CA2021308A1 - Two-component polyurethane adhesive - Google Patents
Two-component polyurethane adhesiveInfo
- Publication number
- CA2021308A1 CA2021308A1 CA002021308A CA2021308A CA2021308A1 CA 2021308 A1 CA2021308 A1 CA 2021308A1 CA 002021308 A CA002021308 A CA 002021308A CA 2021308 A CA2021308 A CA 2021308A CA 2021308 A1 CA2021308 A1 CA 2021308A1
- Authority
- CA
- Canada
- Prior art keywords
- adhesive
- component
- isocyanate
- weight
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6529—Compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6552—Compounds of group C08G18/63
- C08G18/6558—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/657—Compounds of group C08G18/63 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
Abstract
Mo3417 LeA 27,094 A TWO-COMPONENT POLYURETHANE ADHESIVE
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a two-component polyurethane adhesive containing a) an isocyanate component, b) an isocyanate-reactive component, and a catalyst for the reaction of a) and b), characterized in that the catalyst used is a compound corresponding to the following formula:
wherein R1 and R2 may be the same or different and represent C1 to C4 alkyl, R3 is a CHO group, H, or a C1 to C4 alkyl optionally substituted by a CHO group, n is an integer of 2 to 4, o is 1 or 2, p is o or 1, and o + p = 2.
Mo3417
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a two-component polyurethane adhesive containing a) an isocyanate component, b) an isocyanate-reactive component, and a catalyst for the reaction of a) and b), characterized in that the catalyst used is a compound corresponding to the following formula:
wherein R1 and R2 may be the same or different and represent C1 to C4 alkyl, R3 is a CHO group, H, or a C1 to C4 alkyl optionally substituted by a CHO group, n is an integer of 2 to 4, o is 1 or 2, p is o or 1, and o + p = 2.
Mo3417
Description
Mo3417 LeA 27,094 A TWO-COMPONENT POLYURETHANE ADHESIVE
BACKGROUND OF THE INVENTION
This invention relat~s to two-component polyurethane adhesives and to a process for bonding materials using the s adhesives according to the invention.
Two-component polyurethane adhesives are known. Thus, U.S. patent 3,274,160 describes the reaction products of polyisocyanates with a mixture containing alcoholic hydroxyl functions. U.S. patents 3,591,561 and 3,725,355 describe the o production of polyurethane elastomers. In the first case, a lactone polyester polyol and a low molecular weight diol are reacted with an organic diisocyanate and the reaction product is crosslinked with a diamine or a polyol, such as glycerol for example. In the second case, the polyurethane elastomer is obtained from polyether polyol, a chain-extending agent and an isocyanate prepolymer using a tin catalyst. U.S. patent 3,577,295 describes polyurethane elastomers for drive belts using polyol mixtures containing polymers of unsaturated monomers, organ;c polyisocyanates and amines as curing agents.
U.S. patent 4,182,898 describes polyurethanes of polyester polyol prepolymers which are reacted with diisocyanates in admixture with low molecular weight polyols. U.S. patent 4,193,832 describes the reaction of polyisocyanates with isocyanate-reactive compounds, in which tertiary amines may serve as catalysts. A process for the production of polyurethane adhesives using excess diisocyanate, polyols and, optionally, chain-extending agents, such as amines for example, is described in U.S. patent 4,156,064. U.S. patents 3,979,364, 4,336,298 and 4,444,g76 and European patent 63,534 relate specifically to the use of amines for producing "nonsagging"
adhesives.
U.S. patent 4,487,909 describes an adhesiYe based on a polyol, for example a polyether polyol, and glycerol as 35376JCGl140 3~
branching agent. U.S. patent 4,530,941 describes a RIM
polyurethane mixture consisting of a high molecular weight polyol, a chain-extending agent, an amine-terminated polyoxyalkylene and a polyisocyanate. U.S. patent 4,55~,340 s describes a polyol mixture ~or the production of polyurethanes from high molecular weight polyalkylene oxide and low molecular weight diol and, optionally, isocyanate-reactive compounds, such as glycerol and diamine. U.S. patent 4,568,717 describes the production of polyurethanes from organic polyisocyanates using a terephthalic acid polyester polyol. U.S. patent 3,714,127 describes two-component polyurethane adhesives based on an isocyanate prepolymer to which an amine is added to increase viscosity and to guarantee non-sagging behavior.
European patent 68,209 describes a two-component polyurethane adhesive with a polyol component which contains a polyester or polyether triol, a phenylene diamine and a tin catalyst. This mixture is reacted with an aromatic diisocyanate.
European patent 248,254 describes a two-component 20 . polyurethane adhesive which is the reaction product of a hydroxyl-~unctional material, a diamine or triamine and an organic isocyanate. The adhesives thus produced are distinguished by excellent properties, but are not entirely satisfactory in regard to high-frequency or microwave curing.
Curing processes such as these are typically used in the production of automotive body parts.
Accordingly, the problem addressed by the present invention was to provide a two-component adhesive system which showed improved high-frequency or microwave curing behavior.
At the same time, however, the system was also to be suitable for curing at room temperature.
Description of the Invention The present invention relates to a two-component polyurethane adhesive containing a) an isocyanate component, b) an isocyanate-reactive component and a catalyst for the Mo3417 2~2 ~ 3~
reaction of a) and b), characterized in that the catalyst used is a compound corresponding to the following formula R ~3 0 3 wherein R1 and R2 may be the same or different and represent C~ to C4 alkyl, particularly methyl and ethyl, R is a CH0 group, H, or Cl to C4 alkyl optionally substituted by a CH0 group, n is an integer of 2 to 4, o is 1 or 2, p is 0 or 1, and o + p = 2.
In one preferred embodiment, component b) comprises:
1) 100 parts by weight of at least one hydroxyl-containing compound having a molecular weight of at least 400 and a hydroxyl funct;onality of at least 2, 2) 2 to 20 parts by weight of at least one aliphatic, aromatic or cycloaliphatic diamine or triamine having a molecular weight of at least 60 and, optionally 3) 5 to 40 parts by weight of at least one hydroxyl-containing low molecular weight chain-extending agent having a molecular weight of at least 62 and a functionality of at least 2.
In one preferred embodiment, components a) and b) also contain typical aux;liaries and additives. In one particularly preferred embodiment, the catalyst is present in component b3.
The catalyst is preferably used in such a quantity that at Mo3417 2~2~ 8 least 0.005 9 tertiary amine nitrogen is present in component b) per 100 g, taking into account any tertiary nitrogen present in component b)l), b~2) and/or b)3) .
Suitable isocyanate components are, above all, compounds 5 corresponding to the following forMula:
Q (NCo)n wherein n = 2 - 4, preferably 2, and o Q is an aliphatic hydrocarbon radical containing 2 to 18 (preferably 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15 (pre~erably 5 to 10) carbon atoms, an aromatic hydrocarbon radical containing 6 to 15 (preferably 6 to 13) carbon atoms or an araliphatic hydrocarbon radical containing 8 to 15 (preferably 8 to 13) carbon atoms.
Particularly preferred isocyanates are hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-20 diisocyanate; cyclohexane-1,3- and -t,4-diisocyanate and mixtures of these isomers; l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane; hexahydro-1,3- and/or -1,4-phenylene diisocyanate; perhydro-~,4'- and/or -4,4'-diphenylmethane diisocyanate; 1,3- and 1,4-phenylene 25 diisocyanate; 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers; diphenylmethane-2,4'- and/or -4,4'-diisocyanate; naphthylene-1,5-diisocyanate;
triphenylmethane-4,4',4"-triisocyanate; and polyphenyl polymethylene polyisocyanates of the type obtained by 30 phosgenation of aniline-formaldehyde condensates.
Suitable relatively high molecular weight polyisocyanates are modification products of the above isocyanates, such as polyisocyanates containing isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units. These modified isocyanates are prepared by methods generally known in Mo3417 2 ~ 3 ~ ~
BACKGROUND OF THE INVENTION
This invention relat~s to two-component polyurethane adhesives and to a process for bonding materials using the s adhesives according to the invention.
Two-component polyurethane adhesives are known. Thus, U.S. patent 3,274,160 describes the reaction products of polyisocyanates with a mixture containing alcoholic hydroxyl functions. U.S. patents 3,591,561 and 3,725,355 describe the o production of polyurethane elastomers. In the first case, a lactone polyester polyol and a low molecular weight diol are reacted with an organic diisocyanate and the reaction product is crosslinked with a diamine or a polyol, such as glycerol for example. In the second case, the polyurethane elastomer is obtained from polyether polyol, a chain-extending agent and an isocyanate prepolymer using a tin catalyst. U.S. patent 3,577,295 describes polyurethane elastomers for drive belts using polyol mixtures containing polymers of unsaturated monomers, organ;c polyisocyanates and amines as curing agents.
U.S. patent 4,182,898 describes polyurethanes of polyester polyol prepolymers which are reacted with diisocyanates in admixture with low molecular weight polyols. U.S. patent 4,193,832 describes the reaction of polyisocyanates with isocyanate-reactive compounds, in which tertiary amines may serve as catalysts. A process for the production of polyurethane adhesives using excess diisocyanate, polyols and, optionally, chain-extending agents, such as amines for example, is described in U.S. patent 4,156,064. U.S. patents 3,979,364, 4,336,298 and 4,444,g76 and European patent 63,534 relate specifically to the use of amines for producing "nonsagging"
adhesives.
U.S. patent 4,487,909 describes an adhesiYe based on a polyol, for example a polyether polyol, and glycerol as 35376JCGl140 3~
branching agent. U.S. patent 4,530,941 describes a RIM
polyurethane mixture consisting of a high molecular weight polyol, a chain-extending agent, an amine-terminated polyoxyalkylene and a polyisocyanate. U.S. patent 4,55~,340 s describes a polyol mixture ~or the production of polyurethanes from high molecular weight polyalkylene oxide and low molecular weight diol and, optionally, isocyanate-reactive compounds, such as glycerol and diamine. U.S. patent 4,568,717 describes the production of polyurethanes from organic polyisocyanates using a terephthalic acid polyester polyol. U.S. patent 3,714,127 describes two-component polyurethane adhesives based on an isocyanate prepolymer to which an amine is added to increase viscosity and to guarantee non-sagging behavior.
European patent 68,209 describes a two-component polyurethane adhesive with a polyol component which contains a polyester or polyether triol, a phenylene diamine and a tin catalyst. This mixture is reacted with an aromatic diisocyanate.
European patent 248,254 describes a two-component 20 . polyurethane adhesive which is the reaction product of a hydroxyl-~unctional material, a diamine or triamine and an organic isocyanate. The adhesives thus produced are distinguished by excellent properties, but are not entirely satisfactory in regard to high-frequency or microwave curing.
Curing processes such as these are typically used in the production of automotive body parts.
Accordingly, the problem addressed by the present invention was to provide a two-component adhesive system which showed improved high-frequency or microwave curing behavior.
At the same time, however, the system was also to be suitable for curing at room temperature.
Description of the Invention The present invention relates to a two-component polyurethane adhesive containing a) an isocyanate component, b) an isocyanate-reactive component and a catalyst for the Mo3417 2~2 ~ 3~
reaction of a) and b), characterized in that the catalyst used is a compound corresponding to the following formula R ~3 0 3 wherein R1 and R2 may be the same or different and represent C~ to C4 alkyl, particularly methyl and ethyl, R is a CH0 group, H, or Cl to C4 alkyl optionally substituted by a CH0 group, n is an integer of 2 to 4, o is 1 or 2, p is 0 or 1, and o + p = 2.
In one preferred embodiment, component b) comprises:
1) 100 parts by weight of at least one hydroxyl-containing compound having a molecular weight of at least 400 and a hydroxyl funct;onality of at least 2, 2) 2 to 20 parts by weight of at least one aliphatic, aromatic or cycloaliphatic diamine or triamine having a molecular weight of at least 60 and, optionally 3) 5 to 40 parts by weight of at least one hydroxyl-containing low molecular weight chain-extending agent having a molecular weight of at least 62 and a functionality of at least 2.
In one preferred embodiment, components a) and b) also contain typical aux;liaries and additives. In one particularly preferred embodiment, the catalyst is present in component b3.
The catalyst is preferably used in such a quantity that at Mo3417 2~2~ 8 least 0.005 9 tertiary amine nitrogen is present in component b) per 100 g, taking into account any tertiary nitrogen present in component b)l), b~2) and/or b)3) .
Suitable isocyanate components are, above all, compounds 5 corresponding to the following forMula:
Q (NCo)n wherein n = 2 - 4, preferably 2, and o Q is an aliphatic hydrocarbon radical containing 2 to 18 (preferably 6 to 10) carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15 (pre~erably 5 to 10) carbon atoms, an aromatic hydrocarbon radical containing 6 to 15 (preferably 6 to 13) carbon atoms or an araliphatic hydrocarbon radical containing 8 to 15 (preferably 8 to 13) carbon atoms.
Particularly preferred isocyanates are hexamethylene diisocyanate; 1,12-dodecane diisocyanate; cyclobutane-1,3-20 diisocyanate; cyclohexane-1,3- and -t,4-diisocyanate and mixtures of these isomers; l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane; hexahydro-1,3- and/or -1,4-phenylene diisocyanate; perhydro-~,4'- and/or -4,4'-diphenylmethane diisocyanate; 1,3- and 1,4-phenylene 25 diisocyanate; 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers; diphenylmethane-2,4'- and/or -4,4'-diisocyanate; naphthylene-1,5-diisocyanate;
triphenylmethane-4,4',4"-triisocyanate; and polyphenyl polymethylene polyisocyanates of the type obtained by 30 phosgenation of aniline-formaldehyde condensates.
Suitable relatively high molecular weight polyisocyanates are modification products of the above isocyanates, such as polyisocyanates containing isocyanurate, carbodiimide, allophanate, biuret or uretdione structural units. These modified isocyanates are prepared by methods generally known in Mo3417 2 ~ 3 ~ ~
the art. Among the modified polyisocyanates, the isocyanate terminated prepolymers having molecular weights of from 400 to 10,000, preferably from 600 to 8,000 and more preferably from 800 to 5,000 are of particular interest. These modified 5 isocyanates are prepared in known manner by reaction of excess quantities of isocyanates of the type mentioned above with organic compounds containing at least two isocyanate-reactive groups, particularly organic polyhydroxyl compounds. Suitable polyhydroxyl compounds are both simple polyhydric alcohols o having molecular weights in the range from 62 to 599 (preferably from 62 to 200), such as for example ethylene glycol, trimethylol propane, propane-1,2-diol or butane-1,2-diol, and relatively high molecular weight polyether polyols and/or polyester polyols of the type known per se from 15 polyurethane chemistry with molecular weights in the range from 600 to 8,000 (preferably from 800 to 4,000) which contain at least 2, and generally 2 to 8 (preferably 2 to 4), primary and/or secondary hydroxyl groups. It is of course also possible to use NCO prepolymers which have been obtained, for 20 . example, from low molecular weight polyisocyanates and compounds containing isocyanate-reactive groups such as, for example, polythioether polyols, hydroxyl-containing polyacetals, polyhydroxy polycarbonates, hydroxyl-containing polyester amides or hydroxyl-containing copolymers of 25 olefinically unsaturated compounds. Compounds containing isocyanate-reactive groups, particularly hydroxyl groups, suitable for the preparation of the NCO prepolymers are, for example, the compounds disclosed by ~ay of example in U.S.
patent 4,218,543, column 7, line 29 to column 9 line 25. In 30 the preparation of the NCO prepolymers, these compounds containing isocyanate-reactive groups are reacted with isocyanates at an NCO:OH equivalent ratio maintained at about - 1.5:1 to 20:1 and preferably at 5:1 to 15:1. The NCO
prepolymers generally have an NCO content of from 2.5 to 25% by 35 weight and preferably from 6 to 22% by weight. In the context Mo3417 2~2~
patent 4,218,543, column 7, line 29 to column 9 line 25. In 30 the preparation of the NCO prepolymers, these compounds containing isocyanate-reactive groups are reacted with isocyanates at an NCO:OH equivalent ratio maintained at about - 1.5:1 to 20:1 and preferably at 5:1 to 15:1. The NCO
prepolymers generally have an NCO content of from 2.5 to 25% by 35 weight and preferably from 6 to 22% by weight. In the context Mo3417 2~2~
of the present invention, "NCO prepolymers" or "isocyanate-terminated prepolymers" are understood to be both the reaction products as such and also mixtures thereof with excess quantities of unreacted starting polyisocyanates which s are often also referred to as "semi-" or "quasi-" prepolymers.
Particularly preferred isocyanates as component a) for the process according to the invention are the commercially available polyisocyanates typically used in polyurethane chemistry, such as hexamethylene diisocyanate;
o 1-isocyanato-3,3,~-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate or IPDI); 4,4'-diisocyanatodicyclo-hexyl methane; 2,4-diisocyanatotoluene, and mixtures thereof with 2,6-diisocyanatotoluene; 4,4'-diisocyanato-diphenyl-methane, and mixtures thereof with the corresponding 2,4'- and 15 2,2'-isomers; polyisocyanate mixtures of the diphenylmethane series, of the type obtained by phosgenation of aniline/formaldehyde condensates; the biuret- or isocyanurate-containing modification products of these polyisocyanates; NCO prepolymers of the type mentioned based on 20 . these polyisocyanates and simple polyols and/or polyether polyols and/or polyester polyols; and mixtures of these polyisocyanates.
The auxiliaries and additives optionally used include, for example, fillers, dyes and pigments. Examples of fillers, 25 particularly fillers having a reinforcing effect, are silicate minerals, for example layer silicates, such as antigorite, serpentine, horn-blendes, amphiboles, chrysotile, talcum; metal oxides, such as kaolin, aluminum oxides, titanium oxides and iron oxides; metal salts, such as chalk, heavy spar; inorganic 30 pigments, such as cadmium sulfide, zinc sulfide; and glass, asbestos flour, and the like. It is preferred to use natural and synthetic fibrous materials, such as asbestos or wollastonite and, in particular, glass fibers of various len~ths which may optionally be si~ed. Fillers may be used 35 individually or in admixture. The fillers are advantageously Mo3417 added to the reaction mixture, if at all, in quant~ties of up to 50% by weight and preferably in quantities of up to 30% by weight, based on the weight of components a) and ~).
Detailed information on typical auxiliaries and additives can be found in the literature, for example in the monograph by J.H. Saunders and K.C. Fr;sch "High Polymers", Vol. XVI, Polyurethanes, Parts 2 and 7, Interscience Publishers, 1962 and 1964.
Component b)l~ of the system according to the invention is o preferably at least one organic compound having a molecular weight in the range from 400 to 12,000 and preferably from 400 to 6,000 and containing 2 to 8 and preferably 2 to 5 hydroxyl functions. The molecular weights mentioned herein may be calculated from the OH value of the substance on the basis of the following relation:
Molecular weight = 56.100 x functionality OH number 20 . It is possible to use polyhydroxy polyethers of the type known Der se from polyurethane chemistry which may be obtained by alkoxyla~;on of suitable starter molecules, such as ethylene glycol, diethylene glycnl, 1,4-dihydroxy butane, 1,6-dihydroxy hexane, trimethylol propane, ~lycerol, pentaerythritol, sorbitol or sucrose. Other suitable starters are ammonia or amines, such as ethylene diamine, hexamethylene diam;ne, 2,4-diaminotoluene, aniline or aminoalcohols. The alkoxylation reaction is carried out using propylene oxide and/or ethylene oxide in any order.
Also suitable are polyester polyols of the type obtainable in known manner by reaction of the low molecular weight alcohols mentioned with polybasic carboxylic acids, such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids.
Mo3417 t3 ~ 8 Relatively high molecular weight polyhydroxy polyethers containing high molecular weight polyadducts or polycondensates or polymers in finely dispersed, dissolved or grafted-on form are also suitable. Modified polyhydroxyl compounds such as these are obtained, for example, by carrying out polyaddition reactions (for example reactions between polyisocyanates and aminofunctio~l compounds) or polycondensation reactions (for example bet~en formaldehyde and phenols and/or amines) in situ in the compounds containing hydroxyl groups. Processes such as o these are described, for example, in German Auslegeschriften 1,168,075, 1,260,142, 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,550,796, 2,550,797, 2,550,833, 2,550,862, 2,633,2~3 and 2,639,254. However, it is also possible in accordance with U.S. patent 3,869,4l3 or German Auslegeschrift 2,550,860 to mix a prepared aqueous polymer dispersion ~ith a polyhydroxyl compound and then to remove the water from the mixture. Polyhydroxyl compounds modified by vinyl polymers, of the type obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. patents 3,383,351, 3,304,273, 3,523,093, and 3,110, 695; German Auslegeschrift 1,152,536) or polycarbonate polyols (German patent 1,769,795; U.S. patent 3,637,909) are also suitable as component b) for the process according to the invention. Where polyether polyols modified in accordance with German Auslegeschriften 2,442,101, 2,644,922 and 2,646,141 by graft polymerization with vinyl phosphonic acid esters and, optionally, (meth)acrylonitrile, (meth)acrylamide or OH
functional (meth)acrylates are used, flame retardant plastics are obtained.
Representatives of the compounds mentioned above suitable for use as compounds b)1) in accordance with the invention are described, for example, in High Polymers, Vol. XVI, ~Polyurethanes, Chemistry and Technology", edited by Saunders-Frisch, Interscience Publishers, New York London, Vol. I, 1962, pages 32 - 42 and pages 44 - 54 and Vol. lI, Mo3417 3 ~ ~
g 1964, pages 5 - 6 and 198 - 199 and in Kunststoff Handbuch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munchen, 1966, for example on pages 45 - 71.
Preferred amines b)2) have a molecular weight in the range from 60 to 300. Particularly pre~erred are diamines, such as 1,4-diaminobenzene, 2t4-diamino-toluene, 2,4'- and/or 4,4'-diaminodiphenylmethane. Particularly preferred are diamines of the type which contain an alkyl substituent at least in one ortho position to the amino groups, particularly those which contain at least one alkyl substituent in the ortho position to the first amino group and two alkyl substituents each containing 1 to 3 carbon atoms in the ortho position to the second amino group and, more preferably, those containing an ethyl, n-propyl and/or isopropyl substituent in at least one ortho position to the amino groups and, optionally, methyl substituents in other ortho positions ~o the amino groups.
These preferred or particularly preferred diamines include 2,4-diaminomesitylene; 1,3,~-triethyl-2,4-diaminobenzene;
1,3,5-triisopropyl-2,4-diaminobenzene; 1-methyl-3,5-diethyl-2,4-diaminobenzene, and mixtures thereof with 1-methyl-3,5-diethyl-2,6-diaminobenzene; 4,6-dimethyl-~-ethyl-1,3-diamino-benzene; 3,5,3',5'-tetraethyl-4,~'-diaminodiphenylmethane;
3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane; or 3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane.
Mixtures of these aromatic diamines may also be used.
Particularly preferred aliphatic diamines are isophorone diamine, bis-(4-aminocyclohexyl)-methane, 1,4-diamino-cyclo-hexane, ethylene diamine and its homologs and piperizine.
Preferred polyols b)3) are low molecular weight polyhydric alcohols haYing molecular weights in the range from 62 to 400.
~ypical of such alcohols are the substances already mentioned as starter molecules under b)l), such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxy hexane, trimethylol propane, glycerol, pentaerythritol, sorbitol or Mo3417 2~2~ ~g sucrose. Polyhydric alcohols having a functionality of 2 are particularly preferred.
Preferred catalysts according to the invention correspond to the following formula:
CH3 \
N-(CH2)n N-R
CH3 \
, N~(CH2)n o CH3 ;n wh;ch n = 2 OR 3 and R = H, CHO or CH3.
Particularly preferred catalysts correspond to the following formulae CH3 \ CH3 \
N-(CH2)3 and / H-(CH2)2 CH3 \ / CH3 \
20 ~ N-(CH2)3 N-~CH2~2 CH3 CH3"' in which R = CHO or H.
Polyol compositions containing the catalysts according to the invention have improved storage stability and reduced phase separation.
The present invention also relates to a process for bonding materials using the system according to the invention.
The system according to the invention is particularly suitable for bonding plastics, metals, wood and glass.
The two-component polyurethane adhesive is preferably applied by continuous mixing of components a) and b) in a stirred mixer, in a static mixer or in a countercurrent mixer Mo3417 ~2~3~g and immediate application of the adhesive thus mixed in the form of a bead to at least one of the two substrates to be bonded. In many cases, there is no need for the substrate surfaces to be pretreated by cleaning, roughening or other 5 pretreatment. The quantitative ratios of isocyanate component to polyol camponent follow the principles generally applied in isocyanate chemistry. A slight excess of isocyanate is preferable used (index range: 100 - 125, preferably 100 - 115).
The substrates provided with adhesive are fitted together, fixed and are either left to cure at room temperature or are subjected to a curing process at e-levated tempera~ure. Hand strength can be reached more quickly at elevated temperature than at room temperature.
The desired open time or curing time may be varied within 15 wide limits through the choice of the curing temperature and the choice of the catalyst b)4).
Another advantage of the adhesive according to the invent;on is that i~ can be applied without solvents.
The invention is further illustrated but is not intended 20 . to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Abbreviations used in the following:
Crude MDI:
4,4'-Diisocyanatodiphenyl methane in admixture with its isomers and higher homologs obtained by phosgenation of aniline-formaldehyde condensates, NCO content: 30.4%, viscosity ~5C:80 mPa.s.
Polvether 1:
A filled polyether is prepared in accordance with Example 1 of German Auslegeschrift 2,638,759 using as "solvent" 5070 parts by weight of a polyether polyol (OH number 35, prepared - by propoxylation of trimethylol propane and ethoxylation of the propoxylation product (PO:EO ratio = 83:17)) only 380 parts by weight hydrazine hydrate (instead of the 670 parts by weight Mo3417 ~2~ ~g reported) and only 1320 parts by weight toluene diisocyanate (instead of the 2310 parts by weight reported). A polyether having an organic filler content of 20% by weight and a hydroxyl value of 28 mg KOH/g is obtained.
H-MDA: 4,4'-methylenebis(cyclohexyl isocyanate) CatalYst 1: Tertiary amine catalyst corresponding to the formula:
~ (CH2)3N(CH3)2 OHC- N
(CH2)2n(CH3)2 Catalvst 2: triethylenediamine (174-diazabicyclo-2,272-octane) Zeolite paste: A 50% zeolite suspension in castor oil.
Exam~le 1 (Comparison Example7 uncatalyzed) 500 parts by weight polyether 1 are mixed with 75 parts by weight butane-174-diol7 25 parts by weight H-MDA and 25 parts by weight zeolite paste.
Example 2 (invention, catalyzed) 500 parts by weight polyether 1 are mixed w;th 75 parts by weight butane-1,4-diol, 25 parts by weight H-MDA and 25 parts by weight zeolite paste. 1.9 Parts by weight catalyst 1 are added to and homogeneously incorporated in the final mixture.
Example 3 (Comparison Example, catalyzed with catalyst 2) 500 Parts by weight polyether 1 are mixed with a solution of 0.5 part by weight catalyst 2 in 75 parts by weight butane-1,4-diol, 25 parts by weight H-MDA and 25 parts by weight zeolite paste.
Several mixtures were then made for testing as set forth in the following table:
Mo3417 Polyol Mixture Quantitative ratio Index Mix-ture Example QH value Crude MDI : Polvol mixture 1 197.1 0.531 : I 100 A
2 196.5 0.529 : :I 100 B
3 197.0 0.531 : :I 100 C
ExamDle 4 (Testing of the adhesive properties of mixtures A, B
and C of the table above) To test the tensile shear strengths in accordance with DIN
53 283, overlap bonds were formed from the plast1cs material to be bonded. The glueline was 0.8 mm thick, the test specimen width was 20 mm and the overlap length was lO mm. The adhesive was left to set at room temperature or was set by microwave or high frequency irradiation.
a) Parts to be joined: Xenoy (a polycarbonate/polybutylene terephthalate blend of General Electric) Setting and test conditions: at room temperature Mixture A B* C
_ Tensile shear strength average values ** [N/mm2] 3.6 6.2 4.3 * mixture according to the invention ** average value of 5 bonds 25 b) Parts to be joined: a polycarbonate/ABS blend containing 65% polycarbonate Setting and test conditions: at room temperature Mixture A B* C
. _ _ Tensile shear strength average values ** ~N/mm2] 4.2 7.0 6.0 Mo3417 ~,~2~
* mixture according to the invention ** average value of S bonds c) Parts to be joined: a polycarbonate/ABS blend containing 70% polycarbonate Setting conditions: microwave oven, 800 W
Test conditions: at room temperature Mixture A B* C
Tensile shear strength average values ** [N/mm23 7.4 10.3 9.4 Time to hand strength [sec]*** 135 40 60 * mixture according to the ;nvention ** average value of 5 bonds *** time elapsing before the part can be handled for further processing.
20 d) Parts to be joined: glass-fiber-reinforced polyester resin - Setting conditions: high-frequency oven, ?7.12 MHz Test conditions: at room temperature Mixture A B* C
Tensile shear strength average values ** [N/mm2] 6.6 8.7 7.5 Maximum HF output PmaX [W] 150*** 600 250 Possible cycle time at PmaX
[sec] 120 15 55 HF output for 40 sec.
Mo3417 2 ~3 r I ~ ~ ~ 8 cycle time [W] not 200 W not reach- reach-able able * mixture according to the invention ** average values of 5 bonds *** danger of thermal degradation of the adhesive at higher outputs.
Although the invention has been descr;bed in detail in the foregoing for the purpose of illustrat;on, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3417
Particularly preferred isocyanates as component a) for the process according to the invention are the commercially available polyisocyanates typically used in polyurethane chemistry, such as hexamethylene diisocyanate;
o 1-isocyanato-3,3,~-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate or IPDI); 4,4'-diisocyanatodicyclo-hexyl methane; 2,4-diisocyanatotoluene, and mixtures thereof with 2,6-diisocyanatotoluene; 4,4'-diisocyanato-diphenyl-methane, and mixtures thereof with the corresponding 2,4'- and 15 2,2'-isomers; polyisocyanate mixtures of the diphenylmethane series, of the type obtained by phosgenation of aniline/formaldehyde condensates; the biuret- or isocyanurate-containing modification products of these polyisocyanates; NCO prepolymers of the type mentioned based on 20 . these polyisocyanates and simple polyols and/or polyether polyols and/or polyester polyols; and mixtures of these polyisocyanates.
The auxiliaries and additives optionally used include, for example, fillers, dyes and pigments. Examples of fillers, 25 particularly fillers having a reinforcing effect, are silicate minerals, for example layer silicates, such as antigorite, serpentine, horn-blendes, amphiboles, chrysotile, talcum; metal oxides, such as kaolin, aluminum oxides, titanium oxides and iron oxides; metal salts, such as chalk, heavy spar; inorganic 30 pigments, such as cadmium sulfide, zinc sulfide; and glass, asbestos flour, and the like. It is preferred to use natural and synthetic fibrous materials, such as asbestos or wollastonite and, in particular, glass fibers of various len~ths which may optionally be si~ed. Fillers may be used 35 individually or in admixture. The fillers are advantageously Mo3417 added to the reaction mixture, if at all, in quant~ties of up to 50% by weight and preferably in quantities of up to 30% by weight, based on the weight of components a) and ~).
Detailed information on typical auxiliaries and additives can be found in the literature, for example in the monograph by J.H. Saunders and K.C. Fr;sch "High Polymers", Vol. XVI, Polyurethanes, Parts 2 and 7, Interscience Publishers, 1962 and 1964.
Component b)l~ of the system according to the invention is o preferably at least one organic compound having a molecular weight in the range from 400 to 12,000 and preferably from 400 to 6,000 and containing 2 to 8 and preferably 2 to 5 hydroxyl functions. The molecular weights mentioned herein may be calculated from the OH value of the substance on the basis of the following relation:
Molecular weight = 56.100 x functionality OH number 20 . It is possible to use polyhydroxy polyethers of the type known Der se from polyurethane chemistry which may be obtained by alkoxyla~;on of suitable starter molecules, such as ethylene glycol, diethylene glycnl, 1,4-dihydroxy butane, 1,6-dihydroxy hexane, trimethylol propane, ~lycerol, pentaerythritol, sorbitol or sucrose. Other suitable starters are ammonia or amines, such as ethylene diamine, hexamethylene diam;ne, 2,4-diaminotoluene, aniline or aminoalcohols. The alkoxylation reaction is carried out using propylene oxide and/or ethylene oxide in any order.
Also suitable are polyester polyols of the type obtainable in known manner by reaction of the low molecular weight alcohols mentioned with polybasic carboxylic acids, such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids.
Mo3417 t3 ~ 8 Relatively high molecular weight polyhydroxy polyethers containing high molecular weight polyadducts or polycondensates or polymers in finely dispersed, dissolved or grafted-on form are also suitable. Modified polyhydroxyl compounds such as these are obtained, for example, by carrying out polyaddition reactions (for example reactions between polyisocyanates and aminofunctio~l compounds) or polycondensation reactions (for example bet~en formaldehyde and phenols and/or amines) in situ in the compounds containing hydroxyl groups. Processes such as o these are described, for example, in German Auslegeschriften 1,168,075, 1,260,142, 2,324,134, 2,423,984, 2,512,385, 2,513,815, 2,550,796, 2,550,797, 2,550,833, 2,550,862, 2,633,2~3 and 2,639,254. However, it is also possible in accordance with U.S. patent 3,869,4l3 or German Auslegeschrift 2,550,860 to mix a prepared aqueous polymer dispersion ~ith a polyhydroxyl compound and then to remove the water from the mixture. Polyhydroxyl compounds modified by vinyl polymers, of the type obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. patents 3,383,351, 3,304,273, 3,523,093, and 3,110, 695; German Auslegeschrift 1,152,536) or polycarbonate polyols (German patent 1,769,795; U.S. patent 3,637,909) are also suitable as component b) for the process according to the invention. Where polyether polyols modified in accordance with German Auslegeschriften 2,442,101, 2,644,922 and 2,646,141 by graft polymerization with vinyl phosphonic acid esters and, optionally, (meth)acrylonitrile, (meth)acrylamide or OH
functional (meth)acrylates are used, flame retardant plastics are obtained.
Representatives of the compounds mentioned above suitable for use as compounds b)1) in accordance with the invention are described, for example, in High Polymers, Vol. XVI, ~Polyurethanes, Chemistry and Technology", edited by Saunders-Frisch, Interscience Publishers, New York London, Vol. I, 1962, pages 32 - 42 and pages 44 - 54 and Vol. lI, Mo3417 3 ~ ~
g 1964, pages 5 - 6 and 198 - 199 and in Kunststoff Handbuch, Vol. VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munchen, 1966, for example on pages 45 - 71.
Preferred amines b)2) have a molecular weight in the range from 60 to 300. Particularly pre~erred are diamines, such as 1,4-diaminobenzene, 2t4-diamino-toluene, 2,4'- and/or 4,4'-diaminodiphenylmethane. Particularly preferred are diamines of the type which contain an alkyl substituent at least in one ortho position to the amino groups, particularly those which contain at least one alkyl substituent in the ortho position to the first amino group and two alkyl substituents each containing 1 to 3 carbon atoms in the ortho position to the second amino group and, more preferably, those containing an ethyl, n-propyl and/or isopropyl substituent in at least one ortho position to the amino groups and, optionally, methyl substituents in other ortho positions ~o the amino groups.
These preferred or particularly preferred diamines include 2,4-diaminomesitylene; 1,3,~-triethyl-2,4-diaminobenzene;
1,3,5-triisopropyl-2,4-diaminobenzene; 1-methyl-3,5-diethyl-2,4-diaminobenzene, and mixtures thereof with 1-methyl-3,5-diethyl-2,6-diaminobenzene; 4,6-dimethyl-~-ethyl-1,3-diamino-benzene; 3,5,3',5'-tetraethyl-4,~'-diaminodiphenylmethane;
3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane; or 3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane.
Mixtures of these aromatic diamines may also be used.
Particularly preferred aliphatic diamines are isophorone diamine, bis-(4-aminocyclohexyl)-methane, 1,4-diamino-cyclo-hexane, ethylene diamine and its homologs and piperizine.
Preferred polyols b)3) are low molecular weight polyhydric alcohols haYing molecular weights in the range from 62 to 400.
~ypical of such alcohols are the substances already mentioned as starter molecules under b)l), such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxy hexane, trimethylol propane, glycerol, pentaerythritol, sorbitol or Mo3417 2~2~ ~g sucrose. Polyhydric alcohols having a functionality of 2 are particularly preferred.
Preferred catalysts according to the invention correspond to the following formula:
CH3 \
N-(CH2)n N-R
CH3 \
, N~(CH2)n o CH3 ;n wh;ch n = 2 OR 3 and R = H, CHO or CH3.
Particularly preferred catalysts correspond to the following formulae CH3 \ CH3 \
N-(CH2)3 and / H-(CH2)2 CH3 \ / CH3 \
20 ~ N-(CH2)3 N-~CH2~2 CH3 CH3"' in which R = CHO or H.
Polyol compositions containing the catalysts according to the invention have improved storage stability and reduced phase separation.
The present invention also relates to a process for bonding materials using the system according to the invention.
The system according to the invention is particularly suitable for bonding plastics, metals, wood and glass.
The two-component polyurethane adhesive is preferably applied by continuous mixing of components a) and b) in a stirred mixer, in a static mixer or in a countercurrent mixer Mo3417 ~2~3~g and immediate application of the adhesive thus mixed in the form of a bead to at least one of the two substrates to be bonded. In many cases, there is no need for the substrate surfaces to be pretreated by cleaning, roughening or other 5 pretreatment. The quantitative ratios of isocyanate component to polyol camponent follow the principles generally applied in isocyanate chemistry. A slight excess of isocyanate is preferable used (index range: 100 - 125, preferably 100 - 115).
The substrates provided with adhesive are fitted together, fixed and are either left to cure at room temperature or are subjected to a curing process at e-levated tempera~ure. Hand strength can be reached more quickly at elevated temperature than at room temperature.
The desired open time or curing time may be varied within 15 wide limits through the choice of the curing temperature and the choice of the catalyst b)4).
Another advantage of the adhesive according to the invent;on is that i~ can be applied without solvents.
The invention is further illustrated but is not intended 20 . to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Abbreviations used in the following:
Crude MDI:
4,4'-Diisocyanatodiphenyl methane in admixture with its isomers and higher homologs obtained by phosgenation of aniline-formaldehyde condensates, NCO content: 30.4%, viscosity ~5C:80 mPa.s.
Polvether 1:
A filled polyether is prepared in accordance with Example 1 of German Auslegeschrift 2,638,759 using as "solvent" 5070 parts by weight of a polyether polyol (OH number 35, prepared - by propoxylation of trimethylol propane and ethoxylation of the propoxylation product (PO:EO ratio = 83:17)) only 380 parts by weight hydrazine hydrate (instead of the 670 parts by weight Mo3417 ~2~ ~g reported) and only 1320 parts by weight toluene diisocyanate (instead of the 2310 parts by weight reported). A polyether having an organic filler content of 20% by weight and a hydroxyl value of 28 mg KOH/g is obtained.
H-MDA: 4,4'-methylenebis(cyclohexyl isocyanate) CatalYst 1: Tertiary amine catalyst corresponding to the formula:
~ (CH2)3N(CH3)2 OHC- N
(CH2)2n(CH3)2 Catalvst 2: triethylenediamine (174-diazabicyclo-2,272-octane) Zeolite paste: A 50% zeolite suspension in castor oil.
Exam~le 1 (Comparison Example7 uncatalyzed) 500 parts by weight polyether 1 are mixed with 75 parts by weight butane-174-diol7 25 parts by weight H-MDA and 25 parts by weight zeolite paste.
Example 2 (invention, catalyzed) 500 parts by weight polyether 1 are mixed w;th 75 parts by weight butane-1,4-diol, 25 parts by weight H-MDA and 25 parts by weight zeolite paste. 1.9 Parts by weight catalyst 1 are added to and homogeneously incorporated in the final mixture.
Example 3 (Comparison Example, catalyzed with catalyst 2) 500 Parts by weight polyether 1 are mixed with a solution of 0.5 part by weight catalyst 2 in 75 parts by weight butane-1,4-diol, 25 parts by weight H-MDA and 25 parts by weight zeolite paste.
Several mixtures were then made for testing as set forth in the following table:
Mo3417 Polyol Mixture Quantitative ratio Index Mix-ture Example QH value Crude MDI : Polvol mixture 1 197.1 0.531 : I 100 A
2 196.5 0.529 : :I 100 B
3 197.0 0.531 : :I 100 C
ExamDle 4 (Testing of the adhesive properties of mixtures A, B
and C of the table above) To test the tensile shear strengths in accordance with DIN
53 283, overlap bonds were formed from the plast1cs material to be bonded. The glueline was 0.8 mm thick, the test specimen width was 20 mm and the overlap length was lO mm. The adhesive was left to set at room temperature or was set by microwave or high frequency irradiation.
a) Parts to be joined: Xenoy (a polycarbonate/polybutylene terephthalate blend of General Electric) Setting and test conditions: at room temperature Mixture A B* C
_ Tensile shear strength average values ** [N/mm2] 3.6 6.2 4.3 * mixture according to the invention ** average value of 5 bonds 25 b) Parts to be joined: a polycarbonate/ABS blend containing 65% polycarbonate Setting and test conditions: at room temperature Mixture A B* C
. _ _ Tensile shear strength average values ** ~N/mm2] 4.2 7.0 6.0 Mo3417 ~,~2~
* mixture according to the invention ** average value of S bonds c) Parts to be joined: a polycarbonate/ABS blend containing 70% polycarbonate Setting conditions: microwave oven, 800 W
Test conditions: at room temperature Mixture A B* C
Tensile shear strength average values ** [N/mm23 7.4 10.3 9.4 Time to hand strength [sec]*** 135 40 60 * mixture according to the ;nvention ** average value of 5 bonds *** time elapsing before the part can be handled for further processing.
20 d) Parts to be joined: glass-fiber-reinforced polyester resin - Setting conditions: high-frequency oven, ?7.12 MHz Test conditions: at room temperature Mixture A B* C
Tensile shear strength average values ** [N/mm2] 6.6 8.7 7.5 Maximum HF output PmaX [W] 150*** 600 250 Possible cycle time at PmaX
[sec] 120 15 55 HF output for 40 sec.
Mo3417 2 ~3 r I ~ ~ ~ 8 cycle time [W] not 200 W not reach- reach-able able * mixture according to the invention ** average values of 5 bonds *** danger of thermal degradation of the adhesive at higher outputs.
Although the invention has been descr;bed in detail in the foregoing for the purpose of illustrat;on, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3417
Claims (10)
1. A two-component polyurethane adhesive containing a) an isocyanate component, b) an isocyanate-reactive component, and a catalyst for the reaction of a) and b), characterized in that the catalyst used is a compound corresponding to the following formula:
wherein R1 and R2 may be the same or different and represent C1 to C4 alkyl, R3 is a CH0 group, H, or a C1 to C4 alkyl optionally substituted by a CHO group, n is an integer of 2 to 4, o is 1 or 2, p is 0 or 1, and o + p = 2.
wherein R1 and R2 may be the same or different and represent C1 to C4 alkyl, R3 is a CH0 group, H, or a C1 to C4 alkyl optionally substituted by a CHO group, n is an integer of 2 to 4, o is 1 or 2, p is 0 or 1, and o + p = 2.
2. The adhesive of Claim 1, wherein component b) comprises b1) 100 parts by weight of at least one hydroxyl-containing compound having a molecular weight of at least 400 and a hydroxyl functionality of at least 2;
b2) 2 to 20 parts by weight of at least one aliphatic, aromatic or cycloaliphatic diamine or triamine having a molecular weight of at least 60 and, optionally b3) 5 to 40 parts by weight of at least one hydroxyl containing low molecular weight chain-extending agent having a molecular weight of at least 62 and a functionality of at least 2.
Mo3417
b2) 2 to 20 parts by weight of at least one aliphatic, aromatic or cycloaliphatic diamine or triamine having a molecular weight of at least 60 and, optionally b3) 5 to 40 parts by weight of at least one hydroxyl containing low molecular weight chain-extending agent having a molecular weight of at least 62 and a functionality of at least 2.
Mo3417
3. The adhesive of Claim 2, wherein component b) comprises b1) a polyol obtainable by alkoxylation of trimethylol propane, b2) methylenebis(cyclohexyl diamine), and b3) a butanediol.
4. The adhesive of Claim 1, wherein the isocyanate component a) is liquid at room temperature.
5. The adhesive of Claim 1, wherein a polyisocyanate of the diphenyl methane series or a derivative thereof is present as isocyanate component a).
6. The adhesive of Claim 1, wherein the catalyst is a compound corresponding to the following formula;
wherein n = 2 or 3 and R = H, CHO or CH3.
wherein n = 2 or 3 and R = H, CHO or CH3.
7. The adhesive of Claim 1, wherein the isocyanate groups are present in an excess over the isocyanate-reactive groups.
8. The adhesive of Claim 1, wherein the catalyst is present in such a quantity that at least 0.005 9 tertiary amine nitrogen is present per 100 9 component b).
9. In a process for bonding substrates by applying a two-component polyurethane adhesive to one or both of the surfaces to be joined, bringing the surfaces together and allowing the adhesive to fully cure, the improvement wherein the adhesive is the adhesive of Claim 1.
Mo3417
Mo3417
10. The process of Claim 9, wherein the adhesive is cured by high frequency or microwaves or at room temperature.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3925790.8 | 1989-08-04 | ||
| DE3925790A DE3925790A1 (en) | 1989-08-04 | 1989-08-04 | TWO-COMPONENT POLYURETHANE ADHESIVE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2021308A1 true CA2021308A1 (en) | 1991-02-05 |
Family
ID=6386491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002021308A Abandoned CA2021308A1 (en) | 1989-08-04 | 1990-07-17 | Two-component polyurethane adhesive |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0411432B1 (en) |
| JP (1) | JP2841111B2 (en) |
| AT (1) | ATE127483T1 (en) |
| CA (1) | CA2021308A1 (en) |
| DE (2) | DE3925790A1 (en) |
| ES (1) | ES2078275T3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254199A (en) * | 1991-03-19 | 1993-10-19 | Bayer Aktiengesellschaft | Process for bonding substrates of glass fiber reinforced polyester resin |
| US6953602B2 (en) | 1999-09-17 | 2005-10-11 | Avery Dennison Corporation | Pattern coated adhesive article |
| US20110064955A1 (en) * | 2008-05-21 | 2011-03-17 | Amcor Flexibles Kreuzlingen Ltd. | Process for manufacturing a flexible laminate for packaging |
| US9567499B2 (en) | 2011-01-18 | 2017-02-14 | Henkel Ag & Co. Kgaa | Two-component polyurethane composition with delayed crosslinking |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2107950C (en) * | 1992-10-22 | 2001-08-14 | Bayer Corporation | Stabilization of rim systems containing acidic additives |
| US5798395A (en) * | 1994-03-31 | 1998-08-25 | Lambda Technologies Inc. | Adhesive bonding using variable frequency microwave energy |
| DE4411666A1 (en) * | 1994-04-05 | 1995-10-12 | Bayer Ag | 2-component polyurethane reactive adhesive compositions can be dosed in a volume ratio of 1: 1 |
| FR2738838B1 (en) * | 1995-09-20 | 1999-12-10 | Gemplus Card Int | METHOD FOR ADHESION OF A POLYURETHANE ON A POLYMER SUBSTRATE |
| US6458860B1 (en) * | 2001-06-01 | 2002-10-01 | Huntsman Petrochemical Corporation | Advances in urethane foam catalysis |
| US6534555B1 (en) * | 2001-09-10 | 2003-03-18 | Huntsman Petrochemical Corporation | Catalyst systems for polyurethane polyester foams |
| US7834123B2 (en) * | 2006-05-19 | 2010-11-16 | Henkel Ag & Co. Kgaa | Two component polyurethane adhesive |
| EP2183294B1 (en) | 2007-07-23 | 2019-01-09 | Dow Global Technologies LLC | Two part polyurethane curable composition having substantially consistent g-modulus across the range of use temperatures |
| BRPI0912919B1 (en) | 2008-08-22 | 2019-04-24 | Dow Global Technologies Llc | BICOMPONENT COMPOSITION AND METHOD FOR BONDING TWO OR MORE SUBSTRATES BETWEEN |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3714127A (en) * | 1971-12-13 | 1973-01-30 | Gen Tire & Rubber Co | Urethane adhesive having improved sag resistance |
| DE2732292A1 (en) * | 1977-07-16 | 1979-02-01 | Bayer Ag | METHOD FOR MANUFACTURING POLYURETHANE PLASTICS |
| DE2854384A1 (en) * | 1978-12-16 | 1980-07-03 | Bayer Ag | METHOD FOR PRODUCING POLYURETHANE PLASTICS |
| AU8230182A (en) * | 1981-04-06 | 1982-10-14 | Goodyear Tire And Rubber Company, The | Two pack polyurethane adhesive |
| US4743672A (en) * | 1987-02-26 | 1988-05-10 | Ashland Oil, Inc. | Sag resistant, two component urethane adhesives |
-
1989
- 1989-08-04 DE DE3925790A patent/DE3925790A1/en not_active Withdrawn
-
1990
- 1990-07-17 CA CA002021308A patent/CA2021308A1/en not_active Abandoned
- 1990-07-24 ES ES90114114T patent/ES2078275T3/en not_active Expired - Lifetime
- 1990-07-24 EP EP90114114A patent/EP0411432B1/en not_active Expired - Lifetime
- 1990-07-24 AT AT90114114T patent/ATE127483T1/en not_active IP Right Cessation
- 1990-07-24 DE DE59009613T patent/DE59009613D1/en not_active Expired - Fee Related
- 1990-08-02 JP JP2204019A patent/JP2841111B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254199A (en) * | 1991-03-19 | 1993-10-19 | Bayer Aktiengesellschaft | Process for bonding substrates of glass fiber reinforced polyester resin |
| US6953602B2 (en) | 1999-09-17 | 2005-10-11 | Avery Dennison Corporation | Pattern coated adhesive article |
| US20110064955A1 (en) * | 2008-05-21 | 2011-03-17 | Amcor Flexibles Kreuzlingen Ltd. | Process for manufacturing a flexible laminate for packaging |
| US9567499B2 (en) | 2011-01-18 | 2017-02-14 | Henkel Ag & Co. Kgaa | Two-component polyurethane composition with delayed crosslinking |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2078275T3 (en) | 1995-12-16 |
| EP0411432B1 (en) | 1995-09-06 |
| DE3925790A1 (en) | 1991-02-07 |
| DE59009613D1 (en) | 1995-10-12 |
| ATE127483T1 (en) | 1995-09-15 |
| JP2841111B2 (en) | 1998-12-24 |
| EP0411432A3 (en) | 1992-04-08 |
| JPH0376777A (en) | 1991-04-02 |
| EP0411432A2 (en) | 1991-02-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |