</td><td>more</td>

<td>preferably</td><td>fur</td><td>any less</td><td>about 1,000;</td><td>and is</td>

<td>preferably</td><td>not</td><td>bigger</td><td>that about 5,000,</td><td>more</td>

<td>preferably</td><td colspan="3">no greater than about 3,000, and the</td><td>more</td>

preferably not greater than about 2,500. A particular example employs a polyol isocyanate reactive compound that has an equivalent weight of about 100 to about 1500, and more specifically about 300 to about 1000.

The isocyanate and the isocyanate-reactive compound can be reacted in the presence of a suitable catalyst. Catalysts for use here may include, for example, a metal complex, such as a stannous or stannous compound. Examples include a stannous salt of carboxylic acid (e.g., stannous octoate, stannous oleate, stannous acetate, and stannous laurate), a trialkyltin oxide, a dialkyl tin dicarboxylate (for example, dibutyl tin dilaurate, dibutyltin diacetate, diethyl tin diacetate, and dihexyl tin diacetate), a dialkltin dihalide, or a dialkyl tin oxide, such as di-2-ethylhexyl tin oxide, or dioctyltin dioxide, a tertiary amine, or a mercapteto. Other catalysts can also be used. For example, tertiary amine catalysts include trialkylamines (e.g., trimethylamine, triethylamine), heterocyclic amines, such as Nalkylmorpholines (e.g., N-methylmorpholine, N14 ethylmorpholine, dimethylaminodiethyl ether, etc.), 1,4diimethylpiperazine, triethylenediamine, etc. Aliphatic polyamines, butanediamine catalysts such as N, N, Ν ', N'-tetramethyl-1,3 can also be used as

A highly preferred catalyst includes a dibutyltin compound and, more specifically, includes or consists essentially of dibutyltin dilaurate. In a particular embodiment, however, the catalyst employed will be one or more catalysts selected from metal salts, such as tin carboxylates, organo silicon titanates, alkyl titanates, bismuth carboxylates, or an ether, such as dimorpholinodiethyl ether (DMDEE) , or alkyl-substituted dimorpholinodiethyl ethers. Preferred catalysts include dimorpholinodiethyl ether and (di- (2- (3,5-dimethylmorpholine) ethyl) ether. Such catalysts, when employed (individually or in combination) are preferably employed in an amount of up to about 1% by weight of the total composition, more specifically less than about 0.8% by weight of the total composition (e.g. about 0.1 to about 0.8% and, more particularly, about 0.3 to about 0.5% In one aspect of the invention, the catalyst employed will be free of any bismuth.

isocyanate and the isocyanate-reactive compound can also be reacted in the presence of a suitable silane (eg an aminosilane) to introduce silicon into the base primer.

The resulting compositions here may include one or more other ingredients, such as a solvent, a stabilizer, a film former, a dye or pigment (eg, carbon black, eg, Raven 420), a load; a UV protector, or any combination of these.

The solvent component of the primer composition is volatile and is preferably a solvent that will dissolve the resin at a temperature in the range of about -10 ° C to about 10 ° C, more preferably from about 0 ° C to about 40 ° Ç. The solvent is preferably anhydrous, in order to assist in preventing the isocyanate groups from reacting prematurely with water. Examples of such solvents include xylene, ethylbenzene, toluene, ethyl acetate, propyl acetate, butyl acetate, butanol, propanol, isopropanol, ethanol, acetone, methyl ethyl ketone, butoxy, 2-buitoxyethanol, 3-methoxybutyl acetate, NMP, n -heptane, petroleum, or any combination thereof, and is preferably butoxy, methyl ethyl ketone, ethyl acetate, or a mixture of these. The solvent may comprise the balance of any of the resulting or intermediate compositions and is preferably used in an amount of at least about 40 percent, more preferably at least about 50 percent, and most preferably at least about 60 percent ; and it is preferably not greater than about 90 percent, more preferably not greater than about 85 percent, and most preferably not greater than about 80 percent, based on the weight of the total primer composition.

In one embodiment, it is further contemplated that a (meth) acrylic film-forming resin may be employed. Suitable film-forming resins include polyacrylate resins, epoxy resins, polyester resins (polymers of a carboxylic acid and a glycol), polyester copolymers, poly (vinyl chloride resins), chlorinated rubber, ethylene vinyl acetate copolymers, polyacrylate copolymers, or any combination thereof. The film-forming resin is preferably soluble in any solvent used in the composition. In a preferred embodiment, the film-forming resin preferably has a molecular weight of more than about 3,000 and more preferably more than about 5,000. The film-forming resin preferably has a molecular weight of less than 50,000 and more preferably less than about 30,000. A specific film-forming resin is a poly (meth) acrylate resin. An example of a particular preferred film forming resin is an acrylic copolymer with an hydroxyl equivalent weight of about 2,000, commercially available in solution from Rohm and Haas Company as Paraloyd^MR B4 8N. The film-forming resin may be present in any suitable amount. For example, it may be present in an amount of about 0.1 part by weight, about 1 part by weight or up to about 5 parts by weight, or more, based on the weight of the primer composition. If used, the concentration of the film-forming resin is preferably less than about 10 parts by weight of the total composition, and more preferably less than about 5 parts by weight of the total composition, and most preferably less than about 5 parts by weight. weight of the total composition, and even more preferably less than about 2 part by weight (e.g., up to about 0.5 part by weight) of the total composition.

Loads commonly used in polymers and polyurethane primers may be used in the compositions of this invention. Suitable fillers can be selected from titanium dioxide, calcium carbonate, superficially treated silica, mica, fumed silica, talc, or any combination of these. If used, the charge concentration is generally less than about 40% by weight of the total composition, and more specifically, from about 5 to about 20% by weight of the total composition, e.g., about 7 to about 15% by weight of the total composition.

Other ingredients may also be used, such as (without limitation), a catalyst, an initiator, a curing agent, a light stabilizer, a flame retardant, a plasticizer, a thixotropic, or any combination of these. Additive illustrations are found, without limitation, in US Patent No. 6,133,398 (incorporated by reference).

A particular preferred composition includes the base primer composition, and the ingredient including an oxazolidine ring or derivative or analog thereof, and additionally may specifically include a stabilizer (e.g., diethyl malonate), an acid (e.g. , phosphoric acid), or both.

For illustrative purposes, the concentrations of the ingredients here are further described. For example, the base primer may be present in an amount of about 20 to about 90 weight percent and more specifically about 30 to about 60 weight percent (e.g., about 40 to about 45 percent by weight). The first adduct, if present, will be present in an amount of up to about 20 weight percent, and more specifically up to about 10 weight percent (e.g., about 2 to about 4 weight percent) ). The second adduct, if present, will be present in an amount of up to about 20 weight percent, and more specifically about 2 to about 10 weight percent (e.g., about 4 to about 6 percent percent by weight). The prepolymer with isocyanate functionality with an isocyanate content greater than about 1%, if present, will be present in an amount of up to about 50 weight percent, and more specifically about 5 to about 30 weight percent ( e.g., about 15 to about 20 weight percent). A specific composition may also include a catalyst (e.g., DMEE) in an amount of up to about 0.8 weight percent, more specifically about 0.1 to about 0.5 weight percent, and even more specifically about 0.13 to about 0.3 weight percent. For an application in which a pigment or dye (eg, carbon black) is used, it can be used in an amount of up to about 40 weight percent, more specifically, about 5 to about 20 weight percent, and even more preferably about 7 to about 15 weight percent. The composition may also include about 0.1 to about 0.5 weight percent of diethyl malonate (e.g., about 0.25%) and about 0.01 to about 0.05 per weight percent phosphoric acid (eg, about 0.03 weight percent).

Anyone familiar with the subject will be familiar with how to prepare the ingredients here. See, generally, US patent No. 6,133,398 (incorporated by reference). In general, the reaction product compositions and their respective ingredients may be prepared by any suitable method, such as by mass polymerization and solution polymerization. The reaction steps, and also preferably the step or steps of mixing all the components with one or more ingredients here are carried out under anhydrous conditions, preferably under an inert atmosphere, such as a nitrogen blanket, to help avoid cross-linking of the groups. isocyanate by atmospheric humidity.

The primer compositions here may be employed in any of a number of applications. A particular approach is to apply the primer composition (eg, as a one-part composition), using procedures disclosed in the art, to a substrate for use on a windshield, a taillight, a side window, a ceiling solar of a motor vehicle, an architectural window, a skylight, a hatch, a door frame, a display case, a lens, among others. Another useful application is for printing labels, packaging, containers (eg, beverage bottles), among others. A preferred application is to use the primer compositions here to make sets of panels substantially transparent. The sets here can be adapted for temporary or permanent assembly to a structure. The sets may be adapted for opening, closing, or otherwise for translation, eg, by sliding, by jointing, by pivoting, by folding, or any combination of these. The sets can thus be used in one or more applications such as taillights, side windows, automotive sunroofs, architectural windows, skylights, hatches, door frames, display cases, among others. The compositions and methods here are also particularly useful when used in combination with pre-applied adhesive systems.

Typically, substrates will be substantially flat or shaped, eg, defining curved surfaces. The substrates will generally be panels that are transparent across at least one surface, and particularly across both facing surfaces, over at least 25% of the surface area and, more specifically, at least a predominant part (e.g. , at least about 60%, 75% or even 90% of the surface area). The substrates here will generally be made of a substantially amorphous material, and particularly an amorphous ceramic (such as glass), a plastic, or a combination of these. Without limitation, examples of suitable substrate materials include poly (meth) acrylates, polycarbonates, vinyls (eg, poly (vinyl chlorides), polyesters ([., Oriented polyesters), polyimides, polyolefins, polyamides, glass , any combinations of these (eg, laminated glass), or the like. In a particular example, the substrates include or even consist essentially of a material selected from glass, poly (meth) acrylates, polycarbonates or any combination thereof. Substrates may have a laminate layer, dye or any combination of these. Substrates may also be injection-molded reaction plastic. Assemblies that include reaction injection molded parts encapsulating a panel, such as a substantially transparent panel, can be connected according to the teachings here. An example of a possible approach to the manufacture of encapsulated panels is disclosed in US patent application serial number 60 / 870,643 (entitled ENCAPSULATED PANEL ASSEMBLIES AND METHODS FOR MAKING SAME, incorporated by reference). The compositions here can also be used to connect a surface of a pinchweld.

Although some applications require the coating of substantially an entire surface of a substrate with the coating composition here, generally the coating compositions will be applied to the substrates selectively, according to a predetermined pattern (eg, substantially over a edge portion of the substrate, around the periphery of the substrate, among others). For example, one approach is to apply the edge coating of the substrate inwardly towards the central portion in a width of about 2, 5, 8 or even 12 cm or more. It is also possible that the coating composition can be applied to define one or more lines, curves, points, or other geometric configurations comprising segments of width, height, length or other constant or variable dimensions.

Any of a variety of standards disclosed in the art can be applied. The primer composition can be applied to a substrate (eg, glass, or coated plastic) using any medium disclosed in the art, such as using a brush, roller, spraying on the surface, inkjet printing, screen printing , and the like. It can be applied using robotic devices disclosed in the technique (eg, one having at least 2 geometric axes of movement). After applying the primer composition to the substrate surface, it is exposed to polymerization conditions.

The substrates here will typically include at least one surface on which the composition is applied. The surface can optionally be treated by improving the bonding strength of the coating to the substrate. For example, with a primer, flame spray, corona treatment, plasma treatment, or some other surface treatment. Consequently, when applied, the coating composition is in direct intimate contact with the substrate, and particularly in the substantial absence of any intermediate interface layer. Of course, after applying the composition to the substrate, it will also be possible to apply, on one or both of the composition and the substrate, an additional layer (eg, a silicone, an acrylic, a polyurethane, or another, to make a protective layer). It is also possible that the coating composition here can be used on, under and / or adjacent to an inorganic or organic frit (e.g., a frit of the type taught in co-pending US patent application Serial No. 11 / 472,119 filed on June 20, 2006 (priority 60 / 692,318, filed on June 20, 2005)), by Baikerikar et al. (incorporated by reference).

When applied, the compositions here will generally have a thickness of up to about 250 microns or greater. Most commonly, they will be less than 150 microns, less than less than about 100 microns or even less than about 50 microns (eg, about 10 to about 30 microns or less).

Examples of adhesives or sealants suitable for use in combination with the primer compositions of the present invention include, without limitation, single-component or multi-component urethane compositions which, in turn, may be curable by moisture. Particularly preferred urethanes are based on MDI, HMDI or a combination of these. Examples of adhesives include, without limitation, those commercially available from The Dow Chemical Company under the designation BETASEAL^MR, such as one or more of types n^the 1759, 1841, 1843, 1965, 2002, or 2002 LVRP. Other suitable commercial examples include, without limitation, those commercially available from The

Dow Chemical Company under the name BETASEAL^MRtypes 15-625, 15-685, 15-845, or the like).

The invention also contemplates kits that include an adhesive or sealant composition and one or more primer compositions. For example, such a kit could include one or more primer compositions according to the present invention, with or without the adhesive or sealant composition (e.g., a single-component or multi-component urethane adhesive). It may also include one or more cleaners, applicators, tapes, tools or any combination of these. The compositions here may be provided in a cartridge, a laminate package or both. The compositions here provide a generally hard coating and abrasion resistance. The compositions are also expected to exhibit excellent adhesion performance and weather resistance. The resulting freshly prepared primer materials in accordance with the teachings here are expected to have good storage stability.

The compositions here are useful for printing a substrate to which an adhesive or other sealant is then applied. Consequently, one aspect contemplates contacting a substrate with the compositions described here. More specifically, the compositions here are useful in methods for attaching a glass panel to a vehicle structure, such as a motor vehicle, which includes the steps of (a) applying (e.g., using any suitable method disclosed in the art) , such as by broaching, brushing, dipping, rubbing, or the like) the primer composition of the invention substantially along the periphery on one side of the glass panel (e.g., window); (b) superimposing a fillet of an adhesive onto the primer composition; and (c) install the glass panel by contacting the sealant (eg, adhesive) with a vehicle frame defining an opening into which the panel is to be placed and allowing the adhesive and primer composition to heal. It is intended that the primer is applied here (eg, over or otherwise contacted with a substrate and subsequently covered with a sealant (eg, an adhesive). Substrates that may be used include non-porous substrates, such as glass (eg, flat glass, glass frit, coated glass, stained glass, reflective glass, tempered glass, annealed glass, or any combination thereof). Any of a number of other substrates can be employed, such as enamel, cured polyurethane, glass encapsulation materials, e-coatings, galvanic zinc coatings, aluminum, steel, paint, plastics, hard coated organic glazing, or any combination of these. The composition can be applied to the substrate using any suitable method. Before applying the composition to the substrate, the substrate may be subjected to a cleaning, drying or drying step or otherwise the surface for the primer is prepared. Any number of adhesives or other sealants can be used.

The present invention allows steps (a) and (b) above to be separated by a period greater than 20 seconds and up to about 1 year (e.g., up to about 3 or up to 6 months) at room temperature. More specifically, a method of the present invention contemplates a step of carrying out step (b) at least a minute, an hour, a day, a week or even a month after step (a) has been carried out. Step (b) can also be performed within one minute to three months of step (a), or from one hour to one month from step (a). The time lag between steps (a) and (b) does not impact the adhesion characteristics resulting from the primer of the invention, with resulting connections still being able to withstand at least 500, 1000, or up to 2000 hours of accelerated weather testing under a natural sunlight simulator (eg, a xenon arc light source, such as by using a climatometer test (WOM) according to SAE J1885, ASTM D2565-99, SAE J1960 or other suitable standard ). For such a weatherometer test, one approach is to provide glass substrates with a black enamel on one side. The polymer applied here is applied to the enamel, and a sealant is applied over the primer. The substances are then bonded together and aged (eg, for 7 days) to cure the seal.

It will also be appreciated that a plurality of ingredients or functional steps can be combined into a single ingredient or step, or the functions or structures of a step or ingredient can be divided between plural steps or ingredients. For example, it should be appreciated that the above contemplates the use of a plurality of individual prepolymers or other ingredients. The ingredients can be combined simultaneously, in sequence or a combination of these. Therefore, combinations of two or more prepolymers or other ingredients may be employed, such as combining the reaction products of two or more of the ingredients after the reaction has occurred giving rise to the reaction product or employing a single ingredient that employs the functional characteristics of multiple ingredients described. Alternatively, functions performed by one of the ingredients can be divided between or performed by other ingredients. The present invention contemplates all such combinations. Unless stated otherwise, concentrations and amounts of the various characteristics shown here are not intended to be restrictive of the invention, and others are possible. In addition, while a feature of the present invention may have been described in the context of just one of the illustrated embodiments, that feature may be combined with one or more other features of other embodiments, for any given application. It will also be appreciated from the above that the manufacture of the unique structures here and the operation of them are also methods according to the present invention.

Percentages expressed here are not intended to be limiting. The declared quantities may be converted to provide quantities of some or all of the ingredients, and such quantities are contemplated as well. For example, if a composition declares 10% by weight of A, 40% by weight of B and 50% by weight of C, the skilled person will recognize that A and B are present in a ratio of 1: 4 parts (e.g. 1 part of A and 4 parts of Β). B and C will be present in a 4: 5 ratio (eg, 4 parts of B and 5 parts of C).

The following illustrations, which are not intended to be limiting, demonstrate the compositions of the present invention and certain preferred embodiments thereof. The values ​​shown are approximate and should not be construed as limiting the invention. Variations in processing parameters are possible. In addition, the expected results shown may also vary (eg, about + 10% of the declared values). For these illustrations, several polyurethane sealants are tested, commercially available as BETASEAL grades^MR The Dow Chemical Company. In general, for the poultice cycle, the samples are placed directly in a climatic chamber at 70 ° C, 100% relative humidity, for 7 days, or wrapped in cotton, moistened with sufficient water and sealed in a polyethylene bag for then stored in an oven at 70 ° C for 7 days. The samples are then placed in a freezer for 16 hours at -20 ° C, after which the sample is left to stand at room temperature for 2 hours. The cycle can be repeated multiple times, after which the samples are removed from the bag and subjected to the rapid knife test. Desirably, there will be no bubble formation and the failure will be cohesive in the sealing layer. For the test results presented in the tables below, only 1 poultice cycle is applied.

A primer, referred to as primer C, is prepared by mixing an example of a base primer, the oxazolidine compound and the adduct and other components in the following proportions (in parts by weight): _

<td>Oxazolidine</td><td>500 pieces</td>

<td>Betaprime^MR 5500</td><td>6100 pieces</td>

<td>First Adduct</td><td>310 pieces</td>

<td>Second Adduct</td><td>500 pieces</td>

<td>Phosphoric acid</td><td>1 part</td>

<td>Carbon Black</td><td>750 pieces</td>

<td>Film Forming Resin</td><td>40 pieces</td>

<td>Solvent Methyl Ethyl Ketone</td><td>1799 pieces</td>

<td></td><td>10,000 pieces</td>

primer (C) from the example above is applied to a substrate coated with a conventional enamel (the type commonly used in the manufacture of motor vehicles in the United States), after the enamel coating has been cleaned with Dow Betaclean^MR BC 3300. Dow Sealant Betaseal^MR 1759 is applied immediately after 3 minutes of primer application. The set is subjected to aging WeatherO-Meter according to SAE J 1960 by exposure to UV radiation for 2000 hours in an Atlas Ci65 instrument. When applying the peeling test (rapid knife test) according to the description below, the bonding of the primer to the sealant fails completely in cohesive mode.

<td>Aim. DIN Cup 53211 (4 mm)</td><td>Fresh</td><td>1 month (40 ° C)</td><td>2 months (40 ° C)</td><td>3 months (40 ° C)</td>

<td>(s)</td><td> 11,8</td><td> 12,7</td><td> 13, 9</td><td> 15,8</td>

For the data in the tables below, a peeling test (quick knife test) of about 4 to 6 cm, and a length of about 100 to 150 cm) is peeled back, at an angle of about 90 °, for a minimum of 3 cm. Any residual fillet is cut through the substrate, at an angle of 90 ° in the direction of the fillet, at approximately 1 cm intervals along the length. Using the Appendix 1 Code Table, the failure mode observed after peeling, on the fracture or delamination surface, is assessed and classified. Any area with cohesive failure is estimated, as a percentage of the area tested, and classified with a number from 1 to 5. Then, the rest of the area is evaluated, against the failure modes listed in the Appendix 1 Code Table, and is designated with the relevant code letters. The results are recorded using the following format: number letter letter letter, with the number indicating the% cohesive failure area and the letters, in descending order, indicating other observed failure modes. For example, a report of 2abv means 25% of cohesive failure, the remainder being delamination that is more of the type a than b and more than v; 2^The/ b would mean 25% cohesive failure, with the remainder being equal proportions of a and b.

The substrate is float glass and the primer is applied using a standard spray application unit. Open times refer to the time elapsed between application to the substrate and the subsequent application of sealant. Unless stated otherwise, open weather conditions (specified for example in seconds (s), minutes (min), days (d), or month (m)) are at a temperature of 32 ° C, and 80% humidity relative (RH) (32/80). 0 aging protocol for a set is also specified, with 7dRT meaning 7 days at room temperature; + 7dH2O meaning an additional 7 days immersed in water (eg, demineralized water (23 ° C)); + 7d90 ° C meaning 7 days at room temperature, followed by another 7 days immersed in water (eg, demineralized water (23 ° C)), followed by +7 days at 90 ° C (in a greenhouse with circulation of air); + 7dCata meaning 7 days at room temperature followed by an additional 7 days immersed in water (eg, demineralized water (23 ° C)), followed by 7 days at 90 ° C (e, u, the air circulating oven ), and a t-day poultice treatment. A suitable climate chamber can be used to derive the appropriate test conditions.

Table 2 shows expected data for BETAPRIME^mr 5500, which is believed to be a one-step primer composition representative of the prior art applied to float glass. It turns out that these are improved results expected using the primers here compared to single component primers in the prior art.

Table 3 shows how the variation of any coating or frit on the glass is not believed to impact the results using the compositions here.

Table 1: Tests after different opening times of primer C on float glass

<td></td><td>Time Open</td><td>Sealant</td><td>7dRT</td><td>+ 7dH2O</td><td>+ 7d90 ° C</td><td>+ 7dCata</td>

<td rowspan="4">Primer Ç</td><td>20s</td><td> 1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>20s</td><td> 2</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>20s</td><td> 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>20s</td><td> 4</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td rowspan="4">Primer Ç</td><td>3 min</td><td> 1</td><td> 5</td><td> 5</td><td>2-3b</td><td>3-4b</td>

<td>3 min</td><td> 2</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>3 min</td><td> 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>3 min</td><td> 4</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td rowspan="4">Primer Ç</td><td>7d3280</td><td> 1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>7d3280</td><td> 2</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>7d3280</td><td> 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>7d3280</td><td> 4</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td rowspan="4">Primer Ç</td><td>1 Mt RT</td><td> 1</td><td> -5^The</td><td> 5</td><td> 5</td><td> 5</td>

<td>1 Mt RT</td><td> 2</td><td>-5ai</td><td> 5</td><td> 5</td><td> 5</td>

<td>1 Mt RT</td><td> 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>1 Mt RT</td><td> 4</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td rowspan="4">Primer Ç</td><td>1 Mt 32/80</td><td> 1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>1 Mt 32/80</td><td> 2</td><td>4bi</td><td>4i</td><td>4i</td><td> 5</td>

<td>1 Mt 32/80</td><td> 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>1 Mt 32/80</td><td> 4</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td rowspan="4">Primer Ç</td><td>3 Mt 32/80</td><td> 1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>3 Mt 32/80</td><td> 2</td><td>4i</td><td> 5</td><td>-5i</td><td> 5</td>

<td>3 Mt 32/80</td><td> 3</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>3 Mt 32/80</td><td> 4</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

Table 2 A: Comparative example: BP 5500 (open time 1 month at 23 ° C, 50% RH)

<td>Sealant</td><td>3d RT</td><td>7d RT</td><td>+ 7dH2O</td><td>+ 7d90 ° C</td><td>+ 7Cata</td>

<td>BS 1759</td><td>4-5z</td><td>4-5z</td><td>4 z</td><td>2-3b</td><td>l-2b</td>

<td>BS 1842</td><td>4-5z</td><td>4-5z</td><td>4 z</td><td>2-3b</td><td>l-2b</td>

<td>BS 1841</td><td>4 z</td><td>4 z</td><td>4 z</td><td>2-3b</td><td>l-2b</td>

<td>BS 1801</td><td>2b</td><td>2b</td><td>lb</td><td>lbv</td><td>lb</td>

<td>BS NC1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BS 1845</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

Table 2 B :. Comparative example: BP 5500 (open time 2 weeks at 32 ° C, 80% RH)

<td>Sealant</td><td>3d RT</td><td>7d RT</td><td>+ 7dH2O</td><td>+ 7d90 ° C</td><td>+ 7Cata</td>

<td>BS 1759</td><td>2-3b</td><td>2-3b</td><td>2b</td><td>2b</td><td>lb</td>

<td>BS 1842</td><td>2-3b</td><td>2-3b</td><td>2b</td><td>2b</td><td>lb</td>

<td>BS 1841</td><td>2-3b</td><td>2-3b</td><td>2b</td><td>2b</td><td>lb</td>

<td>BS 1801</td><td>lb</td><td>lb</td><td>lb</td><td>lbv</td><td>lb</td>

<td>BS NC1</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td>BS 1845</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

Table 3: Primer C adhesion tests

In Different Ceramic Fries

<td>Cleaner</td><td>BC 3300</td><td colspan="4"></td>

<td>Open Time Primer</td><td>Sealant</td><td>7d RT</td><td>+ 7dH2O</td><td>+ 7d90 ° C</td><td>+ 7Cata</td>

<td>3 min</td><td>BS 1759</td><td> 5</td><td> 5</td><td> 5</td><td> -5^The</td>

<td>Open Time Primer</td><td>Sealant</td><td>7d RT</td><td>+ 7dH2O</td><td>+ 7d90 ° C</td><td>+ 7Cata</td>

<td>3 min</td><td>BS 15625</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

<td colspan="6">Nail polish 24-8337</td>

<td>Cleaner</td><td>BC 3300</td><td colspan="4"></td>

<td>Open Time Primer</td><td>Sealant</td><td>7d RT</td><td>+ 7dH2O</td><td>+ 7d90 ° Ç</td><td>+ 7Cata</td>

<td>3 min</td><td>BS 1759</td><td> 5</td><td> 5</td><td> 5</td><td> -5^The</td>

<td>3 min</td><td>BS 15625</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>

The explanations and illustrations presented here are intended to give knowledge to those skilled in the subject of the invention, its principles, and its practical application. Those skilled in the art will be able to adapt and apply the invention in its numerous forms, as it will best adapt to the requirements of a particular use. Consequently, the specific embodiments of the present invention as shown are not intended to be exhaustive or limiting of the invention. Hence, the scope of the invention should be determined not with reference to the above description, but, instead, it should be determined with reference to the attached claims, together with the full range of equivalents to which the claims are entitled. Disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. References to an acrylic or (meth) acrylic (or derived terms, such as acrylate) include methacrylics and acrylics (and corresponding derived terms). Unless stated otherwise, references to adhesive or sealant are interchangeable. Hence, the mention of an adhesive of a particular composition also covers a sealant of that composition.

Although generally disclosed here in the context of use in a one-step primer composition, the second adduct, also referred to here as an adhesion promoter, is thus not limited. This can be used as part of a primer system that includes multiple components, and can be added to any or all components. For example, the adhesion promoter may be incorporated into a urethane activating composition, a fry preparation composition, a fry primer composition, a PVC primer, a locking gasket primer, or the like, such as one or more products from The Dow Chemical Company that have been marketed under the designations U-413, U-555, U-4000, U-401, U-402, or the like.

The present teachings can be used appropriately in combination with one or both: co-pending application serial number 60 / 913,703 US patent

(filed April 24, 2007): Compositions and Methods,

Universal Primer or US Patent Application No. Serial No. 60 / 913,706 (filed April 24, 2007): Improved Primer Adhesion Promoters, Compositions and Methods, both of which are incorporated herein by reference.

Appendix 1

<td> 1</td><td>0% of</td><td>failure</td><td>cohesive</td>

<td> 2</td><td>approx.</td><td> 25%</td><td>cohesive failure</td>

<td> 3</td><td>approx.</td><td> 50%</td><td>cohesive failure</td>

<td> 4</td><td>approx.</td><td> 75%</td><td>cohesive failure</td>

<td> 5</td><td>approx.</td><td> 100%</td><td>cohesive failure</td>

a adhesive with or without primer shows delamination of the substrate b adhesive shows delamination of the primer c if cut from the substrate, some delamination in the layer separation incision in the primer and adhesive / primer or adhesive / sticky substrate f primer system dissolves the substrate surface g bubbles or primer peels from the adhesion surface near the adhesive thread h * delamination of the substrate k corrosion under the thread i bubbles in the adhesive m migration of plasticizer from the adhesive to the substrate n migration of plasticizer from the substrate to the adhesive r bubbles in the coating under the thread adhesive s bubbles in the coating close to the adhesive thread t bubbles in the coating under the adhesive thread and near the adhesive thread u delamination in the coating system v delaminate coating of the substrate w if the substrate coating is cut, it peels off slightly from the adhesive x cohesive failure near the adhesive / primer or primer / adhesive interface y reinforcement fibers stand out from the substrate z delamination at the edge

L cracks in the adhesive

T tunnels in the adhesive * = evaluation always provided with an additional number.

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