One-part curable polyurethane adhesive
Abstract
THE INVENTION REFERS TO AN ADHESIVE COMPOSITION OF A SINGLE COMPONENT, WHICH INCLUDES: A) I) A POLYMERIC PRECURSOR OF POLYURETHANE WITH ISOCIANATE FUNCTIONALITY, WITH A CONTENT OF FREE ISOCYANATE INCLUDING BETWEEN 0.8 AND 2.2% AND PARTICLES THAT THEY INCLUDE A CURING AGENT FOR SUCH A POLYMER PRECURSOR, ENCAPSULATED INSIDE A COATING MATERIAL; OR II) A POLYMERIC PRECURSOR THAT UNDERSTANDS THE REACTION PRODUCT OF ONE OR MORE POLYISOCYANATES; ONE OR MORE COMPOUNDS THAT CONTAIN ON AVERAGE TERM MORE THAN ONE REACTIVE COMPOUND AGAINST ISOCYANATE; AND A TRIOL IN DISPERSION THAT CONTAINS BETWEEN APPROX. 10 AND 60% W / W, BASED ON THE PARTICULAR DISPERSION OF AN ORGANIC POLYMER THAT IS NOT REACTIVE TO THE REACTIVE COMPOUNDS TO THE ISOCYANATE AND TO THE POLYISOCYANATES WITH A PARTICULAR SIZE BETWEEN APPROX. 5 AND 50 MICRONS. SUCH A POLYMER PRECURSOR HAS A FREE ISOCIANATE CONTENT INCLUDED BETWEEN APPROX. 0.8 AND 2.2%; AND B) A CATALYST SUSCEPTIBLE TO CATALYZE THE REACTION OF THE ISOCYANATE FRACTIONS WITH THE REACTIVE FRACTIONS AGAINST THE ISOCYANATE. ANOTHER EMBODIMENT OF THE INVENTION CONSISTS OF A PROCEDURE TO JOIN TWO SUBSTRATES BETWEEN EACH OTHER, WHICH IS TO CONTACT THE ADHESIVE COMPOSITION OF THE INVENTION, WITH AT LEAST ONE OF THE SUBSTRATES, AND TO CONTACT THE SUBSTRATES THROUGHOUT THE PORTION OF THE SUBSTRATE OR SUBSTRATES TO WHICH THE ADHESIVE HAS BEEN APPLIED, BEFORE SUCH ADHESIVE CURES AND ALLOWS SUCH ADHESIVE TO CURE AND JOINS THE SUBSTRATES BETWEEN.
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10 claims: 3 independent, 7 dependent
- 1ES 2 179 224 T3 REIVINDICACIONES 1. Una composiciáon adhesiva de un solo componente, que comprende:A) un prepolámero con funciáon de isocianato, que tiene un contenido de isocianato libre de 0,8 a 2,2% en peso y una viscosidad de 3.000 centipoises a 20.000 centipoises, en la que el prepolámero comprende: i) uno o máas poliisocianatos;ii) de 10 a 30 % en peso, basado en el peso del prepolámero, de un diol;de 15 a 40 % en peso, basado en el peso del prepolámero, de un triol;y de 9 a 18 % en peso, basado en el peso del prepolámero, de un triol de dispersioán, que contiene de 10 a 60 % en peso, basado en el peso de la dispersián de partáculas polámeras orgánicas, que tienen un tamano de partáculas de 10 a 50 μm, en la que el triol tiene un peso molecular de 4.000 a 8.000 y un ándice de hidroxilo de 15 a 75;B) un catalizador capaz de la reacciáon de restos de isocianato con restos reactivos de isocianato;C) opcionalmnte, uno o máas poliisocianatos.
- 2Un adhesivo de un solo componente, de acuerdo con la reivindicacioán 1, en el que el catalizador comprende una mezcla de un carboxilato de bismuto y uno de un dimorfolin-dietileáter o un dimorfolinodialquiláeter con sustituciones alquilo.
- 3Un adhesivo de un solo componente, de acuerdo con la reivindicaciáon 1 oá 2, en el que el adhesivo comprende, ademáas, un agente de curado para un prepoláímero con funciáon de isocianato, encapsulado en un material de revestimiento.
- 4Un adhesivo de un solo componente, de acuerdo con una cualquiera de las reivindicaciones 1 a 3, en el que el agente de curado es un poliol, agua, un agente de reticulacioán latente que contiene un resto de oxazolidina, o una de sus mezclas.
- 5El adhesivo de la reivindicaciáon 3 áo 4, en el que el material de revestimiento es una cera de hidrocarburo parafáínico derivado del petráoleo, una cera de polietileno, un copoláímero de poli(etileno-olefina), una cera de hidrocarburo oxidado que contiene grupos hidroxilo o carboxilo, un polieáster, una poliamida, o una de sus combinaciones.
- 6El adhesivo de una cualquiera de las reivindicaciones 1 a 5, en el que el catalizador comprende una mezcla de octoato de bismuto y dimorfolinodietiláeter.
- 7Un adhesivo de un solo componente, que depende de una cualquiera de las reivindicaciones 1 a 6, que comprende:i) de 55 a 80 partes, en peso, de prepoláímero;ii) de 15 a 40 partes, en peso, de una carga reforzante;iii) de 1 a 20 partes, en peso, de arcilla;iv) de 0,1 a 5,0 partes, en peso, de un catalizador;v) de 5 a 45 partes, en peso, de plastificante;y vi) de 0,1 a 10 partes, en peso, de partáículas de agente de curado encapsulado;en el que el adhesivo contiene 100 partes.
- 8Un máetodo de unir dos sustratos juntos, que comprende poner en contacto un adhesivo de acuerdo con una cualquiera de las reivindicaciones 1 a 7, con al menos uno de los sustratos y poner en contacto los sustratos juntos con la composicioán adhesiva dispuesta entre los sustratos y permitir al adhesivo curar y unir los sustratos juntos.
- 9El máetodo de la reivindicacioán 8, en el que el adhesivo contiene agentes de curado encapsulados en un material de revestimiento, el cual máetodo comprende, ademáas, romper las cáapsulas de agente de ES 2 179 224 T3 curado a fin de poner en contacto el agente de curado con el prepolímero.
- 10El míetodo de la reivindicaciíon 8 oí 9, en el que el adhesivo exhibe una resistencia al cizallamiento por solapamiento de acuerdo con ASTM D-3163, de 206 kPa o mayor, despueís de 60 minutos y el adhesivo presenta un tiempo de trabajo de 6 a 15 minutos. NOTA INFORMATIVA:Conforme a la reserva del art. 167.2 del Convenio de Patentes Europeas (CPE) y a la Disposición Transitoria del RD 2424/1986, de 10 de octubre, relativo a la aplicación del Convenio de Patente Europea, las patentes europeas que designen a España y solicitadas antes del 7-10-1992, no producirán ningún efecto en España en la medida en que confieran proteccián a productos químicos y farmacáuticos como tales. Esta informacioán no prejuzga que la patente estáeonoincluáda en la mencionada reserva.
Independent claims10
157 paragraphs in 14 sections, as filed
IS 2 179 224 T3
DESCRIPTION
One component curable polyurethane adhesive.
This application refers to a one-component, polyurethane-based adhesive, useful for bonding porous and non-porous materials. The adhesive is especially useful for bonding glass to window frames, for example car windshields.
Polyurethane adhesive compositions comprise at least one urethane prepolymer. Adhesives useful for bonding to non-porous substrates, such as crystals to metals, are well known. When installing glass in automobiles on a manufacturing line, a one-component, moisture-curable polyurethane adhesive is preferably used, since the equipment necessary for applying such an adhesive in an automobile assembly plant is less expensive. than the equipment needed to apply a two-component adhesive. One-component polyurethane adhesives are described in US-A-4,374,237 and US-A-4,687,533. US-A-3,707,521 and US-A-4,780,520 describe one-component polyurethane adhesives used in the automotive OEM (Original Equipment Manufacturers) market for bonding window glass in automobiles.
WO-A-96/21688 describes a two-component adhesive composition comprising a polyurethane prepolymer containing reactive isocyanate moieties in one component and a second component comprising a curing composition comprising, in addition, a polyurea comprising a reaction product of a polyamine and a dispersed polyisocyanate in the form of a polyether-polyol-based polyurethane prepolymer, containing reactive hydroxyl moieties, a compound containing at least one oxazolidene moiety and a catalyst capable of catalyzing the reaction of isocyanate and hydroxyl moieties in the presence of moisture. This two-component adhesive provides a reasonable drive-off time for the replacement glass to bond with the car. Driving times are preferably 60 minutes and more preferably 30 minutes, from the application of the adhesive.
US-A-4,118,376 and US-A-5,015,321 (equivalent to EP-A-0275908) describe moisture-cured adhesives, which contain dispersions in the polyurethane prepolymer and which can be cured with oxazolidines.
In the aftermarket automotive parts industry, glass is often bonded to automobiles through the use of two-component, moisture-curable polyurethane adhesives. Two-component polyurethane adhesives are used because they offer a quick initial cure, allowing times to drive off fast. Two-component adhesives require special application devices that mix the two components, in specific proportions, immediately prior to application. These application devices are more difficult and expensive to use than the application devices used for single component adhesives. Additionally, improper application or mixing of two-component adhesives can lead to poor adhesion. Two-component polyurethane adhesives are well known, US-A-4,835,012 and DE-A-4,210,277.
In addition, the market requires simple application systems and fast curing adhesives that allow times to drive out of the river. If the adhesive cures too quickly, then the glass installer loses time to properly install and position the glass in the frame, before the adhesive becomes difficult to work with. Working time is defined as the period from application of the adhesive until the adhesive becomes difficult to work with.
Future regulations in the US will require double air bags in vehicles. During collisions, airbags inflate and put additional pressure on the windshield. Federal Transportation Agency regulations require windshields to remain in place in collisions of up to 30 miles / hour. This requires adhesives that have better mechanical resistance in the time of being able to go out driving. To meet such standards, the lap shear strength of the adhesive should preferably be 1,033 kPa or greater, as determined in accordance with ASTM D-3163 and exhibit a resilience of 12.2 Joules or greater at power time. exit driving projected.
What is needed, therefore, is a one-component polyurethane adhesive that provides a fast drive-off time, meets the impact and mechanical strength requirements defined above, and still provides a reasonable working time for facilitate proper placement of glass in window frames. What is needed, too, is a system
ES 2 179 224 T3 of a single component that meets these requirements so that the disadvantages of two-component systems can be avoided.
In one embodiment, the invention is a polyurethane prepolymer comprising the reaction product of:
A) monoisocyanate polyisocyanates;
B) one or more compounds containing, on average, more than one reactive isocyanate compound; Y
C) a triol dispersion containing 10 to 60% by weight, based on the dispersion of particles of an orgaonic polymer, which is not reactive with reactive isocyanate compounds, and polyisocyanates having a particle size of 5 to 50 µm;
wherein the prepolymer has an isocyanate content of 0.8 to 2.2% by weight.
In another embodiment, the invention is a single component adhesive composition, comprising:
A) i) an isocyanate-functional polyurethane prepolymer, having a free isocyanate content of 0.8 to 2.2% by weight and particles comprising a curing agent for an isocyanate-functional polyurethane prepolymer, encapsulated with a lining material; or ii) a prepolymer comprising the reaction product of one or more polyisocyanates; one or more compounds containing, on average, more than one reactive isocyanate compound; and a triol dispersion containing 10 to 60% by weight, based on the dispersion of particles of an orgaonic polymer that is not reactive with reactive isocyanate compounds and polyisocyanates having a particle size of 5 to 50 µm; wherein the prepolymer has a free isocyanate content of 0.8 to 2.2% by weight; Y
B) a catalyst capable of catalyzing the reaction of isocyanate moieties with reactive isocyanate moieties.
In yet another embodiment, the invention is a method of joining two substrates together, which comprises contacting an adhesive composition of the invention with at least one of the substrates and contacting the substrates together along the portion of the substrate or substrates to which the adhesive has been applied, before the applied adhesive cures and allowing the adhesive to cure and bond the substrates together.
In another embodiment, the invention is a method of bonding two substrates together, which comprises breaking up the encapsulated curing agent particles in order to contact the curing agent with the prepolymer in the adhesive composition, contacting the adhesive composition of the invention with, at least one of the substrates and contacting the substrates together along the substrate or substrates to which the adhesive has been applied before the applied adhesive cures and allowing the adhesive to cure and bond the substrates together.
The prepolymers of this invention facilitate the preparation of adhesives that solve the problems presented to the skilled professional. The adhesives of the invention provide reasonable drive-off times for the replacement of glass they bond in automobiles. Such drive-off times are preferably 60 minutes and more preferably 30 minutes from the application of the adhesive. The adhesive of the invention also provides reasonable working times, preferably 6 to 15 minutes, and most preferably 10 to 12 minutes. Additionally, the overlap shear strengths and resilience at the time of being able to drive away are preferably 1,033 kPa or greater and mine preferably 1,723 kPa or greater, according to ASTM D-3163 and 12.2 Joules or greater, respectively. Additionally, many of the problems associated with two-component adhesives described above are eliminated.
Useful urethane prepolymers in the invention have medium isocyanate functionality, sufficient to allow the preparation of a cure crosslinked polyurethane and not so high that the prepolymers are unstable. In this context, stability means that the prepolymer or adhesive prepared from the prepolymer has a useful life of at least 6 months at room temperature, because it does not show an increase in viscosity during such a period that prevents its application or use. Preferably, the prepolymer or adhesive prepared therewith does not undergo a viscosity increase of less than 50% during the stated period. Preferably the average isocyanate functionality is at least 2.2 and preferably at least 2.4. Below 2.2, the capacity of the
ES 2 179 224 T3 prepolymer to sufficiently crosslink and achieve the desired strength of the cured adhesive. Preferably, the average isocyanate functionality of the prepolymer is 3.0 or less and more preferably 2.8 or less. With an average isocyanate functionality above 3.0, the prepolymer and adhesives made from the prepolymer can exhibit unacceptable stability. The prepolymer preferably has a free isocyanate content that provides acceptable strength in adhesives made from prepolymers after 60 minutes and stability of the prepolymer. Preferably the free isocyanate content is 0.8% by weight or greater, based on the weight of the prepolymer, mine preferably 1.0% by weight or greater, further preferably 1.2% by weight or greater and most preferably 1 , 4% by weight or more and preferably 2.2% by weight or less, still more preferably 2.1% by weight or less and the same preferably 1.8% by weight or less. Above 2.2% by weight, the adhesives prepared from the prepolymer may exhibit overlap shear strengths after 60 minutes that are too low for their intended use and foaming may occur during the cure of the adhesive prepared from the prepolymer. of the prepolymer. Below 0.8% by weight, the prepolymer may exhibit instability, for example, by gelling within 3 days. Preferably, the weight average molecular weight of the prepolymer is 3,000% higher, mine preferably 4,000% higher, even more preferably 5,000% higher, and less preferably 6,000% higher; and it is preferably 20,000 or less, mine preferably 15,000 or less, even more preferably 10,000 or less and lomies preferably 8,000 or less. The prepolymer preferably exhibits a viscosity that facilitates the formulation of a pumpable adhesive having good green strength. Preferably the viscosity of the prepolymer is 20,000 or more and preferably 13,000 or less, preferably 3,000 centipoise or more, and more preferably 6,000 centipoise or more and most preferably 8,000 centipoise or mine. The viscosity of the adhesive can be adjusted with loads, although the loads cannot improve the strength, in the green state, of the final adhesive. Below 3,000 centipoise, the adhesive prepared from the prepolymer may exhibit poor green strength. Above 20,000 centipoise, the prepolymer can be unstable and undergo gelling. The prepolymer can be prepared by any appropriate method, such as by reacting one or more compounds or polymers containing, on average, more than one, and preferably, at least two isocyanate-reactive groups in excess, relative to stoichiometry. , of a polyisocyanate under sufficient reaction conditions to form a prepolymer having an isocyanate functionality and a free isocyanate content that meet the criteria discussed above.
Preferable polyisocyanates for use in preparing the prepolymer include any aliphatic, cycloaliphatic, arylaliphatic, heterocyclic, or aromaitic polyisocyanate, or mixtures thereof, with an average isocyanate functionality of at least 2.0 and an equivalent weight of at least 80. Preferably, the isocyanate functionality of the polyisocyanate is at least 2.0, most preferably at least 2.2 and most preferably at least 2.3; and preferably it is not greater than 4.0, most preferably not greater than 3.5, and mine preferably not greater than 3.0. Higher functionalities can be used, but their use can cause excessive crosslinking, result in an adhesive that is too viscous to handle and apply easily, can cause the cured adhesive to be cold-agile and result in foaming due to bubbling of the carbon dioxide. Preferably, the equivalent weight of the polyisocyanate is at least 100, preferably at least 110, and most preferably at least 120; and preferably not more than 300, mine preferably not more than 250 and mine preferably not more than 200.
Examples of such polyisocyanates include those described in WO 96/21588, see page 3, lines 7-36, published July 18, 1996. Preferably, the polyisocyanate is an aromatic or cycloaliphatic polyisocyanate such as diphenylmethane-4,4'- diisocyanate, isophorone-diisocyanate, tetramethylxylene-diisocyanate, and mine is preferably diphenylmethane-4,4'-diisocyanate.
Polyisocyanates are used in sufficient quantity to form an advanced polyurethane prepolymer having free reactive isocyanate moieties. Preferably, the amount of polyisocyanates 5% by weight or more, based on the starting materials and corn preferably 9% by weight or more and preferably 20% by weight or less, more preferably 15% by weight or less and mine preferably 11% by weight or less.
The term "isocyanate-reactive compound" as used herein includes water and any organic compound that has, on average, more than one and preferably at least two, and preferably no more than 4, moieties reactive with isocyanate, such as a compound containing an active hydrogen moiety or a compound with imino function and are described in WO 96/21688, published July 18, 1996, see page 3, line 37 to page 4, line 9.
Preferable isocyanate reactive compounds are polyols. The term polyol as used herein includes any organic compound that has the term me4
ES 2 179 224 T3 gave more than one, and preferably at least two, and preferably not more than four, isocyanate-reactive hydroxyl moieties. Preferred polyols Useful in the preparation of the prepolymers include, for example, polyether polyols, polyester polyols, poly (alkylene carbonate) polyols, hydroxyl-containing polythioethers, polymeric polyols, and mixtures thereof. Preferably, uatile polyether polyols in the invention are described in WO 96/21688, published July 18, 1996, see page 4, lines 11 to 26.
Polyester polyols are well known in the art and can be prepared by reacting a polycarboxylic acid or its anhydride with a polyhydric alcohol. Examples of preferable carboxylic acids include those described in WO 96/21688, published July 18, 1996, see page 4, lines 29 to 37.
Preferred polymeric polyols include polymer dispersions of vinyl monomers in a continuous polyol phase, particularly styrene / acrylonitrile copolymer dispersions. Also useful are so-called polyisocyanate polyadicioan polyols (PIPAs) (dispersions of polyurea-polyurethane particles in a polyol) and polyurea dispersions in polyols (PHD polyols). Vinyl-type copolymer polyols are described, for example, in US Pat. 4,390,645, 4,463,107, 4,148,840 and 4,574,137.
Preferably, the polyol (s) have an average functionality of at least 1.5, most preferably at least 1.8 and most preferably at least 2.0; and preferably it is not greater than 4.0, most preferably not greater than 3.5 and most preferably, not greater than 3.0. Preferably, the equivalent weight of the polyol or polyols is at least 200, most preferably at least 500 and most preferably at least 1,000; and preferably, it is not greater than 3,500, most preferably not greater than 3,000, and most preferably, not greater than 2,500.
Preferably, the polyol is a mixture of one or more diols and one or more triols. Preferably, the single polyols are polyether polyols and most preferably poly (alkylene oxide) polyols. However, most preferred are polypropylene oxide-based polyols with ethylene oxide caption, for example, those prepared by reacting glycerol with propylene oxide, followed by reacting the product with ethylene oxide.
The polyols are present in an amount sufficient to react with most of the isocyanate groups of isocyanates bearing sufficient isocyanate groups to correspond to the desired free isocyanate content of the prepolymer. Preferably, the polyols are present in an amount of 25% by weight or greater, based on the prepolymer, most preferably 42% by weight or greater and most preferably 48% by weight or greater. Preferably, the polyols are present in an amount of 70% by weight or less, based on the prepolymer, most preferably 58% by weight or less and most preferably 52% by weight or less. In the embodiment where the polyols comprise a mixture of diols and triols, the amount of diols present is preferably 10% by weight or greater, based on the prepolymer, more preferably 17% by weight or greater, and most preferably 19% by weight. weight or greater; and 30% by weight or less, based on the prepolymer, more preferably 23% by weight or less and more preferably 21% by weight or less. In the embodiment where the polyols comprise a mixture of diols and triols, the amount of triols present is preferably 15% by weight or greater, based on the prepolymer, most preferably 25% by weight or greater, and most preferably 28% by weight. weight or greater; and preferably 40% by weight or less, based on the prepolymer, more preferably 35% by weight or less and most preferably 32% by weight or less. The ratio of diol to triol is chosen to achieve the desired isocyanate functionality of the prepolymer.
In a preferred embodiment, the triol may be a dispersion triol, comprising particles dispersed in it of an organically based polymer. The organic-based polymer particles are chosen so that they are not reactive with the isocyanate-reactive moieties or isocyanate moieties of the isocyanates. Preferably, the particles comprise a thermoplastic polymer, rubber modified thermoplastic polymer or a polyurea, dispersed in a triol. Ulatile polyureas preferably comprise the reaction product of a polyamine and a polyisocyanate. Preferable thermoplastic polymers are those based on monovinylidene aromatic monomers and copolymers of monovinylidene aromatic monomers with conjugated dienes, acrylates, methacrylates and / or unsaturated nitriles. The copolymer can be a block or random copolymer. More preferably, the particles dispersed in the triol comprise copolymers of unsaturated nitriles, conjugated dienes and a monovinylidene aromatic compound; a copolymer of an unsaturated nitrile and a monovinylidene aromatic monoomer or a polyurea. Most preferably, the particles comprise a polyurea or polystyrene-acrylonitrile copolymer, with polystyrene-acrylonitrile copolymers being most preferred.
IS 2 179 224 T3
Representative monovinylidene aromatic compounds that may be employed herein include styrene, styrene with alkyl substitutions (eg, alpha-methylstyrene and alpha-ethylstyrene), and styrenes with ring substitutions (eg, vinyl toluene, particularly para-vinyl toluene, ortho-ethylstyrene and 2,4-di-methylstyrene); halogenated styrenes with ring substitutions such as chlorostyrene and 2,4-dichlorostyrene; styrenes substituted with halo and alkyl groups, such as 2-chloro-4-methylstyrene and vinylanthracene. In general, the monovinylidene aromatic compound (s) employed in preparing the styrenic polymeric resin is or are styrene or the combination of styrene and alpha-methylstyrene (advantageously such combinations contain alpha-methylstyrene in amounts of 10 to 50, and more advantageously 15 to 40%, by weight of the total weight of styrene and alpha-methylstyrene); styrene being the most preferred monovinylidene aromatic compound.
Preferred unsaturated nitriles useful herein include acrylonitrile, ethacrylonitrile, methacrylonitrile, and mixtures thereof; most preferred is acrylonitrile. In the preparation of useful copolymers in this invention, the amount of the unsaturated nitrile (s) most advantageously used (s) should vary according to the desired phasic and chemical properties of the copolymer particles. The copolymer should advantageously derive from 5 to 35, preferably from 15 to 25% by weight of the unsaturated nitrile (s), wherein said weight percentage is based on the total weight of the polymer.
Ulatile conjugated dienes in the block copolymer include straight or branched chain aliphatic hydrocarbons, which contain two double bonds attached to adjacent carbon atoms. Preferred dienes contain 4 to 6 carbon atoms and include butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, and mixtures thereof. Most preferably, such conjugated dienes contain 4 to 5 carbon atoms and include, for example, butadiene, isoprene, cis-1,3-pentadiene, trans-1,3-pentadiene, and mixtures thereof. The most preferred dienes are butadiene and isoprene.
To prepare the copolymers based on styrene and optionally other unsaturated compounds, most commonly bulk polymerization techniques or mass / suspension combination are employed. Illustrative bulk polymerization techniques are described in US Patents 2,727,884 and 4,782,127. Procedures for the preparation of block copolymers of monovinylidene aromatic comonaomers and conjugated dienes are described in US Patents 5,242,984 and 5,134,968.
In one embodiment, the thermoplastic polymer particles can be rubber modified. Generally, this involves mixing an elastoomeric or rubbery polymer with the thermoplastic polymer. A preferred rubbery material is acrylonitrile-butadiene-styrene interpolymer. Preferably, the rubber modified polymer particles contain 15 to 25%, by weight, of rubber polymer.
Preferably, the triol is a polyethertriol, most preferably a polyoxyalkylene-based triol and most preferably the triol comprises a polyoxypropylene chain with a polyoxyethylene endcap. A particularly preferred polyetherriol is a 1,2,3-propanetriol initiated polyoxypropylene, with a polyoxyethylene cap. Preferably, such triol has a molecular weight of 4,000 or more, more preferably 5,000 or more, and more preferably 6,000 or more. Preferably, such a triol has a molecular weight of 8,000 or less, and more preferably 7,000 or less. With a molecular weight below 4,000, the elongation and impact properties of the final cured adhesive may be too low for its intended use. With a molecular weight above 8,000, the adhesive prepared from the prepolymer can be excessively elastaomeric for its intended use. The triol preferably has a hydroxyl number that is high enough so that the adhesive prepared from the prepolymer cures quickly enough and provides the desired air exposure times. If the hydroxyl number is too low, the adhesive cures too slowly and the desired air exposure times and driving times cannot be achieved. The hydroxyl number should not be so high as to reduce the elongation of the cured adhesive prepared from the prepolymer. Preferably, the hydroxyl number of the triol is 15 or more, more preferably 20 or more, even more preferably 30 or more, and even more preferably 40 or more. Preferably, the hydroxyl number of the triol is 75 or more less and more preferably 60 or less.
The organic polymer particles dispersed in the triol preferably have a particle size that is large enough to improve the impact properties and elastomeric properties of the finally cured adhesive, but not so large as to reduce the maximum mechanical strength of the adhesive after 60 minutes of curing. Preferably the particle size is 10 µm or larger and more preferably the particle size is 20 µm or larger. Preferably the particle size is 50 µm or less and more preferably the particle size is 40 µm or less. The triol dispersion contains a sufficient quantity of organic polymeric particles so that the adhesive, upon curing, has sufficient hardness for the intended use and not so much that the adhesive
ES 2 179 224 T3 has too much elasticity, as defined by elongation. Preferably the dispersion contains 20% by weight or more of organic polymeric particles based on the dispersion, preferably 30% by weight or mine and more preferably 35% by weight or mine. Preferably, the dispersion contains 60% by weight or less of organic polymeric particles based on the dispersion, preferably 50% by weight less and preferably 45% by weight or less.
If present, the dispersion of organic polymeric particles in a triol is present in the prepolymer in an amount of 9% by weight or more of the prepolymer and more preferably 10% by weight or less, and 18% by weight or less of the prepolymer and more preferably 12% by weight or less.
In one embodiment, the organic polymeric particles comprise a polyurea, which comprises the reaction product of a polyamine and a polyisocyanate. The polyurea preferably does not react with reactive isocyanate moieties or isocyanate moieties. Preferably, the polyurea is prepared by reacting a polyamine, preferably a diamine, with a polyisocyanate, and preferably a diisocyanate. The polyisocyanate and polyamine mix and undergo an immediate reaction at room temperature. Subsequently, the polyurea is contacted with triols, preferably under high shear conditions, to disperse the polyurea in the triol. Preferably, the isocyanate used to prepare the polyurea is an aliphatic or cycloaliphatic polyisocyanate, since the use of aliphatic and cycloaliphatic isocyanates facilitates the handling and stability of the polyurea. Preferably, the polyurea has a urea functionality of 8% or more, more preferably 10% or more, and more preferably 15% or more. Preferably, the polyurea has a functionality of 40% or less and more preferably 20% or less. The term "functionality" as used herein relating to polyureas refers to the percentage by weight of urea groups present in the polyurea.
The polyurethane prepolymers of the invention may further comprise a plasticizer. Useful plasticizers in the prepolymer are common plasticizers useful in polyurethane adhesive applications and well known to those of skill in the art. The plasticizer is present in an amount sufficient to disperse the prepolymer in the final adhesive composition. The plasticizer can be added to the adhesive during preparation of the prepolymer or during mixing of the adhesive composition. Preferably, the plasticizer is present in 1% by weight or more of the prepolymer formulation (mine prepolymer plasticizer), more preferably 18% by weight or more and more preferably 22% by weight or more. Preferably, the plasticizer is present in the amount of 32% by weight or less of the prepolymer formulation and more preferably 25% by weight or less.
The polyurethane prepolymer can be prepared by any appropriate method, such as bulk polymerization and solution polymerization. The reaction to prepare the prepolymer is carried out under anhydrous conditions, preferably in an inert atmosphere such as a nitrogen blanket, to avoid crosslinking of the isocyanate groups by atmospheric humidity. The polyurethane prepolymer is preferably prepared by contacting the compound or polymers containing the reactive moieties with isocyanate in the absence of a catalyst and heating the mixture to 45 ° C or more, and more preferably 48 ° C or more. The mixture is heated to a temperature of 55 ° C or less, and more preferably 49 ° C or less. The polyisocyanate is then added to the mixture and the mixture is subjected to a mixing operation in order to uniformly disperse the polyisocyanate in the reaction mixture. The polyurethane catalyst is then added. After the addition of the catalyst, an exotherm generally occurs, preferably the peak of the exotherm is 58 ° C or higher and more preferably 60 ° C or higher. Preferably, the exotherm peak is 70 ° C or less and more preferably 65 ° C or less. Above 70 ° C, the reaction mixture gels. The plasticizer can then be added after the exotherm recedes, that is, the temperature drops, to dilute the reactants and attenuate the reaction. The reaction should be carried out in such a way that all free isocyanate reactive moieties are reacted with isocyanate moieties. The reaction mixture preferably contains a standard polyurethane catalyst, as described in WO 94/09046 published April 28, 1994, see page 6, lines 30 to 34. The amount of catalyst used is generally between 0.005 and 5 % by weight of the catalyzed mixture, depending on the nature of the isocyanate. The relative ratio of isocyanate groups to isocyanate-reactive groups should be such that the resulting prepolymer has no free isocyanate-reactive groups, since such groups should react prematurely. Preferably, the ratio of isocyanate groups to isocyanate reactive groups is such that reasonable progress occurs. Preferably, the equivalent ratio of isocyanate groups to isocyanate-reactive groups is 1.2 or more and more preferably 1.4 or more. The equivalent ratio should not be so low as to avoid complete reaction of the reactive moieties with isocyanate. Preferably, the equivalent ratio of isocyanate groups to isocyanate-reactive groups is 2.0 or less and most preferably 1.6 or less.
IS 2 179 224 T3
In one embodiment, the adhesive composition contains particles comprising a curing agent for an isocyanate functional polyurethane prepolymer, encapsulated with a coating material. The particles function as a latent curing system. When curing agents are dislodged from the coating material, the curing agents function to accelerate the cure of the adhesive so that the desired properties are achieved. The particles should be of a size that can be broken to release the curing agent and not so large that residual coating material remaining in the adhesive interferes with the adhesive or cohesive strength of the cured adhesive. The mean particle size is preferably 10 µm or larger, more preferably 700 µm or larger, and most preferably 1,000 µm or larger. The mean particle size of the particles is preferably 2,100 µm or less, more preferably 1,400 µm or less and most preferably 1,200 µm or less.
The particles contain a curing agent for polyurethane prepolymers with polyisocyanate function. Any material that can cure such prepolymers can be used as a curing agent, and such materials are isocyanate-reactive materials, as defined above. Preferably, the isocyanate-reactive compound useful as a curing agent is a polyol, water, a latent crosslinking material containing at least one oxazolidine moiety or a mixture thereof. Preferred curing agents are short chain polyols, such as those commonly used as initiators for polyether polyols as described above, water, a latent crosslinking material containing at least one oxazolidine moiety, or mixtures thereof. Examples of latent crosslinking materials include those described in US Patents 4,396,681; 3,743,626; 4,118,376; 4,192,937 and 5,235,062. In one embodiment, such latent crosslinkers comprise bis-oxazolidines, which are the reaction product of a diisocyanate with an oxazolidone with hydroxy-alkyl substitutions, such as an N-hydroxyethyl-oxazolidone. Preferred isocyanates are aliphatic and cycloaliphatic isocyanates such as hexamethylene diisocyanate. A preferred oxazolidone-containing compound is commercially available from Mobay under the Hardener designation OZ, which is carbaimic acid, 1,6-hexanediyl-bis-, bis {2- [2- (1-methylethyl) -3-oxazolidinyl ] ethyl} ester. Most preferably, the curing agent is water, diethylene glycol, butanediol, a bisoxazolidine such as Hardener OZ or mixtures thereof.
The coating material is insoluble with respect to the curing agent, and preferably the prepolymer, and preferably has a melting point in the range of 40 ° C to 200 ° C. The coating material is most preferably a paraffinic hydrocarbon wax derived from petroleum. ; a polyethylene wax, a poly (ethylene-olefin) copolymer, an oxidized hydrocarbon wax containing hydroxyl or carboxyl groups, a polyether, a polyamide, or combinations thereof. Mine preferably, the coating material is a paraffinic hydrocarbon wax derived from petroleum, a polyethylene-olefin copolymer, or a polyethylene wax or combinations thereof. Preferred polyethylene waxes preferably have a weight average molecular weight in the range of from 500, most preferably 1,000 to 3,000, and most preferably 2,000 Daltons. These tin waxes exemplified by Polywax<sup>R</sup> 500, Polywax<sup>R</sup> 1000, and Polywax<sup>R</sup> 2000, or its mixtures, and preferably a mixture, of 75:25, of polywax<sup>R</sup> 1000 and Polywax<sup>R</sup> 2000. (Polywax is a trademark of Petrolite Corporation).
The curing agent can be encapsulated using the apparatus described in US Patent 3,389,194. The curing agent is pumped through the center tube and the coating material is pumped through the annulus of the nozzle, in order to extrude a fluid rod of curing agent encased in a shell of coating material in a fluid. carrier. Subsequently, the rod is broken into individual particles. The particles are transported along a conveyor to harden the coating material. The particles are collected on a sieve. The preferred carrier fluid for the coating material is water. The temperature of the coating material and the carrier fluid should be chosen so that the coating material formulation is pumpable and extrudable. During cooling, the particles are brought into contact with a cold fluid, such as water, which is at the temperature at which the coating material solidifies. The coating material can be heated separately, preferably to the temperature at which it is liquid, before being contacted with the carrier fluid.
Alternatively, the particles can be prepared by the following procedures:
a) dispersing the curing agent into the coating material at a temperature sufficient to melt the coating material;
b) forming curing agent droplets intermixed with the coating material, and
c) cooling the droplets to solidify the coating material.
Optionally, the procedure can include, in addition:
IS 2 179 224 T3
d) contacting the droplets with a solvent that dissolves the curing agent, but does not dissolve the coating material, in order to separate the curing agent from the surface of the coating material.
This procedure is described in WO 96/09883, published April 4, 1996, see page 2, lines 26 to 30 and page 4, lines 5 to 23. In a preferred embodiment, solidified particles of coating material intermixed with curing agent are collected and contacted with a solvent that dissolves the curing agent, but does not dissolve the coating material, which solvent is described in the document. WO 96/09883, published April 4, 1996, on page 4, lines 23 to 35.
The concentration of curing agent in the particles is preferably 1% by weight or more, preferably 20% by weight or more, and more preferably 25% by weight or more. The concentration of curing agent in the particles is preferably 70% by weight or less, mine preferably 65% by weight or less, even more preferably 50% by weight or less, and mine preferably 45% by weight or less, based on the total weight of curing agent and coating material.
The polyurethane prepolymers are present in the adhesive composition in sufficient quantity so that when the resulting adhesive cures, the substrates bond together. Preferably, the overlap shear strengths of bonds so formed is 206 kPa or greater after 60 minutes and more preferably after 30 minutes. Preferably, the polyurethane prepolymers are present in an amount of 55 parts by weight of the adhesive composition or greater, preferably 60 parts by weight or greater and most preferably 69 parts by weight or greater. Preferably, the polyurethane prepolymers are present in an amount of 80 parts by weight of the adhesive composition or less, more preferably 75 parts by weight or less and still more preferably 70 parts by weight or less.
The curing agent-containing particles are present in the adhesive composition in sufficient quantity to achieve the desired air exposure time. Preferably, the adhesive composition contains the particles in an amount of 0.1% by weight or greater based on the weight of the adhesive composition, more preferably 0.3% by weight or greater and the same preferably 0.7% by weight or higher. Preferably, the adhesive composition contains the particles in an amount of 10% by weight or less based on the weight of the composition, mine preferably 5.0% by weight or less and mine preferably 2.0% by weight or less.
The adhesive of the invention can be formulated with fillers and additives known in the art for use in adhesive compositions. By adding such materials, physical properties, such as viscous flow, can be modified. However, to avoid premature hydrolysis of the moisture sensitive groups of the polyurethane prepolymer, the fillers should be thoroughly dried before mixing with it.
Optional components of the adhesive of the invention include reinforcing fillers. Such fillers are well known to those skilled in the art and include carbon black, titanium dioxide, cyalcium carbonate, surface-treated silicas, titanium ioxide, fumed silica, and talc. Preferred reinforcing fillers comprise carbon black. In one embodiment, mine of a reinforcing filler can be used, of which one is carbon black and a sufficient amount of carbon black is used to provide the adhesive with the desired black color. Reinforcing fillers are used in amounts sufficient to increase the mechanical strength of the adhesive and provide thixotropy properties to the adhesive. Preferably, the reinforcing filler is present in an amount of 1 part by weight of the adhesive composition or greater, more preferably 15 parts by weight or greater and the same preferably 17 parts by weight or greater. Preferably, the reinforcing filler is present in an amount of 40 parts by weight of the adhesive composition or less, more preferably 25 parts by weight or less and the same preferably 23 parts by weight or less.
Among the optional materials in the adhesive composition are clays. Preferred clays useful in the invention include kaolin, surface treated kaolin, calcined kaolin, aluminum silicates and anhydrous surface treated aluminum silicates. Clays can be used in any form that facilitates the formulation of a pumpable adhesive. Preferably the clay is in the form of a fine powder, spray dried beads, or finely ground particles. The clays can be used in an amount of 0 parts by weight of the adhesive composition or more, preferably 1 part by weight or more and preferably 6 parts by weight or more. Clays are preferably used in an amount of 20 parts by weight or less of the adhesive composition and preferably 10 parts by weight or less.
IS 2 179 224 T3
The adhesive composition of the invention may further comprise one or more known catalysts to promote curing of polyurethanes in the presence of moisture. Preferable catalysts include metal salts such as tin carboxylates, silicon organotitanates, alkyl titanates, bismuth carboxylates, and dimorpholinodiethylene ether or dimorpholinodiethyl ethers with alkyl substitutions. Among the preferred catalysts are bismuth octoate, di-morpholinodiethyleether and di- [2- (3,5-dimethylmorpholino) ethyl] ether. Such catalysts, when employed, are preferably employed in an amount, based on the weight of the adhesive composition, of 0 part by weight or greater, more preferably 0.1 part by weight or greater, even more preferably 0.2 part by weight. weight or greater and more preferably 0.4 parts by weight or greater. Such catalysts are preferably employed in an amount, based on the weight of the adhesive composition, of 5 parts by weight or less, more preferably 1.75 parts by weight or less, more preferably 1 part by weight or less, and most preferably 0.6 part by weight or less.
The adhesive composition of this invention may further comprise plasticizers in order to modify the rheological properties to the desired consistency. Such materials should be water-free, inert to isocyanate groups, and compatible with a polymer. Appropriate plasticizers are well known in the art and preferable plasticizers include alkyl phthalates, such as dioctyl phthalate or dibutyl phthalate, partially hydrogenated terpene available commercially as "HB-40", trioctyl phosphate, epoxy plasticizers, toluene para sulfamide, chlorofin , esters of adapic acid, castor oil, toluene and alkyl-naphthalenes. The amount of plasticizer in the adhesive composition is the amount that gives the desired rheologic properties and is sufficient to disperse the catalyst in the system. The amounts described herein include the amounts added during the preparation of the prepolymer and during the adhesive mixing operation. Preferred plasticizers are used in the adhesive composition in an amount of 0 parts by weight or greater, based on the weight of the adhesive composition, most preferably 5 parts by weight or greater and most preferably 10 parts by weight or greater. The plasticizer is preferably used in an amount of 45 parts by weight or less, based on the total amount of the adhesive composition and more preferably 40 parts by weight or less.
The adhesive of this invention may also comprise stabilizers that act to protect the adhesive composition from moisture, thereby inhibiting advancement and preventing premature crosslinking of isocyanates in the adhesive formulation. Included among such stabilizers are diethyl malonate and alkylphenol alkylates. Such stabilizers are preferably used in an amount of 0.1 part by weight or more, based on the total weight of the adhesive composition, preferably 0.5 part by weight or more, and more preferably 0.8 part by weight or more. Such stabilizers are used in an amount of 5.0 parts by weight or less, based on the weight of the adhesive composition, most preferably 2.0 parts by weight or less and most preferably 1.4 parts by weight or less.
Optionally, the adhesive composition may further comprise a thixotrope. Such thixoatropes are well known to those skilled in the art and include alumina, limestone, talc, zinc oxides, sulfur oxides, calcium carbonate, pearlite, shale dust, salt (NaCl), and cyclodextrin. The thixoatrope can be added to the adhesive of the composition in sufficient quantity to give the desired rheologic properties. Preferably, the thixotrope is present in an amount of 0 parts by weight or greater, based on the weight of the adhesive composition, and preferably 1 part by weight or greater. Preferably, the optional thixotrope is present in an amount of 10 parts by weight or less, based on the weight of the adhesive composition and more preferably 2 parts by weight or less.
The adhesive composition may further comprise several polyisocyanates. The polyisocyanates that may be present are those described above.
Other components commonly used in adhesive compositions can be used in the adhesive composition of this invention. Such materials are well known to those skilled in the art and can include ultraviolet radiation stabilizers and antioxidants.
As used herein, all parts by weight relative to the adhesive composition components are based on 100 total parts by weight of the adhesive composition.
The adhesive composition of this invention can be formulated by mixing the components together using means well known in the art. Generally, the components are mixed in appropriate mixers. Such mixtures are preferably carried out in an inert atmosphere, in the absence of oxygen and atmospheric humidity to avoid premature reaction. It may be advantageous to add some plasticizers to the reaction mixture to prepare the isocyanate-containing prepolymer, so that such a mixture can be easily mixed and handled. Alternatively, plasticizers can be added
ES 2 179 224 T3 during the mixing of the components. Once the adhesive composition is formulated, it is packaged in an appropriate container so that it is protected from atmospheric moisture and oxygen. Contact with atmospheric moisture and oxygen could lead to premature crosslinking of the isocyanate groups contained in the polyurethane prepolymer.
The encapsulated curing agent particles can be combined or mixed into the adhesive formulation using different procedures, at different stages of production. The encapsulated curing agent particles can be mixed into the prepolymer after it has been synthesized. This prepolymer, with the mixed encapsulated curing agent particles, is then used for mixing into the adhesive. The encapsulated curing agent particles can also be mixed directly into the adhesive after the compounding step. After the cycle of mixing and wetting the batches within the blending or mixing apparatus is completed, the encapsulated curing agent particles are added to achieve a good dispersion. The encapsulated curing agent particles can be dry or slurry coextruded with the prepolymer directly into the container during the filling and packaging step.
The adhesive composition of the invention is used to bond porous and non-porous substrates together. The adhesive composition is applied to one substrate and the adhesive on the first substrate is then contacted with a second substrate. In preferred embodiments, the surfaces to which the adhesive is applied are cleaned and primed prior to application, see for example US Patents 4,525,511, 3,707,521 and 3,779,794. Generally, the adhesives of the invention are applied at room temperature in the presence of atmospheric humidity. Exposure to atmospheric moisture is sufficient to cause the adhesive to cure. Curing is accelerated by the addition of the encapsulated curing agent particles. Curing can also be accelerated by applying heat to the adhesive to be cured by conventional heat, or microwave heating. Preferably, the adhesive of the invention is formulated to provide a working time of 6 minutes or more, and more preferably 10 minutes or more. Preferably the working time is 15 minutes or less and more preferably 12 minutes or less.
In the embodiment where encapsulated curing agents are used, during the application of the adhesive of the invention, the particles are broken to loosen the curing agent so that it can accelerate the curing of the adhesive. This breaking of the particles can be carried out by the application of heat, shear forces, ultrasoin waves or microwaves during the application of the adhesive. In many embodiments the dispensing apparatus has incorporated the apparatus necessary to break up the particles. The dispensing apparatus may incorporate a heating element, means of shearing the particles, or applying ultrasound or microwaves. In a preferred embodiment, the adhesive is forced through a screen which, at its smallest point, is smaller than the smallest particles. In such an embodiment it is preferable if the sieve has long slots that have very large openings facing the adhesive to be extruded and smaller openings facing the dispensing nozzle, in which the smallest opening is smaller than the smaller particles. and my big opening is bigger than my big particles. The design reduces the pressure drop that results from pushing the adhesive containing the particles through the screen.
The adhesive composition is preferably used to bond glass to other substrates such as metals or plastics. In a preferred embodiment, the first substrate is a glass window and the second substrate is a window frame. In another preferred embodiment, the first substrate is a glass window and the second substrate is a car window frame.
Preferably the adhesive compositions of the invention have an overlap shear strength, after 60 minutes from application to substrates, of 206 kPa or greater, mine preferably 412 kPa or greater and most preferably 548 kPa or greater. Overlap shears are determined in accordance with ASTM D-3163. Preferably, the cured adhesive compositions of the invention exhibit an elongation of 200% or greater as determined according to ASTM D-638-91, more preferably 300% or greater and preferably greater than 600%. Preferably, the elongation is 700% or less.
Viscosities, as described herein, are determined according to the procedure described in WO 96/21688, published July 18, 1996, on page 12, lines 24-30.
Molecular weights as described herein refer to weight average molecular weights and are determined according to the procedure described in WO 96/21688, published July 18, 1996, on page 12, lines 31 to 13 line 2.
IS 2 179 224 T3
With reference to polyurethane prepolymers, the average isocyanate functionality is determined according to the procedure and formula described in WO 96/21688, published July 18, 1996, page 13, lines 3 to 17.
The following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight, unless otherwise indicated. Prepolymer preparation
Examples 1-6
A polyether-polyurethane prepolymer, with a low degree of branching will be prepared by mixing 545.52 g of a polyoxypropylene diol, having an average molecular weight of 2,000, commercially available from PPG under the trade name "PPG<sup>R</sup> 2025 ", with 790.56 g of a polyoxypropylene triol having an average molecular weight of 4,500 and commercially available from Olin Chemical, under the trade name" POLY G<sup>R</sup> 85-36 ". The mixing was carried out in a reactor, while the mixture was heated to 55 ° C. 240.9 g of diphenylmethane-4,4'-diisocyanate and 0.25 g of stannous octoate were added to the mixture. The mixture was reacted for 1 hour. 788.16 g of a plasticizer, dialkyl phthalate, was added to the mixture and the mixing was continued for one hour.
Preparation of adhesive compositions
Examples 1-6
Adhesive compositions were prepared by introducing the prepolymer, previously prepared, into a planetary mixer, and degassing the mixture for 20 minutes. Carbon black and clay were added to the mixer and the mixing was continued for 20 minutes under vacuum. Dimorpholinodiethyl ether (DMDEE) was added as a catalyst to the mixture and mixed for another 20 minutes. The encapsulated curing agents were randomly dispersed within the adhesive composition. The adhesive composition was packaged in tubes. The components, and the amounts of the components of the adhesive compositions prepared are presented in Table I. In Example 1, no encapsulated curing agent will be used. In Examples 2 and 3, the encapsulated curing agent was water in an amount of 50% by weight, encapsulated in a mixture of 45% by weight Boler paraffin wax<sup>R</sup> 1426, 45% by weight of Piccolyte 5-115 hydrocarbon resin and 10% by weight of polyethylene Epolene C-16. In Examples 4 to 6, the encapsulated curing agent was a 50:50 mixture of diethylene glycol and a urethane-bisoxazolidine (Hardener OZ available from BASF) present in a total amount of 35% by weight in the encapsulated curing agent particles. , in which the coating material was as described above.
TABLE I
<td>Compositions adhesive Example</td><td>1* (g)</td><td>two (g)</td><td> 3 <sup>(</sup>g)</td><td> 4 <sup>(</sup>g)</td><td> 5 <sup>(</sup>g)</td><td> 6 <sup>(</sup>g)</td>
<td>Prepolymer</td><td> 648,38</td><td> 648,38</td><td> 324,19</td><td> 778,05</td><td> 648,38</td><td> 713,21</td>
<td>Carbon black</td><td> 255,96</td><td> 255,96</td><td> 127,98</td><td> 307,15</td><td> 255,96</td><td> 281,55</td>
<td>Clay</td><td> 72</td><td> 72</td><td> 36</td><td> 86,4</td><td> 72</td><td> 79,2</td>
<td>Dimorpholinodiethylather</td><td> 2,28</td><td> 2,28</td><td> 1,14</td><td> 2,73</td><td> 2,28</td><td> 2,5</td>
<td>Encapsulated curing agent</td><td> 0</td><td> 55</td><td> 55</td><td> 66</td><td> 110</td><td> 242</td>
* Comparative example
The adhesives were tested in terms of working time and skin formation time, according to the methods described below and the resistance to overlap shear according to
IS 2 179 224 T3
ASTM D-3163. Skinning time was determined by the following procedure. A 6.35 x 6.35 mm bead of adhesive was distributed on release paper. Every two minutes, a throat spatula was lightly pressed onto the surface of the adhesive bead. The first time that there was no adhesive residue on the throat patella after compressing it, it was taken as skin formation time. To measure working time, a drop of adhesive on release paper as described above was reduced to half its size, with a throat swab, every minute. The time after depositing, when the drop of adhesive no longer stains by pressure from the throat patella, is the highest Emit of the working time. The results are presented in Table II.
TABLE II
<td></td><td> 1*</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>wt% encapsulated curing agent</td><td> 0</td><td> 0,5</td><td> 1,0</td><td> 0,5</td><td> 1,0</td><td> 2,0</td>
<td>% curing agent in encapsulated particles</td><td> 0</td><td> 50</td><td> 50</td><td> 35</td><td> 35</td><td> 35</td>
<td>Working time (minutes)</td><td> 20</td><td> 8</td><td> 5</td><td> 13</td><td> 9</td><td> 5</td>
<td>Skin formation time</td><td> 15</td><td> 6</td><td> 4</td><td> 8</td><td> 6</td><td> 2</td>
<td>Resistance to shear due to overlap to 30 minutes, (KPa)</td><td> 9</td><td> 20</td><td> 11,31</td><td> 18</td><td> 20</td><td> 26</td>
<td>at 60 minutes (kPa)</td><td> 19</td><td> 41</td><td> 52</td><td> 47</td><td> 61</td><td> 70</td>
<td>at 90 minutes (kPa)</td><td> 28</td><td> 52</td><td> 71</td><td> 81</td><td> 108</td><td> 131</td>
* Comparative example
Prepolymer preparation
Examples 7 to 10
A polyether-polyurethane prepolymer was prepared by mixing 651.5 g of a polyoxypropylene diol, having an average molecular weight of 2,000, with 947.2 g of polyoxypropylene triol having an average molecular weight of 4,500 and 480 g of a disperse styrene-acrylonitrile. in polyoxypropylene triol, with an average molecular weight of 5,400. The mixing was carried out in a reactor, heating the mixture to 48 ° C. 320 g of diphenylmethane-4,4'-diisocyanate and 0.17 g of stannous octoate were added to the mixture. The whole mixture was then reacted for one hour. Finally, 800 g of a dialkyl phthalate plasticizer was added to the mixture and the mixture was continued for one hour.
Adhesive composition preparation
Examples 7-10
An adhesive composition was prepared using 1,127 g of prepolymer from this example in a planetary mixer, degassed for 20 minutes, 376 g of carbon black and 96 g of clay were added to the mixer and mixed for 20 minutes under vacuum. Finally, 8 g of dimorpholinodiethyl ether (DMDEE) and 4 g of bismuth octoate (OBi) were added, as a catalyst, to the mixture and mixed for
ES 2 179 224 T3 my minutes and it was packed in tubes.
Polyurethane prepolymers and additional adhesive compositions were prepared as described using the components and amounts described in Table III.
TABLE III
<td>Prepolymer Components / Example</td><td>7 (g)</td><td>8 (g)</td><td>9 (g)</td><td>10 * (g)</td>
<td>Polyoxypropylene diol<sup>1</sup></td><td> 651/5</td><td> 320</td><td> 640</td><td> 363,68<sup>4</sup></td>
<td>Polyoxypropylenetriol<sup>2</sup></td><td> 947,2</td><td> 384</td><td> 768</td><td> 527,05<sup>5</sup></td>
<td>SAN dispersed in polyoxypropylenetriol<sup>3</sup></td><td> 480</td><td> 288</td><td> 576</td><td> 0</td>
<td>Diphenylmethane-4,4'-diisocyanate</td><td> 320</td><td> 176</td><td> 320</td><td> 160,0</td>
<td>Stannous octoate</td><td> 0,17</td><td> 0,08</td><td> 0,17</td><td> 0,17</td>
<td>Dialkyl phthalate</td><td> 800</td><td> 432</td><td> 896</td><td> 525,44</td>
<td colspan="5">Adhesive composition</td>
<td>Prepolymer</td><td> 1.127</td><td> 564</td><td> 1.127</td><td> 270,16</td>
<td>Carbon black</td><td> 376</td><td> 188</td><td> 376</td><td> 136,65</td>
<td>Clay</td><td> 96</td><td> 48</td><td> 96</td><td></td>
<td>Dimorpholinodiethyl ether</td><td> 8</td><td> 8</td><td> 8</td><td> 0,95</td>
<td>Bismuth octoate</td><td> 4</td><td> 4</td><td> 4</td><td></td>
<td>Plasticizer</td><td></td><td> 8</td><td> 8</td><td></td>
* Comparative example <sup>1</sup> 2,000 molecular weight - available from Olin Chemical under the trade name Poly G<sup>R</sup> 55-56.
<sup>2</sup> 4,500 molecular weight - available from BASF under the trade name TPE 4542.
<sup>3</sup> Molecular weight 5,400 - available from BASF under the trade name 994 LV.
<sup>4</sup> Polyoxypropylene diol having a molecular weight of 2,000 available from PPG under the trade name PPG 2025.
<sup>5</sup> Polyoxypropylenetriol having a molecular weight of 4,500 available from Olin Chemical under the trade name Poly G 85-36.
In Example 10, the reaction mixture was heated to 55 ° C prior to the addition of the polyisocyanate and catalyst.
The adhesives of Examples 7 to 10 were tested for skinning time and lap shear strength, as described above. The results are presented in Table IV.
IS 2 179 224 T3
TABLE IV
<td>Adhesive</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>Example 10 *</td>
<td>% bismuth octoate</td><td> 0,23</td><td> 0,23</td><td> 0,47</td><td> 0,00</td>
<td>% of DMDEE</td><td> 0,47</td><td> 0,47</td><td> 0,47</td><td> 0,3</td>
<td>% plasticizer</td><td> 0,47</td><td> 0,47</td><td> 0,00</td><td> 0,00</td>
<td>Working time</td><td> 10,5</td><td> 13</td><td> 10</td><td> 20</td>
<td>Overlap shear strength, 30min, kPa</td><td> 82,2</td><td> 119</td><td> 75,4</td><td> 17,1</td>
<td>60 minutes, kPa</td><td> 223</td><td> 256</td><td> 274</td><td> 102</td>
<td>90 minutes, kPa</td><td> 627</td><td> 536</td><td> 587</td><td> 274</td>
* Comparative example.
The comparison of Examples 7 and 10 demonstrate that the use of a styrene-acrylonitrile copolymer dispersed in a triol, when compared to a triol without the copolymer, results in a lower skinning time and shear strengths. highest overlap at 30, 60 and 90 minutes. Example 11
Prepolymer preparation
A polyether-polyurethane prepolymer was prepared by mixing 609.6 g of a polyoxypropylene diol, having an average molecular weight of 2,000, with 862.5 g of a polyoxypropylene triol having an average molecular weight of 4,500 and 435 g of styrene-acrylonitrile, dispersed in polyoxypropylene-triol, with an average molecular weight of 5,400. The mixture was carried out in a reactor, heating the mixture to 48 ° C. 315 g of diphenylmethane-4,4'-diisocyanate and 0.15 g of stannous octoate were added to the mixture. The whole mixture was then reacted for one hour. Finally, 735.6 g of a dialkyl phthalate plasticizer was added to the mixture and the mixture was continued for one hour.
Preparation of adhesive composition
An adhesive composition was prepared, using 2,432.5 g of prepolymer from the above formulation, in a planetary mixer and degassed for 20 minutes under vacuum. 815.5 g of carbon black and 210 g of clay were added to the mixer and mixed for 30 minutes under vacuum. Finally, 17.5 g of dimorpholinodiethyl ether (DMDEE) and 7 g of bismuth octoate (OBi) were added, as a catalyst, to the mixture and the mixture was continued for another 20 minutes.
An adhesive composition, with an encapsulated curing agent, was prepared using 498 g of the adhesive set out in the example above, mixed with 2 g of the encapsulated curing agent. The curing agent had a composition of 20% diethylene glycol and 80% bisoxazolidine (Hardener OZ). The encapsulated curing agent has a curing agent loading of 31% and coating material of 69%, with a mean size distribution between 1,000 and 2,000 µm. The coating material is the same coating material used in Examples 1 to 6.
IS 2 179 224 T3
Behavioral properties of the above adhesive
<td>- Working time</td><td>12 minutes</td>
<td>- Skin formation time</td><td>8 minutes</td>
<td>- Shear resistance</td><td></td>
<td>by overlapping to:</td><td></td>
<td>- 30 minutes</td><td>165 kPa</td>
<td>- 60 minutes</td><td>551 kPa</td>
<td>- 90 minutes</td><td>737 kPa</td>
Contents14
24 members in 14 offices
Priority claims10
| Document | Office | Kind | Date |
|---|---|---|---|
| 19960585143 | United States of America | – | |
| 19960585223 | United States of America | – | |
| 58514396 | United States of America | A | |
| 58514396 | United States of America | A | |
| 58522396 | United States of America | A | |
| 58522396 | United States of America | A | |
| 585143 | – | – | – |
| 585223 | – | – | – |
| US19960585143 | – | – | – |
| US19960585223 | – | – | – |
Members24
| Document | Office | Kind | |
|---|---|---|---|
| CA2242333A1 | Canada | A1 | |
| WO9725360A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU1356297A | Australia | A | |
| EP0873369A1 | European Patent Office (EPO) | A1 | |
| MX9805619A | Mexico | A | |
| CN1209145A | China | A | |
| AR005429A1 | Argentina | A1 | |
| BR9612478A | Brazil | A | |
| US5922809A | United States of America | A | |
| KR19990077153A | Republic of Korea | A | |
| US5976305A | United States of America | A | |
| AU724913B2 | Australia | B2 | |
| US6133398A | United States of America | A | |
| JP2000515173A | Japan | A | |
| EP0873369B1 | European Patent Office (EPO) | B1 | |
| AT224409T | Austria | T | |
| ATE224409T1 | Austria | T1 | |
| DE69623817D1 | Germany | D1 | |
| ES2179224T3This record | Spain | T3 | |
| CN1111552C | China | C | |
| DE69623817T2 | Germany | T2 | |
| KR100496779B1 | Republic of Korea | B1 | |
| JP3988892B2 | Japan | B2 | |
| CA2242333C | Canada | C |
Numbers
- Publication
- 2179224
- Publication, DOCDB
- 2179224
- Publication, EPODOC
- ES2179224T
- Application
- 96945115
- Application, DOCDB
- 96945115
- Application, EPODOC
- ES19960945115T
Titles2
- Spanish
- ADHESIVO DE POLIURETANO CURABLE EN UN COMPONENTE.
- English
- CURABLE POLYURETHANE ADHESIVE IN ONE COMPONENT.
Classification
- CPC, 7
- C08G18/10
- C09J175/04
- C08G18/12
- C08G18/4072
- C08G18/409
- C08G18/4812
- C08G18/40
- IPC, 6
- C08L75 04
- C08G18 10
- C08G18 12
- C08G18 40
- C08G18 48
- C09J175 04