JP2011505481A - One component polyurethane adhesive - Google Patents

Abstract

The present invention seeks to provide an adhesive mixture that is easy to handle, and more particularly, an adhesive mixture that enables optimal orientation of a member to be bonded for a building.
The objects are: a) a polyisocyanate, b) a relatively high molecular weight compound having a group that reacts with isocyanate, c) a foaming agent, d) a foam control additive, e) a catalyst, and f) as appropriate. And an isocyanate group-containing adhesive mixture obtained by mixing with other additives and using polyisocyanate a) in an amount such that it contains more isocyanate groups than groups which react with isocyanates. A method of adhering an article by applying to at least one article to be adhered, wherein the foam control additive (d) comprises silicone oil, and the adhesive mixture is immediately applied to the adhesive area after decompression This is achieved by the method applied to
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Description

  The present invention relates to a) polyisocyanates, b) relatively high molecular weight compounds having groups that react with isocyanates, c) blowing agents, d) foam control additives, e) catalysts, and f) An isocyanate group-containing adhesive mixture obtained by mixing with an additive and using polyisocyanate a) in such an amount that it contains more isocyanate groups than the group that reacts with isocyanate is adhered from a high pressure vessel. A method of adhering an article by applying to at least one article, wherein the foam control additive (d) comprises silicone oil and the adhesive mixture is applied immediately to the adhesive area after decompression Regarding the method.

  Further embodiments of the invention are apparent from the claims, the description and the examples. It will be understood that the above-described features of the inventive subject matter, as further described below, can be used not only in the respective combinations described, but also in other combinations without departing from the scope of the present invention. The

  One-component polyurethane foam from aerosol containers is often a steel for the installation of building doors or windows, and also a filling material for cavities or openings in buildings through walls for pipe installation Assembling means adopted as This type of aerosol container contains a NCO-terminated polyurethane prepolymer with a blowing agent and an adjuvant. The required foam is produced through discharge of the contents with a blowing agent and through subsequent foaming and curing of atmospheric moisture. Mainly these forms are used as assembly forms. A great advantage of such assembled foams is their ease of handling.

  One such one-component assembly form is described in Patent Document 1, for example. In addition to its use as an assembled foam, it can also be used as a spray adhesive, for example, for the assembly of window and door posts or for the filling of hollow foam. In that case, for example, the insulating plate and the roof covering are bonded to each other or to the substrate.

  A drawback to the use of known one-component assembled foams as adhesives is that following their application, they tend to undergo post-expansion. In other words, the bubbles continue to foam at the adhesive joint, so that the bonded articles do not stay in their predetermined positions. In particular, in the case of adhesion between the heat insulating plate and the exterior surface of the building, a non-flat surface can be formed on the completed surface.

WO2005 / 054324

  It was therefore an object of the present invention to provide an adhesive mixture that is easy to handle, and more particularly, an adhesive mixture that allows for optimal orientation of a member to be bonded for a building. More specifically, it was an object of the present invention to provide a method of bonding articles with an adhesive mixture that is free of post-expansion.

  Surprisingly, the objects described by the present invention are: a) a polyisocyanate, b) a relatively high molecular weight compound having a group that reacts with isocyanate, c) a blowing agent, d) a foam control additive, e An isocyanate group-containing adhesive which is obtained by mixing with other additives, and is used in such an amount that the polyisocyanate a) contains more isocyanate groups than groups which react with isocyanates. A method of adhering an article by applying an agent mixture from a high pressure container to at least one article to be adhered, wherein the foam control additive (d) comprises silicone oil and the adhesive mixture is This is achieved by a method characterized in that it is applied to the adhesive area immediately after depressurization.

  The adhesive mixture of the present invention is applied from the high pressure container to the article to be bonded. This adhesive mixture may be applied to the article to be bonded exclusively by vigorous internal pressure inside the aerosol can. This internal pressure is produced by evaporation or decompression of the propellant gas mixture. An alternative possibility is to release the adhesive mixture from the aerosol can with the help of a gas (eg compressed air) under pressure and apply the adhesive mixture to the bonded area of the article to be bonded. . In this case, it is essential for the present invention that the foam control additive (d) contains silicone oil and the adhesive mixture is applied immediately after decompression. This is the case, for example, when the adhesive mixture according to the invention is applied from a pressure vessel with the aid of a metering gun. For such a metered hand gun, the entire gun content is the same pressure as the momentum inside the pressure vessel. Where the contents of the pressure vessel are subjected to discharge, i.e., the valve opens from its gun to the outlet, and substantially at this valve the pressure drops to external pressure. The effect according to the invention is not achieved when the adhesive mixture first passes after a pressure drop has occurred, for example when passing through a metering tube.

  Examples of suitable polyisocyanates include aliphatic, cycloaliphatic, and more particularly aromatic diisocyanates or polyisocyanates. Specific examples are: hexamethylene 1,6-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, at least two of the above-mentioned C6 alkylene diisocyanates, pentamethylene 1, Aliphatic diisocyanates such as 5-diisocyanate and mixtures of butylene 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), cyclohexane 1,4-diisocyanate , 1-methylcyclohexane 2,4- and 2,6-diisocyanates and the corresponding mixtures of isomers, dicyclohexylmethane 4,4 ′-, 2,4′- and 2,2′-diisocyanates and also the corresponding Different A cycloaliphatic diisocyanate such as a mixture of bodies, preferably naphthalene 1,5-diisocyanate (1,5-NDI), tolylene 2,4- and 2,6-diisocyanate (TDI), and mixtures thereof Aromatic diisocyanates such as 2,4′-, 2,2′-, and preferably 4,4′-diisocyanate (MDI), and also mixtures of at least two of these isomers, 2 or more Polyphenyl-polymethylene-polyisocyanate (polymeric MDI, PMDI), a mixture of PMDI and tolylene diisocyanate, polyphenyl polyisocyanate, urethane-modified liquid diphenylmethane 4,4'- and / or 2,4 Diisocyanates and 1,2-bis (4-isocyanatopheny ) Including ethane.

  It is also possible to use isocyanate prepolymers or low monomer isocyanates as polyisocyanates a), for example as described in EP1518874, WO2005 / 054324 or DE10311607.

  As isocyanate prepolymers, it is possible to use reaction products from the reaction of at least one diisocyanate and / or polyisocyanate and / or a compound which reacts with at least one isocyanate with at least one diisocyanate and / or polyisocyanate. The production of these isocyanate-functional prepolymers can be carried out by known methods. As a reaction product containing an isocyanate group, it is preferable to use a prepolymer having an NCO content of 4 to 30%.

The use is more particularly made as polyisocyanates a) of PMDI having a viscosity at 25 ° C. of preferably less than 600 mPas, more preferably 100 to 400 mPas and particularly preferably 150 to 300 mPas. Use, more specifically,
35 ± 17% by weight of 2-ring MDI, 26 ± 6% by weight of 3-ring MDI, 12 ± 4% by weight of 4-ring MDI, 5 ± 3% by weight of 5-ring MDI, 23% of 6-ring MDI Crude MDIs containing ± 10% by weight and further polycyclic MDIs are made.

  As relatively high molecular weight compounds b) having groups which react with isocyanates, typical compounds having groups which react with isocyanates can be used. It is preferred to use polyetherols and / or polyesterols, more specifically polyetherols.

  The polyetherols of the present invention can be obtained by known methods, for example, by anionic polymerization of an alkali metal hydroxide or alkali metal alkoxide as a catalyst and the addition of at least one starting molecule containing 2 to 4 bonded hydrogen atoms. Alternatively, it is prepared by cationic polymerization with a Lewis acid such as antimony pentachloride or boron fluoride-etherate containing one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene group. Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, and preferably ethylene oxide and 1,2-propylene oxide. Further, as the catalyst, a composite metal cyanide compound known as a DMC catalyst can be used. The alkylene oxides can each be used alternately one after the other or as a mixture. It is preferred to use a mixture of 1,2-propylene oxide and ethylene oxide, which ethylene oxide end block ("EO cap") such that the resulting polyol has 70% or more primary OH end groups. ")" Is used in an amount of 10 to 50% in the shape.

  Suitable starting molecules are water or 2-, 3- and 4-valent, preferably trivalent alcohols such as glycerol, trimethylolpropane, ethanolamine, diethanolamine, triethanolamine, and other trihydric alcohols. Or an amine having three active hydrogen atoms.

  The polyether polyol, preferably polyoxypropylene-polyoxyethylene polyol, has a functionality of 2 to 4, preferably 2.5 to 3.5, more preferably 2.6 to 3.4, preferably Has a number average molecular weight of 600 to 8000 g / mol, more preferably 1000 to 6000 g / mol, more particularly 1000 to 4000 g / mol.

  As a compound having a relatively high molecular weight and having a group which reacts with isocyanate, b), polyetherol (b1) produced from a trifunctional starting material having a number average molecular weight of 4000 ± 2000 g / mol, 1000 Polyethers produced from trifunctional starting materials having an average molecular weight of ± 200 g / mol (b2) and poly produced from bifunctional starting materials (b3) having a number average molecular weight of 600 ± 100 g / mol A mixture of etherols is preferred. Particularly preferably, as polyetherols (b1) produced from trifunctional starting materials, polyetherols produced from glycerol based on propylene oxide and ethylene oxide are produced from trifunctional starting materials. Polyetherols (b2) based on propylene oxide and ethylene oxide, polyetherols prepared starting from glycerol, and polyetherols (b3) prepared from difunctional starting materials based on ethylene oxide, Polyetherols produced starting from ethylene glycol are used. In this case, the mass ratio of (b1) :( b2) :( b3) is preferably 4 ± 1: 8 ± 2: 1 ± 0.5.

  The compound b) having a relatively high molecular weight and having a group which reacts with isocyanate further has a molecular weight of 350 to 1000 g / mol, more preferably 450 to 600 g / mol and preferably has a functionality of 2 to 4. Brominated polyetherols having the following may be included. More particularly, as brominated polyether polyols, polyols that are prepared from difunctional and / or trifunctional starting materials and are based on epichlorohydrin and brominated to remove chlorine and hydrogen Is used. Suitable brominated polyetherols are commercially available, for example, under the trade name IXOL® from Solvay. More specifically, IXOL® M125 and IXOL® B251 can be used as brominated polyetherols.

  In addition to the polyols described above, compounds having a relatively high molecular weight and a group that reacts with isocyanates, b) are further customary hydroxy-functional compounds such as ethylene glycol, propylene glycol as chain extenders, Short chain diols such as butane-1,4-diol, short chain alcohols having at least three functionalities such as glycerol or trimethylolpropane as crosslinking agents, and / or monools as molecular weight regulators But it ’s okay. It is preferred that no chain extender, crosslinker, or molecular weight modifier be present.

  Examples of the blowing agent include compounds having a boiling point in the range of −40 ° C. to 120 ° C. under atmospheric pressure, gaseous and / or liquid blowing agents such as carbon dioxide, isobutane, propane, n-butane or isobutane, and pentane. , And cycloalkanes and / or cycloalkanes such as diethyl ether, methyl isobutyl ether, and ethers such as dimethyl ether, nitrogen, oxygen, helium, argon, laughter, halogenated hydrocarbons such as dichlorofluoro Halogenated hydrocarbons such as methane, monofluorotrifluoromethane, trifluorotrichloroethane and / or, for example, trifluoromethane, 1,1-dichloro-1-fluoroethane, monochlorotetrafluoroethane, monochlorotrifluoroethane, monochrome Known blowing agents such as partially halogenated hydrocarbons such as uroethane, difluoroethane, dichlorodifluoroethane, pentafluoroethane, tetrafluoroethane, or dichloromonofluoroethane, or these Mixtures containing at least two of the exemplified blowing agents can be used.

  Typically, the blowing agent is added in an amount of 0.5 to 40% by weight, preferably 10 to 32% by weight, based on the weight of components a) to f).

  As the foam control additive d), all known foam control additives including silicone oil can be used. In this connection, it is preferable to use dimethylsiloxane having a viscosity at 25 ° C. of 10 to 1000 mPas. Furthermore, like silicone oil, the foam control additive d) may contain typical foam stabilizers and / or liquid paraffin. A saturated aliphatic hydrocarbon can be used as the liquid paraffin. The liquid paraffin used is preferably liquid at 25 ° C. Foam stabilizers that can be used include, for example, polyalkylene glycol polysiloxane copolymers, preferably Goldschmidt's product under the trade name Tegostab®, more preferably Tegostab® B2219 or Tegostab. (Registered trademark) BF2270.

  A particularly preferred mass of foam stabilizer, silicone oil, and liquid paraffin is 150 ± 50: 2 ± 1.2: 2 ± 1.2. The proportion of foam control additive d) is preferably 0.5-5% by weight, more preferably 1-3% by weight, based on the total weight of components a) -f). The proportion of silicone oil is preferably 0.02 to 0.2% by weight, based on the total weight of components a) to f).

  As catalyst e), more particularly as catalyst e) for accelerating the reaction between the NCO group of the diisocyanate and the hydroxyl group of the polyalcohol, the typical prior art, for example 2,3-dimethyl-3, Strong bases such as 4,5,6-tetrahydropyrimidine, tris (dialkylaminoalkyl) -s-hexahydrotriazine (for example, tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine) Amides, and preferably triethylamine, tributylamine, dimethylbenzylamine, N-ethyl, N-methyl, n-cyclohexylmorpholine, dimethylcyclohexylamine, dimorpholinodimethyl ether, 2- (dimethylaminoethoxy) ethanol, 1,4-diazabicyclo [2.2.2] Octane, 1-a Bicyclo [3.3.0] octane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylbutanediamine, N, N, N ′, N′-tetra Methylhexane-1,6-diamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, N, N'-dimethylpiperazine, 1,2-dimethylimidazole, di (4-N, N- Typical tertiary amines such as dimethylaminocyclohexyl) methane, and the like, and also iron compounds such as titanium esters, iron (III) acetylacetonate, for example tin compounds such as , Tin (II) salts of organic carboxylic acids (eg tin (II) diacetate, 2-ethylhexanoic acid) Tin (II) salt of (tin (II) octoate), tin (II) dilaurate, or, for example, dibutyltin (IV) diacetate, dibutyltin (IV) dilaurate, dibutyltin (IV) malate, diacetyltin (IV) diacetyl Use organometallic compounds such as acetate, or the like, and also dibutyltin (IV) dimercaptide or a mixture of at least two of the above-described catalysts, and also a cooperative combination of strong base amines and organometallic compounds be able to. Particular preference is given to using dimorpholinodiethyl ether as catalyst e). Catalyst e) can be used, for example, in a typical amount of 0.002 to 5% by weight, based on b) a compound having a relatively high molecular weight and a group that reacts with isocyanate.

  Auxiliaries and additives f) include, for example, fillers, flame retardants, nucleating agents, oxidation inhibitors, dyes and pigments, reaction inhibitors, stabilizers against hydrolysis, light, heat or fading, organic and / or Alternatively, inorganic fillers, reinforcing agents, and / or plasticizers can be used.

  Further details of the abovementioned auxiliaries and additives can be found in the technical literature, e.g. H. Saunders and K.C. C. Frisch research book "High Polymers", Volume 16, Polyethanes Part 1 and 2 (Interscience Publishers 1962 and 1964), "Kunststoff-Handbuch", Volume 7, Polythenes, 3rd Edition, 1993 Oertel, Carl-Hanser-Verlag, Munich), or DE 2901774.

In order to produce the adhesive mixture according to the invention, the isocyanate a) has a relatively high molecular weight compound b), a foaming agent c), a foam control additive d), a catalyst e). , And, where appropriate, with other additives f) are introduced into the container, the container is sealed and components a) to f) are homogenized. In this case, polyisocyanate a) is used in excess compared to the group which reacts with isocyanate.
Preferably, components a) to f) are introduced separately into the pressure vessel, after which the pressure vessel is sealed and the components are homogenized, for example by shaking. Otherwise, the reaction of polyisocyanate a), compound b) having a high molecular weight and a group capable of reacting with isocyanate, and catalyst e) may be carried out outside the pressure vessel. The resulting reaction product is then introduced into the pressure vessel along with the blowing agent c), the foam control additive d), and optionally other additives f).

  The method of the invention is remarkably suitable for the adhesion of articles, in particular for building components, and more particularly for inorganic substrates. In this application, a feature of the adhesive mixture of the present invention is that there is no post-expansion of the bondline. Thereby, the method of the present invention is more particularly suitable for the adhesive of the exterior part, for example, an exterior material or an inorganic material such as mortar, stone, or other components of building materials. It is suitable for application of a heat insulating plate. Such a bonded article will remain in the selected position, leading to an increased likelihood of optimal orientation of the cladding, for example.

  The invention is illustrated below by means of examples.

Manufacture of polyol component Polyetherol produced from glycerol as a starting material based on propylene oxide and ethylene oxide, 330 g of polyetherol having a number average molecular weight of 1000 g / mol, glycerol as a starting material, and propylene oxide Polyetherol produced on the basis of ethylene oxide with a number average molecular weight of 4000 g / mol, 147 g / mol of polyetherol and 40 g of polyethylene glycol with a number average molecular weight of 600 g / mol, approximately 31% by weight Brominated polyether triol having a bromine content of 60 grams of Solvay trade name “Ixol® B251” and a foam stabilizer (trade name Tegostab® B2219 of Goldschmidt) 25 g of all polysiloxane-polyoxyalkylene block copolymers, 0.3 g of Bayerone's Baysilone® M100 trade name polydimethylsiloxane, 60 g of diacetone alcohol, 8 g of 2,2-dimorpholinodiethyl ether as catalyst Is mixed with 330 g of trichloropropyl phosphate to produce a polyol component.

Preparation of the adhesive mixture in an aerosol container A 1 L aerosol can is filled with 286 g of the polyol component described above, and also 394 g of PMDI having a viscosity of approximately 200 mPas at 25 ° C. Seal the aerosol can with a gun valve. Next, an aerosol can is metered through the valve with 43 g of dimethyl ether, 27 g of an industrial gas mixture of 30% propane and 70% by weight butane, and finally 79 g of tetrafluoroethane (R134a). To do.

  Homogenize the contents of the can by vigorous shaking. A prepolymer reaction that results in warming of the aerosol can results.

  After storage for 24 hours under high temperature conditions up to 50 ° C., the prepolymerization reaction is completed to the extent that the contents can be used as an adhesive.

Use as a one-component adhesive An aerosol can is screwed onto a foam gun and the contents of the can are homogenized by shaking. Through the gun firing operation, the generated foam mixture is applied to the surface of the heat insulating plate in the form of a foam string having a width of about 3 cm.

Flatten out a crushing foam with a somewhat coarse foam in a string to allow for sufficient adhesion. The insulation board with the adhesive foam is then fixed to the concrete wall. There is no post-expansion and the insulation plate remains in place.

Claims (9)

a) Polyisocyanate
b) a relatively high molecular weight compound having a group which reacts with isocyanate,
c) blowing agent,
d) foam control additive,
e) a catalyst, and f) an isocyanate group which is obtained by mixing with other additives as appropriate and is used in such an amount that the polyisocyanate a) contains more isocyanate groups than groups which react with isocyanates. A method of adhering an article by applying a containing adhesive mixture from a high pressure vessel to at least one article to be adhered,
A method for adhering an article, wherein the foam control additive (d) comprises silicone oil and the adhesive mixture is applied immediately after decompression.   The method of claim 1, wherein the foam control additive d) comprises liquid paraffin, foam stabilizer, and silicone oil.   3. The foam control additive d) comprises a foam stabilizer, silicone oil, and liquid paraffin in a mass ratio of 150 ± 50: 2 ± 1.2: 2 ± 1.2. the method of. A relatively high molecular weight compound b) having a group that reacts with the isocyanate,
A polyether polyol b1) having an average functionality of 2.9 ± 0.4 and a number average molecular weight of 4000-600 g / mol;
4. A process according to any one of claims 1 to 3, characterized in that it comprises a mixture comprising a brominated polyether polyol b2) having a number average molecular weight of 500 ± 100 g / mol. Polyether polyol b1)
Polyetherols based on propylene oxide and ethylene oxide, produced starting from glycerol and having a number average molecular weight of 4000 ± 2000 g / mol;
Polyetherols based on propylene oxide and ethylene oxide, produced starting from glycerol and having a number average molecular weight of 1000 ± 200 g / mol;
5. A mixture of polyetherols based on ethylene oxide and starting from ethylene glycol and containing a number average molecular weight of 600 ± 100 g / mol. The method described.   6. Process according to any one of the preceding claims, wherein the catalyst e) comprises dimorpholine diethyl ether.   7. Process according to any one of the preceding claims, characterized in that the polyisocyanate a) is PMDI having a viscosity of less than 500 mPas at 25 [deg.] C.   The method according to any one of claims 1 to 7, wherein the article is adhered to an inorganic substrate.   The method according to claim 1, wherein the exterior material or the heat insulating plate is bonded to the building.