Single-component glass primer containing oxazolidine

FIELD: chemistry.

SUBSTANCE: present invention relates to a single-component primer composition for substrates made from glass and/or plastic, having setting time of at least 1 month. Said composition includes: a base primer composition including (a) an isocyanate functional prepolymer derived from the reaction of an aliphatic polyisocyanate and a polyol, and which is partially reacted with an amino group of a secondary aminosilane, wherein the aminosilane includes two or three methoxy groups bound to a silicon atom, two or three ethoxy groups bound to a silicon atom, or a combination thereof; (b) an isocyanate functional prepolymer with an isocyanate content greater than 1%, which is the reaction product of an aromatic polyisocyanate and a polyol of M_n>300; and (c) at least one solvent for the components (a) and (b); and an ingredient including an oxazolidine ring or derivative thereof; a second adduct (i) of an aromatic polyisocyanate and (ii) mercaptosilane, aminosilane or both; a film-forming polymer. The invention also describes glued structure having a glass or plastic panel, containing the said composition, a method of gluing the glass panel to the frame of a vehicle, comprising a step for applying said composition and a glued structure made using said method.

EFFECT: obtaining primer with long setting time, which exhibits excellent stability during storage, during application of which the surface does not swell.

13 cl, 4 tbl

The APPLICATION for approval of PRIORITY

This application claims the benefit of the registration date of the provisional application No. 60/913700 (registered 24 April 2007), the content of which is incorporated herein in its entirety by reference.

The technical FIELD TO WHICH the INVENTION RELATES.

The present invention relates to a primer, in particular to the primer to bind one or more sealants with a non-porous substrate, for example for bonding glass panel to the car.

The prior art TO WHICH the INVENTION RELATES.

In the field of technology related to the installation of glass, there is a need in the primer, which can be used in several conditions. One of the required assignments primer is the treatment of the glass surface to ensure a strong connection glass sealant (e.g., an adhesive). In one case, the application of adhesive or other sealant is applied after a short period of time after application of the primer. In another case, the application of adhesive or other sealant is applied after a considerable period of time. For all of these applications it is important that the primer maintains effectiveness when applied adhesive or sealant. Commonly called field the amount of time, during which the primer retains its effectiveness, its setting time. It usually refers to the time interval between application of the primer and the time that the adhesive or other sealant cannot be applied to the primer and the best way to use for gluing. Namely, if the primer cures too quickly and becomes nedlasting in order to work with it, in practical application, including the installation of glass in the vehicle, the device for installing Windows is not enough time to install and fit the glass in the frame of the vehicle. For the purposes of mounting the glass in question (in particular, for practical applications associated with the production of cars, as a rule, the best use of bonding implies that the fracture behavior of adhesive or other sealant at the primer is predominantly cohesive, and more specifically, in essence, a fully cohesive.

Examples from the literature, in which it considered applicable in this field priming materials are published patent application U.S. No. US20010041782A1, 20030100676A1, U.S. patents№№ 5010202, 4874805, 4396681, 4367313, 6875470, Eurasian patent № 1217049A1, the publication of patent applications Japan No. JP2003-336008, JP2003-128988, JP2002-309182 and JP2002-309163, all the C are represented in this application by reference. You can apply two-component primer and it is known that many of them manifest as signs of a short setting time, and evidence of prolonged setting time. However, as a rule, for two-component primers required additional stages associated with work operations and processing.

In U.S. patent 6133398 described one-component adhesive composition comprising a polyurethane prepolymer, which can be used a compound containing at least one oxazolidinone group.

BRIEF description of the INVENTION

In General, the present invention is directed to obtaining a one-component primer composition with a long setting time, which includes basic primer composition (preferably dispergirovannoyj or dissolved in a volatile solvent)containing (a) isocyanate functional prepolymer ("prepolymer (a)"), which is produced by the interaction of aliphatic MDI with a polyol and which is partially reacted with the secondary amine groups of aminosilane where aminosilane contains two or three metoxygroup associated with the silicon atom, two or three ethoxypropan associated with the silicon atom, or a combination thereof, (b) isocyanate functional prepolymer ("the prepolymer (b)") with the contents Izolan is the shaft groups more than about 1%, which is a reaction product of aromatic MDI and polyol with M_n>300 (e.g., the product of the interaction of aromatic diisocyanate with poliferation), and also ingredient containing oxazolidinone ring or its derivative, or its analogue, where the primer has a setting time constituting at least about 1 week, more preferably at least about 1 month, and even more desirable, at least about 3 months or more.

This primer composition may also contain one compound from among (1) the first addend (i) aliphatic isocyanate and (ii) mercaptoethane, aminosilane (for example, secondary aminosilane) or both (in particular, for example, silane with two or three methoxy and/or ethoxypropane associated with the silicon atom), or (2) of the adhesion promoter, such as one that includes the second adduct (i) aromatic MDI and (ii) mercaptoethane, aminosilane (for example, secondary aminosilane) or both (in particular, for example the silane with two or three methoxy and/or ethoxypropane associated with the silicon atom), or a combination of both. For example, for use in the adhesion promoter is possible aromatic polyisocyanate contains thiophosphate, phosphate, tiofosfonovoi group, or any combination. Specifically, it can is be a Tris(isocyanatophenyl)thiophosphate.

These compositions may also include a dye or pigment (e.g., black carbon). Ingredients dispersed and/or dissolved in a suitable solvent and, if desired, may include a suitable catalyst.

Ingredient containing oxazolidinone ring or its derivative, or its analog, includes isoxazolidine and is contained in an amount of about 2 to 8 wt.%. the whole composition. For example, it may include carbamino acid, 1,6-hexanediol bis-, bis(2-(2-(1-methylethyl)-3-oxazolidinyl)ethyl) ether and contained in the final composition in an amount of about 4 to 6% wt. the whole composition.

It is possible that in this composition will use the second adduct in an amount in the range from approximately 0 to 20% wt. the whole composition, for example from about 2 to 10% wt. the whole composition or, more specifically, from about 4% to 6% wt. the whole composition. This composition can also contain one connection from the number forms (meth)acrylate film compound present in an amount of about less than 10% wt. the whole composition, of a filler, a stabilizer, such as diethylmalonate, or acids, such as phosphoric acid, or any combination.

The present invention also considered ways of using the compositions described herein, which include stage nanese the Oia priming composition on the first substrate, wait at least for 20 seconds, 1 minute, 3 minutes or more, applying adhesive to the primer composition and bonding the second substrate to the adhesive substance. For example, one method of bonding glass pane to the design of the vehicle may include a stage (a) primer according to this invention, essentially around the perimeter of one side of the glass pane (b) imposing on the primer composition of the strips of adhesive and (c) install the glass panel through the implementation of contact of adhesive with the design of the vehicle that defines a hole for installation of the glass panel. Stage (a) and (b) can be separated by a period of time more than 20 seconds and less than 3 months at room temperature, period of time more than 1 day at room temperature, or even a period of time longer than 1 week or even 1 month at room temperature. The present invention also considered the resulting bonded structure or other structures that include described herein primer.

DETAILED description of the INVENTION

In the form in which they are used in this document, all of the weight parts are defined relative to 100 parts described composition, unless otherwise specified (for example, weight soo is wearing). If the resulting composition this means that mass is defined relative to 100 parts of the resulting final composition. It should be understood that it is possible to use larger or smaller amounts described in this document. Typically, mutual shares described ingredients will remain the same. Thus, for example, if the idea of the invention provides 30 parts of component a and 10 parts of component B, the skilled in the art specialist will take into account the fact that this idea also includes the idea of using the component a and component B in the mutual ratio of 3:1.

In one aspect of the present invention is aimed at obtaining basic primer composition containing (a) isocyanate functional prepolymer ("prepolymer (a)"), which is produced by the interaction of aliphatic MDI with a polyol and at least partially reacted with the secondary amine groups of aminosilane where aminosilane contains two or three metoxygroup associated with the silicon atom, two or three ethoxypropan associated with the silicon atom, or a combination thereof, (b) isocyanate functional prepolymer ("prepolymer (b)") with a content of isocyanate groups of more than about 1%and (c)at least one solvent for (a) and (b), and the ingredient is aderrasi oxazolidinone ring or its derivative, or equivalent.

In another aspect the present invention provides an improved one-component primer composition with a long setting time, which includes a basic primer composition ingredient containing oxazolidinone ring or its derivative, or its analogue, the first adduct (i) aliphatic isocyanate and (ii) mercaptoethane, aminosilane (for example, secondary aminosilane) or both (in particular, for example, silane with two or three methoxy and/or ethoxypropane associated with the silicon atom), and an adhesion promoter containing the second adduct (i) an aromatic isocyanate and (ii) mercaptoethane, aminosilane (for example, secondary aminosilane) or both (in particular, for example, silane with two or three methoxy and/or ethoxypropane associated with the silicon atom). Preferably, the composition additionally contains a dye or pigment (e.g. carbon black) and a solvent. In one approach, the above composition of the substances used to obtain basic primer composition comprising at least one isocyanate of the prepolymer, which contains silicon (for example, which at least partially cililitan amidofunctional the silane).

Ingredient containing oxazolidinone ring or its derivative, or its counterpart, with whom according to the present invention can be any suitable ingredient, and preferably, so he could be the ingredient which hydrolyzes when exposed to moisture with the formation of reactive hydroxyl and amidofunctional groups to interact with the audience isocyanates. In one specific example, it includes isoxazolidine. However, it is possible that it includes isoxazolidine. You can also use derivatives or analogs of oxazolidines, such as those that contain oxazolidinone group, oxazolidinediones group, or a combination of both. In the private aspect of the present invention the preferred azole is a connection-based isoxazolidine with functionality of at least 2, and more preferably a functionality of 4. It is desirable that the ingredient had the ignition temperature greater than about 50°C., for example approximately 60 or even 75°C or higher, and, in addition, could have NH/OH equivalent weight of approximately 80 or more. For example, it is possible that ingredient represents an aliphatic polyominoes on the basis of reabilitation. Examples of compounds containing oxazolidone is karamanova acid, 1,6-hexanediol bis-, bis(2-(2-(1-methylethyl)-3-oxazolidinyl)ethyl) ether. Examples of commercially available ingredients suitable for this invention are Incozol 4 or Incozol LV, comprises the controlled company Industrial Copolymers Ltd., or Hardener OZ offered by Bayer MaterialScience. Ingredient containing oxazolidinone ring or its derivative, or its equivalent, as a rule, is contained in an amount of about 1 to 10% wt. the whole composition, preferably from about 2 to 8 wt.%. the whole composition, and more preferably from about 4% to 6% wt. the whole composition. If desired, ingredient containing oxazolidinone ring or its derivative, or its equivalent, provide as having coated or included in the capsule particles or droplets, for example, according to the idea of U.S. patent No. 6133398 (represented by reference).

Isocyanate functional prepolymer (b) with a content of isocyanate groups of more than about 1%, generally is a reaction product of a polyol with a functionality of approximately greater than 2, and the molecular mass (M_n)greater than about 300, and isocyanate, preferably an aromatic MDI. In one aspect of the preferred isocyanate is a diisocyanate, such as the one that has a functionality of at least 2 (e.g., trifunctionally) diisocyanate. For example, the diisocyanate may be an aromatic diisocyanate, such as the choice of the number of TDI, MDI, or combinations thereof. Specific preferred diisocyanate includes MDI or its prepolymer, nab is emer, one that contains approximately 97% of 4,4'-diphenylmethanediisocyanate and 3% of 2,4'-diphenylmethanediisocyanate. A commercially available example of one such isocyanate is Isonate ® M125 MDI offered by the company The Dow Chemical Company. Although you can choose other polyols, particularly preferred polyol is a triol, and especially one that has a hydroxyl number of at least about 200. An example of one such polyol is a polyol, offered by the company The Dow Chemical Company under the name VORANOL™ CP260.

The first adduct is typically a product of the interaction of (i) aliphatic isocyanate (ii) mercaptoethanol, aminosilanes (for example, secondary aminosilanes) or both (in particular, for example, a silane with two or three methoxy and/or ethoxypropane associated with the silicon atom). Specific preferred diisocyanate is aliphatic isocyanates, and particularly trifunctionally aliphatic polyisocyanate, for example, on the basis of hexamethylenediisocyanate (HDI) (an example of which is a product commercially available under the trade name Desmodur® N100 from Bayer MaterialScience). Although you can choose other mercaptoethane, particularly preferred is mercaptopropionylglycine (such as that commercially available as ynasilan™ MTMO from the company Degussa, or as Silquest™ A-189 from the company General Electric). It is desirable that the molecular weight of mercaptoethane does not exceed about 2000, preferably does not exceed about 900, and more preferably does not exceed about 500 (e.g., approximately 200 or even about 80). The third prepolymer, if present, is typically present in amount in the range from approximately 0 to 20% wt. the whole composition, preferably about 1 to 10% wt. the whole composition, and more preferably from about 2 to 4% wt. the whole composition.

The second adduct usually performs the function of an adhesion promoter, which, as a rule, is a product of the interaction organofunctional silane with isocyanate. More specifically, as will be discussed, as adhesion promoter use an adhesion promoter, which contains at least one aromatic polyisocyanate, which more specifically includes phosphorus.

In one embodiment, one component of the second adduct may include aminosilane, and more specifically secondary aminosilane. A preferred silane contains at least two silyl groups with three methoxypropane associated with each of the silicon atoms, steric hindering secondary amino group, or any combination thereof. An example of one such commercially available aminosilane is bis(trimethoxysilyl who yl)amine, such as Silquest A-1170 from GE Advanced Materials-Silicones. Additional information suitable for use in this invention the substances constituting the silanes represented in the incorporated by reference U.S. patent No. 4374237. Other examples of silanes are without restrictions (individually or in combination with bis(triethoxysilylpropyl)amine) silanes with hydroxyl functional groups, mercaptamine functional groups or both parties, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, 3-mercaptopropionylglycine, 3-mercaptopropionate, 3-mercaptopropionylglycine, (N-cyclohexylamine)metildigoxin, (N-cyclohexylamine)triethoxysilane, (N-phenyliminomethyl)metaldimension, (N-phenyliminomethyl)trimethoxysilane, N-ethylenediaminetetramethylene, 4-amino-3,3-dimethylethoxysilane or any combination thereof.

The second adduct contains as one of its components an aromatic isocyanate, and in particular, trifunctionally isocyanate. In a particularly preferred embodiment, it contains at least one isocyanate containing phosphorus. P is the iMER one isocyanate represented by the following formula 1, described mainly in U.S. patent No. 6974500 presented as links:

Formula 1

One possible isocyanate is a Tris(para-isocyanato)tiffopen. Particularly preferred isocyanate is thiophosphate with the isocyanate group, such as a solution of Tris(para-isocyanatophenyl)thiophosphate in ethyl acetate, sold under the trademark DESMODUR RFE and commercially available from Bayer Corporation, Pittsburgh, PA. Other examples of isocyanates (which can be used individually or in combination with Tris(para-isocyanatophenyl)thiophosphate) include trifunctional isocyanates, which may be aromatic or aliphatic (e.g., aliphatic polyisocyanate based on HDI and, if possible, with a content of isocyanate groups of from about 15 to 25 percent). Examples of suitable trifunctional isocyanates include those commercially available under the brand names Desmodur N-100, Desmodur N 3300 or Tolonate HDT.

Typically, the second adduct is obtained by mixing the silane with the isocyanate, in particular in an amount of about 1 mol of isocyanate with about 1 to 3 moles of silane (for example, aminosilane, mercaptoethane or combinations thereof), and more specifically, about one mole of the isocyanate with about 2 or 3 moles of silane (for example, aminoil is a, mercaptoethane or combinations thereof).

One particular approach to obtaining the second adduct is at least a partial interaction of the aromatic polyisocyanate with a functionality of approximately greater than 2, with silane (for example, aminosilanes (such as secondary amidofunctional silane), mercaptoethanol or their combination), where the silane contains a number of alkoxygroup associated with the silicon atom (for example, two or three metoxygroup associated with the silicon atom, two or three ethoxypropan associated with an atom of silicon, a combination or similar).

Typically, the compositions according to this invention based on the combination of ingredients with a basic primer that includes at least a first prepolymer (a)obtained by the interaction of at least one MDI, at least one polyol, and in particular, which contains free isocyanate. In a more specific aspect of the main primer contains isocyanate functional prepolymer, which is obtained by the interaction of aliphatic MDI with a polyol. In one very particular embodiment, a basic primer contains isocyanate functional prepolymer, which is obtained by the interaction of aliphatic MDI with polio the om and at least partially reacted with the amine groups of the silane, and in particular aminosilane (for example, secondary aminosilane), where aminosilane contains a number of alkoxygroup associated with the silicon atom (for example, two or three metoxygroup associated with the silicon atom, two or three ethoxypropan associated with an atom of silicon, a combination or similar), and the second prepolymer (b), described herein, and preferably at least one solvent for the two prepolymers. Examples of commercially available primers that can be used according to the idea of the present invention, without limiting cover Betaprime™ 5500.

Without intending to be bound by theory, believe that compositions according to this invention determine the best application of specific molecular structure in which at least a portion of the molecule contains silicon (for example, it Sieniawa), and the portion of the molecule contains functionality such as isocyanate functional group which is able to communicate with the main primer, for example, through the formation of a molecular mesh between the primary coating and a combination of aliphatic isocyanate prepolymer with an aromatic isocyanate of the prepolymer. Such prepolymers can be a part of the core primer to the notizie.

Isocyanates suitable for the present invention, it is possible to choose from a number of diisocyanates, triisocyanate or any combination. Suitable isocyanates can include aliphatic, cycloaliphatic, analiticheskii, heterocyclic, aromatic isocyanate, or any combination of them. Preferred examples may include isocyanates, selected from among hexamethylenediisocyanate (HDI), isophoronediisocyanate (IPDI), methylenediphenyl-4,4'-diisocyanate (MDI) or any combination, and more preferred isocyanate selected from among isophorondiisocyanate (IPDI), methylenediphenyl-4,4'-diisocyanate (MDI), colordistance (TDI) or any combination. As noted, also consider the polymeric derivatives of any of the described in this document isocyanates.

Preferably polyisocyanates used had an average isocyanate functionality, component, at least roughly 2.0 and an equivalent weight equal to at least about 80. Preferably, the isocyanate functionality MDI was at least roughly 2.0, more preferably at least about 2.2, and most preferably at least about 2.4, and preferably it does not exceed about 4.0, more preferably does not exceed about 3.5, and most preferably n is exceeded approximately 3.0V. You can also use the polyisocyanates of higher functionality, however, this can cause excessive binding and lead to the formation of adhesive, which is too viscous to work with it and is easy to apply, and may be the reason that the cured primer becomes too fragile. Preferably, the equivalent weight of MDI was, at least about 100, more preferably at least about 110, and most preferably at least about 120, and preferably to no more than about 300, more preferably does not exceed about 250, and most preferably does not exceed about 200.

Examples of compounds able to interact with isocyanate groups, can be an organic compound at least two groups capable of interaction with isocyanate groups, for example a compound containing a group including an active hydrogen atom, or immunofunctional connection. For the purposes of the present invention under the group containing active hydrogen atom"is meant a group containing a hydrogen atom which, because of their position in the molecule exhibits significant activity according to the test of Caravanette (Zerewitnoff), described by Volera (Wohler)in publicat and The Journal of the American Chemical Society, Vol. 49, p. 3181 (1927). Examples of such groups containing an active hydrogen atom are-COOH, -OH, -NH₂, -NH-, -CONH₂, -SH, and-CONH-. Preferred compounds containing an active hydrogen atom are polyols, polyamine, polymercaptan and polyacid.

Suitable polyols may include, for example, a simple polyether polyols complex polyether polyols polyalkyleneglycols, hydroxycobalamin simple polythioether, polymer polyols, and mixtures thereof. Simple polyether polyols may constitute, for example, one or more diols, triolo or tetraol based polyoxyethylenated, polyoxypropylene, polyoxyethylenated and/or polytetramethylene simple ether. As a rule, simple polyether polyols produced by polymerization of alkalisation in the presence containing active hydrogen compound initiator. However, the most preferred are acceleratedly polyols with terminal reactive groups.

Preferably, the compound capable of interacting with isocyanate groups possessed a functionality equal to at least about 1.5, more preferably at least about 1.8, and most preferably at least approximately to 2.0, and preferably to no more than about 4.0, more preferably about 3.5, and is, most preferably about a 3.0. Preferably, the equivalent weight of a compound capable of interacting with isocyanate groups, comprised of at least about 200, more preferably at least about 500, and most preferably at least about 1000, and preferably to no more than about 5000, more preferably about 3000, and most preferably about 2500. In one particular example uses polyol as one compound capable of interacting with isocyanate groups, which has an equivalent weight from about 100 to 1500, and more preferably from about 300 to 1000.

Isocyanate and a compound capable of interacting with isocyanate groups can react in the presence of a suitable catalyst. The catalysts which are used according to this invention, may include, for example, complex metal, such as a compound of divalent or tetravalent tin. Examples are containing divalent tin salt of carboxylic acid (e.g., octoate tin, tin oleate, tin acetate and tin laurate)oxide triamcinolone, in primary forms dialkylamino (for example, dilaurate dibutylamine, diacetate dibutylamine, diacetate titilola and diacetate Vexillology), dihalogenide dialkylamino or oxide dialkylamino, such as oxide, di-2-ethylhexylamine or ICSID dactylology, tertiary amine or mercaptide tin. You can also use other catalysts. For example, catalysts, representing tertiary amines include trialkylamine (for example, trimethylamine, triethylamine), heterocyclic amines, such as N-alkylphosphine (for example, N-methylmorpholine, N-ethylmorpholine, dimethylaminomethylene ether and so on), 1,4-dimethylpiperazine, triethylenediamine etc. as catalysts can also be used aliphatic polyamine, such as N,N,N',N'-tetramethyl-1,3-butanediamine. One particularly preferred catalyst is a compound dibutylamine, and more specifically, it represents dilaurate dibutylamine. However, in a particular embodiment, the used catalyst is one or more catalysts selected from among metal salts such as tin carboxylates, organosilicon titanates, alkylsilane, bismuth carboxylates, or a simple ester, such as demoralization ether (DMDEE), or alkyl substituted demoralization esters. Among the preferred catalysts are demoralization ether and di(2-(3,5-dimethylmorpholine)ethyl ester. In practice, such catalysts (individually or in combination) is preferably used in an amount of about 1% wt. the entire composition, more specifically about m what it is 0.8% wt. the whole composition (for example, from about 0.1 to 0.8%, and preferably from about 0.3 to 0.5%). In one aspect of the present invention is applied, the catalyst does not contain bismuth.

Isocyanate and a compound capable of interacting with the isocyanate can also react in the presence of a suitable silane (for example, aminosilane) for the introduction of silicon into the main wash.

The resulting compositions according to this invention can include one or more components such as a solvent, stabilizer, foaming agent, dye or pigment (e.g. carbon black, for example, Raven 420), a filler, a substance that protects against exposure to ultraviolet radiation, or any combination.

The component representing the solvent primer composition is volatile and preferably, it was a solvent which dissolves the polymer at a temperature in the range of from about -10°C. to 100°C., more preferably from about 0°C to 40°C. Preferably, the solvent does not contain water to prevent premature interaction of the isocyanate groups with water. Examples of such solvents include xylene, ethylbenzene, toluene, ethyl acetate, propyl, butyl acetate, butanol, propanol, isopropanol, ethanol, acetone, methyl ethyl ketone, butoxy is, 2-butoxyethanol, 3-methoxybutyl, NMP, n-heptane, kerosene or any combination thereof and preferably are butoxy, methyl ethyl ketone, ethyl acetate or a mixture thereof. The solvent will contain the balance of any resulting or intermediate compositions, and preferably used in amounts of at least about 40%, more preferably at least about 50%, and most preferably at least about 60%, and preferably not exceeding about 90%, more preferably not greater than about 85%, and most preferably not greater than about 80% wt. all primer composition.

In one embodiment, in addition, consider the possible use of the polymer, forming the (meth)acrylic film. Suitable film-forming polymers include polyacrylate polymers, epoxy resins, representing polyesters, polymers (polymers of carboxylic acid and glycol), representing polyesters, copolymers, vinyl polymers, chlorinated rubber, ethylenevinylacetate copolymers, polyacrylate copolymers or any combination. Preferably, the film-forming polymer dissolved in a particular solvent to be used in this composition. In one preferred variant is NTE implementation is desirable, to the film-forming polymer had a molecular weight greater than about 3000, and more preferably greater than about 5000. It is desirable that the film-forming polymer had a molecular weight of about less than 50,000, and more preferably less than approximately 30000. One particular film-forming polymer is a poly(meth)acrylate polymer. An example of one particularly preferred film-forming polymer is an acrylic copolymer with hydroxyquinolines weight of approximately 2000, commercially available as Paraloid™ B48N from the company Rohm and Haas Company in the form of a solution. Film-forming polymer may be present in any suitable amount. For example, it may be present in an amount of about 0.1 parts, about 1 parts, or even about 5 parts or more by weight primer composition. In the case of film-forming polymer, it is preferable that the concentration was approximately less than 10 parts by weight of the entire composition, and more preferably less than 5 parts by weight of the entire composition, and more preferably less than 2 parts (for example, about 0.5 parts) by weight of the entire composition.

In the compositions according to this invention it is possible to enter the fillers commonly used for polymers and polyurethane primers. Suitable fillers can be selected from : the titanium dioxide, calcium carbonate, silicon dioxide with a machined surface, mica, colloidal silicon dioxide, talc or any combination. In the case of using the filler concentration, as a rule, is less than approximately 40 wt.%. the whole composition, and more specifically is about 5 to 20% wt. the whole composition, for example from about 7 to 15 wt.%. the whole composition.

You can also use other components, such as (without limitation) the catalyst, initiator, curing agent, light, giving the refractory properties of the additive, plasticizer, thixotrop or any combination. Examples of additives without limitation presented in U.S. patent No. 6133398 (represented by reference).

One particularly preferred composition includes a basic primer composition and ingredient containing oxazolidinone ring or its derivative, or its equivalent, and, in addition, can contain a stabilizer (for example, diethylmalonate), acid (e.g. phosphoric acid) or both of these compounds.

Further, as an example, describes the concentration of the components of the primer composition according to this invention. For example, a basic primer may be in the amount of from about 20 to 90 wt.%, and more preferably from about 30 to 60 wt.% (for example, from about 40 is about 45 wt.%). The first adduct, if present, is contained in an amount of about 20 wt.%, and more preferably about 10 wt.% (for example, from about 2 to 4 wt.%). The second adduct, if present, is contained in an amount of about 20 wt.%, and more preferably from about 2 to 10 wt.% (for example, from about 4 to 6 wt.%). Isocyanate functional prepolymer with a content of isocyanate groups of more than about 1%, if present, is contained in an amount of about 50 wt.%, and more preferably from about 5 to 30 wt.% (for example, about 15 to 20 wt.%). One specific composition may also include a catalyst (for example, DMDEE) in an amount up to about 0.8 wt.%, more preferably from about 0.1 to 0.5 wt.%, and more preferably from about 0.13 to 0.3 wt.%. In the case of practical applications, which use pigment or dye (e.g., black carbon), it can be used in amounts up to about 40 wt.%, more preferably from about 5 to 20 wt.%, and more preferably from about 7 to 15 wt.%. This composition can also contain from about 0.1 to 0.5 wt.% diethylmalonate (for example, about 0.25 per cent) and from about 0.01 to 0.05 wt.% phosphoric acid (for example, about 0.03 wt.%).

Skilled in the art specialist know how to get the components described in this invention, See, in General, U.S. patent No. 6133398 (represented as links). Typically, compositions and their components, the reaction product can be obtained in any suitable way, such as polymerization in bulk and polymerization in solution. Stages of the reaction, and preferably stage or stages of mixing all components with one or more of the ingredients described in this invention is carried out in the absence of moisture, preferably in an inert atmosphere such as nitrogen atmosphere, to prevent crosslinking isocyanate groups under the influence of atmospheric moisture.

Primer compositions according to this invention can be used in any of a number of practical applications. One particular approach is to apply using disclosed in the art methods primer composition (for example, in the form of a one-component composition) on a substrate for use in the installation of windshields, rear lights, side Windows, doors, structural Windows, skylights, viewing openings, door openings, the indicator elements, diffusers vehicles or other. Another useful practical application is in the field of printing on labels, packaging, packaging containers (such as bottles for beverages or other. The preferred application of C is enabled to use the primer compositions according to the invention for the manufacture, essentially transparent panel designs. Design according to this invention can be adapted for the purposes of temporary or permanent mounting to the base part. These structures can be adapted for opening, closing or other motion, for example, by sliding, by means of rotation by means of a hinged joint, by means of rotation around the axis, by means of folding or any combination. These structures, therefore, can be used for one or more practical applications, such as rear lights, side Windows, skylights, structural Windows, skylights, inspection openings, doorways, indicator elements of motor vehicles or other. Compositions and methods according to this invention are also particularly useful when used in conjunction with pre-applied adhesive compositions.

Usually the substrate is essentially flat or have a certain form, for example, to define a curved surface. The substrate, typically a panel that is transparent, at least one surface, and in particular on both opposite surfaces, at least 25% of the surface area, and more specifically, at least the greater part of the surface (for example, m is Nisha least approximately 60%, 75% or even 90% of surface area). The substrate according to this invention, as a rule, are made essentially of amorphous substances, and specifically amorphous ceramics (such as glass), plastic or combinations thereof. Examples of suitable materials for substrates comprise without limitation poly(meth)acrylates, polycarbonates, vinyls (e.g., PVC), polyesters (for example, oriented polyesters, polyimides, polyolefins, polyamides, glass, any combination (for example, laminated glass) or the like. In a particular example, the substrate include or even consist mainly of substances selected from among glass, poly(meth)acrylates, polycarbonates or any combination. The substrate may have a laminated layer, tint or any combination. The substrate can also be a cure in the form of molded plastic. Design that includes part of the cure in the form of molded plastic that cover shell panel, such as the essentially transparent panel can be glued according to the ideas of this invention. An example of one possible approach to the production of coated panels is disclosed in patent application U.S. ser., No. 60/870643 (entitled “ENCAPSULATED PANEL ASSEMBLIES AND METHODS FOR MAKING SAME”; incorporated by reference). Compositions according to wannamoisett can also be used for fastening the surface of the structure of that part of the frame of the vehicle, where glass paste.

Although some applications may require coating the substrate surface covering composition according to this invention, essentially entirely, usually covering compositions are applied to the substrate selectively according to a predetermined pattern (for example, essentially along the edge area of the substrate about the perimeter of the substrate or otherwise). For example, one approach is to apply the coating from the edge of the substrate inward toward the Central part of a width of approximately 2, 5, 8 or even 12 cm or more. It is not excluded that the covering composition can be applied to delineate one or more lines, curves, dots, or other geometric configurations, including areas with constant or varying width, height, length, or other dimension.

You can use any of the variety disclosed in the art templates. The primer composition can be applied onto a substrate (e.g. glass or with a plastic coating), applying any disclosed in the art methods such as drawing with a brush, roller, by spraying on the surface, using inkjet printing, screen printing and the like. It can be applied using disclosed in the art robot the technical application of the device (for example, one that has at least 2 degrees of freedom). After applying the primer composition to the substrate for her to create the conditions under which polymerization occurs.

The substrate according to this invention typically include at least one surface, on which is applied the composition. If desired, the surface can be treated to improve the strength of the connection cover to the substrate, for example, by using primers, flame spraying, processing, corona discharge, plasma processing, or some other surface treatments. However, in one specific example, the outer surface is essentially not subjected to any processing. Accordingly, when applying the covering composition is in direct contact with the substrate, and in particular essentially in the absence of any intermediate boundary layer. Goes without saying that after application of the composition to the substrate is also possible to apply an additional layer (e.g., silicone, acrylic polymer, polyurethane or other to create a protective top layer) over part or the entire surface of either the substrate or the composition or compositions, and substrates. It is also possible that the covering composition according to this invention can be applied on top, bottom, and/or near his summe is zi inorganic or organic Frits (for example, Frit of the type specified are simultaneously pending application ser.№ 11/472119 registered 20 June 2006 (priority application 60/692318, recorded June 20, 2005)according Bikeracer with co-authors (Baikerikar et al.) (incorporated by reference).

In practice, the compositions according to this invention generally have a thickness of about 250 microns or more. Often it is less than about 150 microns, less than approximately 100 microns or even less than approximately 50 microns (e.g., about 10 to 30 microns or less).

Examples of suitable adhesives or sealants for use in combination with the primer compositions of the present invention encompass, without limitation single-component or two-component urethane composition, which, in turn, can be cured when exposed to moisture. Especially preferred urethanes are urethanes based on MDI, HMDI or combinations thereof. Examples of commercially available adhesives without restrictions include those available from the company The Dow Chemical Company under the name BETASEAL™, such as one or more of those that have brand№№ 1759, 1841, 1843, 1965, 2002 or 2002 LVRP. Other suitable commercial examples without limiting cover those available from the company The Dow Chemical Company under the name BETASEAL™ (for example, stamp number is 15-625, 15-685, 15-845 or similar).

This invention also considers the sets, which include adhesive or sealant composition, and one or more primer compositions. For example, such set may include one or more primer compositions according to the present invention with an adhesive or sealant composition (e.g., one-component or two-component urethane urethane adhesive) or without it. It may also include one or more cleaners, devices for coating, adhesive tapes, tools, or any combination thereof. Compositions according to this invention can be provided in the cartridge, package of thin film or as a cartridge and a pack of thin films.

Compositions according to this invention provides, in a General sense, hard and abrasion-resistant coating. In addition, expect that these compositions will exhibit different behavior with respect to adhesion and resistance to weathering. Also expect that the resulting priming materials, freshly prepared according to the ideas of the present invention have good stability during storage.

Compositions according to this invention are also useful for priming the substrate, the cat is the ROI then applied adhesive or other sealant. Accordingly, in one aspect, consider the contact of the substrate with the compositions according to this invention. More specifically, the compositions according to the invention are suitable for use in the methods used for fixing the glass panel to the vehicle structure, such as a vehicle, which includes the stages of (a) applying a primer composition according to the invention (for example, using any suitable unveiled in the art method, such as application of a swab, brush, spray, dipping, rubbing, or otherwise), essentially around the perimeter of one side glass panel (for example, Windows), (b) applying on top of the primer composition strips of adhesive and (c) install the glass panel by contact of sealant (e.g., adhesives) with the design of the vehicle that defines a hole in which to place the glass panel, and providing the gluing substance and the primer composition of the possibility of curing. Primer according to this invention is designed for application to a substrate or to another contact with the substrate, and then coating with a sealant (e.g., an adhesive). Substrates that can be used to cover non-porous substrates such as glass (for example, sheet glass, glass Frit, glass coated, tinted glass, reflective glass, tempered glass, annealed glass, or any combination). You can use any one of a number of other substrates, such as enamel, the cured polyurethane coated glass shell materials that are applied using electricity colorful coating, zinc coating, aluminium, steel, paint, plastic, organic glass sheets with a hard coating, or any combination. This composition can be applied to the substrate using any suitable method. Before applying the composition to the substrate can be subjected to a stage or stages of cleaning, drying, or to carry out other surface preparation for application of primer. You can use any of a number of adhesives or other sealants.

The present invention allows to divide the above stage (a) and (b) the period of time that is longer than 20 seconds, accounting for approximately 1 year (for example, up to about 3 or even 6 months) at room temperature. More specifically, one method according to the present invention assumes that stage (b) is carried out for at least one minute, one hour, one day, one week or even one month after carrying out stage (a). Stage (b) can also be carried out within the one minute to three months after stage (a) or from one hour to one month after stage (a). The amount of time between stages (a) and (b) does not have a significant influence exerted by the adhesion properties of the primer according to this invention, and the resulting connection is still able to withstand at least 500, 1000 or even 2000 hours of accelerated weathering device that simulates natural sunlight (for example, exposure to a xenon arc light source, such as the one used during the test using the apparatus for testing the resistance of materials to the effects of light and atmospheric conditions ("WOM") according to SAE J1885, ASTM D2565-99, SAE J1960 or other appropriate standard). In case of such testing apparatus for testing the resistance of materials to the effects of light and atmospheric conditions, one approach is to provide glass substrates with black enamel on one side. The primer according to this invention is applied to the enamel and sealant is applied over the primer. Then the substrates are glued together and incubated (e.g., within 7 days) for curing the sealant.

It should, furthermore, be understood that many functional ingredients or stages can be combined into a single(th) ingredient or stage either function or structure of a single(what about) the stage or ingredient can be divided into a number of stages or ingredients. For example, it should be understood that the above considers the use of multiple individual prepolymers or other ingredients. The ingredients can be connected simultaneously, sequentially or a combination of simultaneous and serial connections. Thus, it is possible to use a combination of two or more prepolymers or other ingredients, for example, by connecting the reaction products of two or more ingredients after the interaction, leading to the formation of a reaction product, or through the use of a single ingredient, which has the functional properties of several of the described ingredients. Alternatively, the functions performed by one of the ingredients can be divided among other ingredients, or by other ingredients. The present invention considers all of these combinations. Unless otherwise specified, does not imply that the concentration and quantity of the various elements described in this document is limited to the invention and others are possible. In addition, despite the fact that element according to the present invention can be described in the context of only one of the illustrated embodiments, such an element can be combined with one or more elements of the other options on the westline for any given practical application. From the foregoing it should also be understood that the manufacturer original parts according to this invention and their operation is also of the methods according to the present invention.

Do not imply that percentage according to this invention are restrictive. Describes the number can be converted into a proportional number of some or all of the ingredients and a similar number also consider. For example, if the composition comprises 10 wt.% And, 40 wt.% B and 50 wt.% In, skilled in the art specialist realizes that assume that a and B are present in a proportion of 1:4 (e.g. 1 part a and 4 B). Alternatively, B and C are in the ratio 4:5 (for example, 4 B and 5 parts).

The following examples, which do not imply that they are limiting, illustrate compositions according to the present invention and certain preferred embodiments of the invention. The values given are approximate and should not be construed as limiting the invention. Possible variation of the process parameters. In addition, given the expected results can also show deviations (e.g., approximately +/- 10% of these values). In these examples, RA test the various polyurethane sealants, commercially available as grade BETASEAL™ from the company The Dow Chemical Company. Varieties BETASEAL™ 1759, 1841, NC-1 and 1843 indicated in table 1 as a sealant 1, 2, 3, and 4, respectively. In General, in the case katoplastik cyclic tests, the samples are placed directly on the 7 days a camera for climatic tests at 70°C, relative humidity of 100%, or Packed in cotton wool, moistened with sufficient water and sealed in a plastic bag in order to stand in an oven at 70°C for 7 days. Then the samples are placed in the freezer for 16 hours at -20°C, after which the sample allow to remain at room temperature for 2 hours. The cycle can be repeated many times, after which the samples extracted from the package and tested for adhesive strength at a quick cut. Preferably, there was no swelling of the surface, and the destruction of the layer of sealant was cohesive. In the case of tests, the results of which are shown in the following tables, used only 1 metaplasticity cycle.

Primer labeled primer To get the mixture in the following proportions (in parts by weight) sample basic primer, oxazolidinone compound and the adduct, as well as other components:

The primer (C) of the above example is applied to the substrate, covered with traditional enamel (usually used in the United States in the production of motor vehicles), then covered with enamel substrate is cleaned with a cleaner Dow Betaclean™ 3300 BC. Sealant Sealant Dow Betaseal™ 1759 put exactly 3 minutes after applying the primer. This design is subjected to aging under test their resistance to the effects of light and atmospheric conditions according to the standard SAE J 1960 by UV radiation over 2000 hours in the apparatus C65 manufactured by Atlas. When tested for peel (test quick cut) as described below destruction achieved in the bonding primer sealer is a fully cohesive mode.

Primer (C) of the above example demonstrates excellent stability during storage, as it's only a slight increase in viscosity over time. For example, the measurement of viscosity (4 mm Cup DIN 53211) leads to the following approximate values.

The results presented in the tables below, get, applying the test for exfoliation (test quick cut). Utverzhdennuyu and aged strip (approximately 4 to 6 cm and a length of approximately 100 to 150 cm) prepare the chin from the substrate at an angle of about 90° with a minimum 3 see Any remaining strip cut to the substrate under at the scrap of about 90° relative to the direction of the strips at intervals of approximately 1 cm in length. Using the code table given in Annex 1, evaluate and classify the nature of the destruction observed after detachment on the surface of the destruction or damage. The area of any surface area with cohesive destruction is defined as the percentage of tested surface area and evaluate a number from 1 to 5. Then expect the rest of the area depending on the characters of destruction that are listed in the code table in Appendix 1, and denote the corresponding code letters. The results recorded using the following format: "number letter letter letter", and the number means the % of the area of cohesive fracture, and the other letters mean observed species destruction in the order of waning. For example, write "2abv" means cohesive failure at 25% of the surface area, and the remaining surface area is characterized by the detachment which largely explains the code letter "a"than the code letter "b", and more code letter "b"than the code letter "v"and the "entry 2a/b" means cohesive failure at 25% of the surface area, and the remaining surface area is characterized by the detachment which describes the code letters "a" and "b" in equal measure.

The substrate is a float glass, and the primer is applied, use the ua standard device for coating by spraying. The time setting refer to the periods of time that passes between coating on a substrate and then applying the sealant. Unless otherwise specified, the setting time (specified, for example, in seconds (s), minutes (min), days (d) or months (months)determine at a temperature of 32°C and relative humidity of 80% ("RH") ("32/80"). Indicate the Protocol excerpts for this design, and "7dRT" means exposure for 7 days at room temperature, "+7dH2O" means exposure for 7 additional days when immersed in water (for example, demineralized water (23°C)), "+7d90°C" means exposure for 7 days at room temperature, followed by immersion for 7 days in water (for example, demineralized water (23°C)), followed by aging for 7 days at a temperature of 90°C (in an oven with circulating air), "+7dCata" means exposure for 7 days at room temperature, followed by immersion for 7 days in water (for example, demineralized water (23°C)), followed by aging for 7 days at a temperature of 90°C (in an oven with circulating air) and 7 days metaplasticity processing. To create appropriate conditions for testing you can use the right camera for climatic tests.

Table 2 shows the expected results for BETAPRIME™ 5500 to the I, considered to be a typical produced in one stage with a primer composition prior art, applied to float glass. It is seen that when using primers according to this invention are expecting better results compared to those who receive, using one-component primer prior art.

Table 3 shows that the change of any sort of cover or fritted glass does not have a significant impact on the results obtained by the use of compositions according to this invention.

Enamel 24-8337

Explanations and examples in this document are qualified in this field of technology professionals to explore with this invention, its principles, and its practical application. Those experts who are skilled in the art can modify and apply the invention in its numerous forms, as it can be the best way to approach the requirements of a particular use. Accordingly, do not imply that the specific embodiments of the present invention, in the form in which they are stated, are exhaustive or limiting of this is Britanie. The scope of the invention should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims along with the full scope of equivalents to which such claims has powers. The disclosures of all articles and references, including patent applications and publications, are included in all respects by reference. Links to acrylic or (meth)acrylic (or derivative terms such as "acrylate") consider the methacrylates and acrylates (and related derivative terms). Unless otherwise indicated, references to "an adhesive" or "sealant" are vzaimozavisimy. Thus, the mention of an adhesive substance with a specific composition also covers the sealant with a similar composition.

Despite the fact that the second adduct, also referred to in this document, the adhesion promoter, disclosed in this document, usually in the context of use obtained in a single stage primer composition, its use is not so limited. You can also use them as part primer system, which includes several components and can be added to any or all components. For example, the adhesion promoter can be included in a composition of urethane activator, fritolay preparative comp the stand, Pittaway primer composition, PVC primer, a primer for the part of the frame of the vehicle, where the glass paste, or others, such as one or more products from the company The Dow Chemical Company, sold under the name U-413, U-555, U-4000, U-401, U-402, or the like.

The idea of the present invention can suitably be used in combination with one being simultaneously pending patent applications ser., No. 60/913703 (registered 24 April 2007) Universal Primer Compositions and Methods or ser no. 60/913706 (registered 24 April 2007) “Improved Primer Adhesion Promoters, Compositions and Methods”, incorporated herein by reference, or by them both.

Appendix 1

1 Cohesive failure at 0% surface area

2 Cohesive fracture by approximately 25% surface area

3 Cohesive fracture by approximately 50% surface area

4 Cohesive destruction of approximately 75% of the surface area

5 Cohesive fracture by approximately 100% surface area

and Adhesive primer or without peel from the backing sheet

b Adhesive is peeled from the primer

c If cut to the substrate, a peeling when trimming

d the Separation layer in the primer composition

e Sticky surface of the partition adhesive/primer is the WHC or adhesive/substrate

f Primer dissolves the surface of the substrate

g Primer vzdumaet or rasseivaet surface adhesion near the strip of adhesive

h* Delamination of the substrate

k corrosion under the bar

i Bubbles in the adhesive substance

m Migration of plasticizer from the adhesive into the substrate

n Migration of the plasticizer from the substrate in adhesive

r bubbles in the floor under the strip of adhesive

's bubbles in the floor next to the strip of adhesive

t bubbles in the floor under the primer and near the strip of adhesive

u Delamination in covering songs

v Coating peeled from the substrate

w If you cut the coating of the substrate, it is a little flake with an adhesive substance

x Cohesive fracture near the interface adhesive/primer or adhesive/substrate

y Reinforcing fibers are separated from the substrate

z Delamination from the edge

L cracks in the adhesive substance

T Channels in the adhesive substance

* = Estimation is always shown with optional digit

1. One-component primer composition for substrates of glass and/or plastic, which includes
basic primer composition comprising (a) isocyanate functional prepolymer, which is obtained by the interaction of the aliphatic MDI with what Yalom and which is partially reacted with the secondary amine groups of aminosilane, where aminosilane contains two or three metoxygroup associated with the silicon atom, two or three ethoxypropan associated with the silicon atom, or a combination thereof, (b) isocyanate functional prepolymer with a content of isocyanate groups of more than 1%, which is a reaction product of aromatic MDI and polyol with M_n>300, and (C)at least one solvent for components (a) and (b);
ingredient containing oxazolidinone ring or its derivative;
the first adduct (i) aliphatic isocyanate and (ii) mercaptoethane, aminosilane or both;
the second adduct (i) aromatic MDI and (ii) mercaptoethane, aminosilane or both;
film-forming polymer;
where the primer has a setting time of at least 1 month.

2. The composition according to claim 1, where the isocyanate functional prepolymer with a content of isocyanate groups of more than 1% is a reaction product of an aromatic diisocyanate and poliferation.

3. The composition according to claim 1, where the aromatic polyisocyanate contains thiophosphate, phosphate or tiofosfonovoi group.

4. The composition according to claim 3 where the aromatic polyisocyanate is a Tris(isocyanatophenyl)thiophosphate.

5. Composition according to any one of preceding claims 1 to 4, where the composition further comprises a dye or pigment, solvent is or catalytic Converter.

6. Composition according to any one of preceding claims 1 to 4, where ingredient, including oxazolidinone ring or its derivative includes isoxazolidine and is contained in an amount of from 2 to 8 wt.% by weight of the entire composition.

7. Composition according to any one of preceding claims 1 to 4, where ingredient, including oxazolidinone ring or its derivative includes carbamino acid, 1,6-hexadienyl bis-, bis(2-(2-(1-methylethyl)-3-oxazolidinyl)ethyl) ether and is contained in an amount of from 4 to 6 wt.% by weight of the entire composition.

8. Composition according to any one of preceding claims 1 to 4, where the first adduct is in an amount up to 20 wt.% by weight of the entire composition, and the second adduct is contained in an amount of from 0 to 20 wt.% by weight of the entire composition.

9. Composition according to any one of preceding claims 1 to 4, where the composition includes a (meth)acrylic film former in an amount less than 10 wt.% by weight of the entire composition, and optionally a filler, diethylmalonate, acid or any combination.

10. The method of bonding glass pane to the design of the vehicle, including the stage (a) primer according to any one of claims 1 to 9, essentially, on the perimeter of one side of the glass pane (b) applying on top of the primer composition strips of adhesive and (C) installation of the glass pane by means of a contact adhesive with constructioncompanies means, defining the hole, which set the glass panel.

11. The method according to claim 10, in which stage (a) and (b) separated by a period of time longer than 1 month at room temperature.

12. Glued containing glass or plastic panel design, including utverzhdennuyu primer composition according to any one of preceding claims 1 to 9.

13. Glued construction, manufactured according to the method according to claim 10.