CA1192341A - Adhesive composition and composite made therewith - Google Patents
Adhesive composition and composite made therewithInfo
- Publication number
- CA1192341A CA1192341A CA000403884A CA403884A CA1192341A CA 1192341 A CA1192341 A CA 1192341A CA 000403884 A CA000403884 A CA 000403884A CA 403884 A CA403884 A CA 403884A CA 1192341 A CA1192341 A CA 1192341A
- Authority
- CA
- Canada
- Prior art keywords
- adhesive
- triol
- mixture
- weight
- phenylene diamine
- 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.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/324—Polyamines aromatic containing only one aromatic ring
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 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
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31616—Next to polyester [e.g., alkyd]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Abstract
ABSTRACT OF THE DISCLOSURE
An adhesive system that can be used for bonding together fiberglass reinforced polyester (FRP) panels is provided. The adhesive system is comprised of a "hardener component" containing a polyester or polyether triol, para-phenylene diamine or ortho-phenylene diamine, and desirably a tin compound catalyst, and a "base component" containing an aromatic diisocyanate. The two components are mixed together just prior to bonding and the mixture is spread on the FRP panel surfaces desired to be bonded together. The panels are assembled and held clamped together until the adhesive sets.
An adhesive system that can be used for bonding together fiberglass reinforced polyester (FRP) panels is provided. The adhesive system is comprised of a "hardener component" containing a polyester or polyether triol, para-phenylene diamine or ortho-phenylene diamine, and desirably a tin compound catalyst, and a "base component" containing an aromatic diisocyanate. The two components are mixed together just prior to bonding and the mixture is spread on the FRP panel surfaces desired to be bonded together. The panels are assembled and held clamped together until the adhesive sets.
Description
~234~
This invention relates to an adhesive com-position and composite made therewith, more especially the invention is concerned with a two-part adhesive system and a laminate employing an adhesive deri~ed from the system.
In an endeavor to lessen the weight of passenger cars and to reduce car body rusting, it has been proposed to expand the use of fiberglass reinforced polyester (FRP) panels to replace some or all of the metal body panels currently being used in car bodies.
In the use of the FRP panels~ the panels which form the complete body customarily are ioined together with an adhesive bondine system.
To be satisfactory, the adhesive system must produce a strong bond ~35 kgf/cm2 minimum3 within a relatively short period of time (desirably within about 7-8 minutes) at ambient production area tempe-ratures (which normally range from about 20C to 35C) and withstand the relatively high temperatures developed within the engine compartment of modern cars.
The adhesive also must have su~ficient resist-ance to flow during the time which elapses after applica-tion to the FRP panels and before it sets to resist flowing outside the prescribed "bond line" between the assembled par.els even if` the assembled panels are up-ended for movement to the next assembly point before the adhesive has had an opportunity to set.
One adhesive material which has been proposed for bonding FRP panels is based upon a polyurethane composition obtained by reacting together 100 parts of`
a polyester or polyether polyol or a polyesteramide with a molecular weight between 700 and 4500, 38 to 80 parts of an organic polyisocyanate, 5 to 200 parts of filler, a catalyst, and sufficient monomeric nitrogen contain-ing polyol having f`rom 3 to 6 hydroxyls to react with :1 ,.~
~3~3 ,~
the excess polyisocyanate material in the system (see V.S. Patent 3,812,003).
The present invention provides an adhesive for bonding together FRP panels which utilizes an adhesive composition, more especially a polyurethane, that has excellent resistance to flow between the time that it is applied ~`
to the panels and the time the adhesive sets. The excel-lent flow resistant properties of the adhesive composition pre~ents objectionable ~low of the adhesive beyond the de-sired "bond line" between the assembled panels while the adhesive is in a ~luid condition. In accordance with the present invention, para-phenylene diamine or ortho-phenyl-ene diamine is included in the adhesive composition for bonding the FRP panels together, along with a polyester or polyether triol, to produce the desired resistance to ~low.
In addition to the para-phenylene diamine or ortho-phenyl-ene diamine and the polyester or polyether triol, the ad-hesive composition includes an aromatic diisocyanate and a tin compound catalyst to accelerate the reaction between the triol and the isocyanate.
DETAILED DESCRIPTION QF THE INVENTION
The adhesive system of the present invention utilizes a "two- part" adhesive (a "base component" and a "hardener component"), the parts of which are mixed to-gether just prior to being used for bonding the FRP panels together. The "hardener component" contains the polyester or polyether triol, the para-phenylene diamine or ortho-phenylene diamine and, desirably, the tin compound catalyst, while the "base component" includes the aromatic diisocya-nat~. The "base component" desirably is formulated to provide a composition that has a viscosity of from 20,000 to 55,000 centipoise per second (cps) at 25C., while the "hardener component" desirably is formulated to provide a composition that has a viscosity o~ ~rom ~00 to 4,000 cps at 25C.
The polyester triols or polyether triols used in the "hardener component" are those having a molecular weight between about 400 and 1,000. The polyester triols generally are condensation products of a polycaxboxylic acid or its anhydride (such as adipic aGid or phthalic anhydride) with a triol ~such as trimethylolpropane, 1~2r6 hexanetriol or l,l,l-trimethylolethane). The polyether triols include 23~
the poly (oxyal~ylene) derivatives of polyhydric alcohols, exemplified by glycerol, J,l,l-trimethylolpropane and 1,2,6-hexanetriol and the poly(o~ypropylene) aaducts o glycerol, l,l,l-trimethylolpropane and 1,2,6-hexanetriol.
The para-phenylene diamine or ortho-phenylene diamine or mixtures thereof are included in the adhesive system to produce the desired excellent resistance to flow in the adhesive during the period after the two components of the system are mixed together and before setting of the adhesive occurs. Although the amount of para-phenylene diamine or ortho-phenylene diamine or mixtures thereof added to the adhesive system in order to produce the de-sired flow resistance can vary, usually from 1.8 to 3.0 parts by weight of the diamine(s) per 100 parts by weight 15 of the polyester or polyether triol are used in the adhesive system.
The tin compound catalyst desirably is included in the "hardener component" of the adhesive system and is present in an amount to cause the adhesive to "gel" or "set" within an acceptable time period at the ambient temperature of the work area. Generally, it is desired that the adhesive used for bonding FRP panels "gel" or "set" within about 7-8 minutes at temperatures normally experienced in the production area which range normally ~5 between about 20C and 35C, although a set time of up to about 15 minutes is acceptable. Usually from 0~01 to 0.2 parts by weight of the tin compound catalyst per 100 parts by weig~t of the polyester or polyether triol is adequate to impart an acceptable "gel" or "set" time to the adhesive 30 system. Although dibutyl tin dilaurate is preferred for use in the adhesive system, other tin compound catalysts for uretharle reactions can be used (for example, dialkyl tin dioc~ate, dibutyl tin maleate and dibutyl tin amyl mercaptide). Tin compound catalysts for urethane reactions 35 may be represented by the formula SnX4 where one or all of the X's may be the same or different ana where X may be a hydrocarbon radicall a halo~en, or an oxygenated or 3~
thionated hydrocarbon.
The aromatic diisocyanate component of the adhesive system is included in the "base component" of the system and, desirably, has a functionality of from about 2.3 to 2.7 and an equivalent weight of about 85 to 150. Representative aromatic diisocyanates are m-phenyl-ene diisocyanate, p-phen~lene diisocyanate, methylene di-p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyle~e di-isocyanate and 1,8-naphthylene diisocyanate. Ideally, the aromatic diisocyanate is present in a stoichiometric quantity to just react with all of the functionally active hydroxyl and amine groups in the adhesive system. However, to insure complete reaction of th~ functionally active hydroxyl and amine groups, a slight excess of the aromatic diisocyanate is used in the adhesive system. Preferably, an amount of the aromatic diisocyanate in excess of that amount required to stoichiometrically react with the polyester or polyether triol in the "hardener component" is used in the adhesive system, and an additional amount of a diol or tetrol free of nitrogen ~ro~ps or combination thereof ~for example, 1,4-butanediol or the reaction product of pentacrythritol and propylene oxide) is added to the adhesive system to react stoichiometrically with the excess isocyanate groups.
An inert powdery filler normally is added to the "base component" of the adhesive system and aids in con~
txolling the viscosity of the "base component". The amount of such filler may vary, but desirably 20 to 100 parts by weight of filler is added to the "base component" for every 100 parts by weight o~ aromatic diisocyanate present in the adhesiveO Representative filler materials are limestones, hydrous magnesium silicate (talc) and carbon black.
If desired, a colorant may be added to either the 'Ihardener component" or the "base component" of the adhesive system or to both of the components.
This invention relates to an adhesive com-position and composite made therewith, more especially the invention is concerned with a two-part adhesive system and a laminate employing an adhesive deri~ed from the system.
In an endeavor to lessen the weight of passenger cars and to reduce car body rusting, it has been proposed to expand the use of fiberglass reinforced polyester (FRP) panels to replace some or all of the metal body panels currently being used in car bodies.
In the use of the FRP panels~ the panels which form the complete body customarily are ioined together with an adhesive bondine system.
To be satisfactory, the adhesive system must produce a strong bond ~35 kgf/cm2 minimum3 within a relatively short period of time (desirably within about 7-8 minutes) at ambient production area tempe-ratures (which normally range from about 20C to 35C) and withstand the relatively high temperatures developed within the engine compartment of modern cars.
The adhesive also must have su~ficient resist-ance to flow during the time which elapses after applica-tion to the FRP panels and before it sets to resist flowing outside the prescribed "bond line" between the assembled par.els even if` the assembled panels are up-ended for movement to the next assembly point before the adhesive has had an opportunity to set.
One adhesive material which has been proposed for bonding FRP panels is based upon a polyurethane composition obtained by reacting together 100 parts of`
a polyester or polyether polyol or a polyesteramide with a molecular weight between 700 and 4500, 38 to 80 parts of an organic polyisocyanate, 5 to 200 parts of filler, a catalyst, and sufficient monomeric nitrogen contain-ing polyol having f`rom 3 to 6 hydroxyls to react with :1 ,.~
~3~3 ,~
the excess polyisocyanate material in the system (see V.S. Patent 3,812,003).
The present invention provides an adhesive for bonding together FRP panels which utilizes an adhesive composition, more especially a polyurethane, that has excellent resistance to flow between the time that it is applied ~`
to the panels and the time the adhesive sets. The excel-lent flow resistant properties of the adhesive composition pre~ents objectionable ~low of the adhesive beyond the de-sired "bond line" between the assembled panels while the adhesive is in a ~luid condition. In accordance with the present invention, para-phenylene diamine or ortho-phenyl-ene diamine is included in the adhesive composition for bonding the FRP panels together, along with a polyester or polyether triol, to produce the desired resistance to ~low.
In addition to the para-phenylene diamine or ortho-phenyl-ene diamine and the polyester or polyether triol, the ad-hesive composition includes an aromatic diisocyanate and a tin compound catalyst to accelerate the reaction between the triol and the isocyanate.
DETAILED DESCRIPTION QF THE INVENTION
The adhesive system of the present invention utilizes a "two- part" adhesive (a "base component" and a "hardener component"), the parts of which are mixed to-gether just prior to being used for bonding the FRP panels together. The "hardener component" contains the polyester or polyether triol, the para-phenylene diamine or ortho-phenylene diamine and, desirably, the tin compound catalyst, while the "base component" includes the aromatic diisocya-nat~. The "base component" desirably is formulated to provide a composition that has a viscosity of from 20,000 to 55,000 centipoise per second (cps) at 25C., while the "hardener component" desirably is formulated to provide a composition that has a viscosity o~ ~rom ~00 to 4,000 cps at 25C.
The polyester triols or polyether triols used in the "hardener component" are those having a molecular weight between about 400 and 1,000. The polyester triols generally are condensation products of a polycaxboxylic acid or its anhydride (such as adipic aGid or phthalic anhydride) with a triol ~such as trimethylolpropane, 1~2r6 hexanetriol or l,l,l-trimethylolethane). The polyether triols include 23~
the poly (oxyal~ylene) derivatives of polyhydric alcohols, exemplified by glycerol, J,l,l-trimethylolpropane and 1,2,6-hexanetriol and the poly(o~ypropylene) aaducts o glycerol, l,l,l-trimethylolpropane and 1,2,6-hexanetriol.
The para-phenylene diamine or ortho-phenylene diamine or mixtures thereof are included in the adhesive system to produce the desired excellent resistance to flow in the adhesive during the period after the two components of the system are mixed together and before setting of the adhesive occurs. Although the amount of para-phenylene diamine or ortho-phenylene diamine or mixtures thereof added to the adhesive system in order to produce the de-sired flow resistance can vary, usually from 1.8 to 3.0 parts by weight of the diamine(s) per 100 parts by weight 15 of the polyester or polyether triol are used in the adhesive system.
The tin compound catalyst desirably is included in the "hardener component" of the adhesive system and is present in an amount to cause the adhesive to "gel" or "set" within an acceptable time period at the ambient temperature of the work area. Generally, it is desired that the adhesive used for bonding FRP panels "gel" or "set" within about 7-8 minutes at temperatures normally experienced in the production area which range normally ~5 between about 20C and 35C, although a set time of up to about 15 minutes is acceptable. Usually from 0~01 to 0.2 parts by weight of the tin compound catalyst per 100 parts by weig~t of the polyester or polyether triol is adequate to impart an acceptable "gel" or "set" time to the adhesive 30 system. Although dibutyl tin dilaurate is preferred for use in the adhesive system, other tin compound catalysts for uretharle reactions can be used (for example, dialkyl tin dioc~ate, dibutyl tin maleate and dibutyl tin amyl mercaptide). Tin compound catalysts for urethane reactions 35 may be represented by the formula SnX4 where one or all of the X's may be the same or different ana where X may be a hydrocarbon radicall a halo~en, or an oxygenated or 3~
thionated hydrocarbon.
The aromatic diisocyanate component of the adhesive system is included in the "base component" of the system and, desirably, has a functionality of from about 2.3 to 2.7 and an equivalent weight of about 85 to 150. Representative aromatic diisocyanates are m-phenyl-ene diisocyanate, p-phen~lene diisocyanate, methylene di-p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyle~e di-isocyanate and 1,8-naphthylene diisocyanate. Ideally, the aromatic diisocyanate is present in a stoichiometric quantity to just react with all of the functionally active hydroxyl and amine groups in the adhesive system. However, to insure complete reaction of th~ functionally active hydroxyl and amine groups, a slight excess of the aromatic diisocyanate is used in the adhesive system. Preferably, an amount of the aromatic diisocyanate in excess of that amount required to stoichiometrically react with the polyester or polyether triol in the "hardener component" is used in the adhesive system, and an additional amount of a diol or tetrol free of nitrogen ~ro~ps or combination thereof ~for example, 1,4-butanediol or the reaction product of pentacrythritol and propylene oxide) is added to the adhesive system to react stoichiometrically with the excess isocyanate groups.
An inert powdery filler normally is added to the "base component" of the adhesive system and aids in con~
txolling the viscosity of the "base component". The amount of such filler may vary, but desirably 20 to 100 parts by weight of filler is added to the "base component" for every 100 parts by weight o~ aromatic diisocyanate present in the adhesiveO Representative filler materials are limestones, hydrous magnesium silicate (talc) and carbon black.
If desired, a colorant may be added to either the 'Ihardener component" or the "base component" of the adhesive system or to both of the components.
2~
The use of the monomeric nitrogen containing polyol with from 3 to 6 hydroxyls suggested as a component of the FRP adhesive system described in U.S. Patent 3,812,003 is not used in the adhesive system of the present invention because of the presence of the para-phenylene diamine or ortho-phenylene diamine in the adhesive system hexein des-cribed, since the combination would produce an adhesive material that has an objectionably short gel or set time once the adhesive components are mixed together.
In the use of the adhesive sys-tem of the present invention, the surfaces of the FRP panels to be bonded together first are "wiped" or sprayed with an FRP primer, such as a solvent solution of an organic polyisocyanate.
The two components of the adhesive system (i.e., the "hardener component" and the "base component") are mixed together (desirably by feeding the two components to a portable hand-held mixing head) to form a reaction mixture comprised of (a) 100 parts by weight of a polyester triol or a polyether triol having a molecular weiyht between about 400 and 1000, (b) an aromatic diisocyanate having a functionality o from about 2.3 to 2.7 and an equivalent weight of about 85 to 150, said isocyanate being present in an amount in excess of the amount to stoichoimetrically react with the polyester triol or polyether triol in the mixture, (c) sufficient para-phenylene diamine or ortho-phenylene diamine or a mixture thereof to produce a desired flow resistance in the reaction mixture, (d) sufficient tin compound catalyst to achieve setting of the reaction mixture within 15 minutes after the two components of the adhesive system are mixed together, and ~e) suEficient amount of polyol free of nitrogen groups to provide fllnctional hydroxyl groups to stoichiometrically react with at least essentially all of the excess reactive isocyana~e groups in the reaction mixture. A thin film of the reaction mixture is spread on one or both of the surfaces of the FRP panels to be ;23~
bonded together and the two panels are clamped together until the adhesive mixture sets. Setting of the adhesive mixture can be accelerated by heating the assembly (desir-ably, to a temperature between 100C. to 175C.).
Although the adhesive system has been described for bonding two FRP panels together, the system also can be used for FRP-to-metal bonding and for metal-to-metal bonding.
The invention will be more fully understood from the following examples.
EXAMPLE I
A two-part adhesive system comprised of a "hard-ener component" and a "base component" was formed according to the following formulations:
Hardener_Component MaterialParts by Wei~ht Polyether triol (Pluracol TP440*) 100.0 1,4-Butanediol 7.4 Tetrol (Pluracol PEP450**) 20 3 Para-Phenylenediamine 3.19 Dibutyltin dilaurate 07 Total130.96 *Reaction product of trimethylolpropane and propylene oxide having a molecular weight of about 425, a viscosity of 600 cps at 25C., and an apparent pH
of 6.5, produced by BASF Wyandotte Corporation.
**Reaction product of pentaerythritol and propylene oxide with an equivaIent weight of about 100, sold by Wyandotte Chemical Company. (Pluracol is a trade mark.) ~2341~l The ~Ihardener component" was formed by mixing the ingredi ents together in a reactor a-k 100C at a pressure of less than 100 millimeters (mm) of merc~lry for one and one half hours .
Base Component Material Parts by Weight Polyol (Pluracol 220*) 100.0 Polyether triol (Pluracol TP440**) - 9.4 Limestone filler 75.0 Aromatic diisocyanate (PAPI 901***) 107.0 Total 291.4 *Polyol having a molecular weight of about 2600, a viscosity of 1200 cps at 25C, and an apparent pH of 6.5, manufactured by BASF ~yandotte Corporation.
**Reaction product of trlmethylolpropane and propylene oxide having a molecular weight of about 425, a vis-cosity of 600 cps at 25C., and an apparent pH of 605J
produced by BASF Wyandotte Corporation.
***A polymethylene polyphenylene isocyanate having a functionality of 2.3, an isocyanate equivalent of 133, and a viscosity of 80 cps at 25C, manufactured by Upjohn Polymer Chemicals.
The functional hydroxyl groups of the polyols in the l'base component" react with aromatic diisocyanate which provides a composition having a desirable viscosity. The limestone filler improves of the compatibility of the polyol and diisocyanate components.
In the preparation of the "base component"~ the ingredients (with the exception of the diisocyanate) were mixed together and degassed in a reactor at 100C
under a vacuum o~ less than 100 mm of mercury for three hours. The degass~d mixture was cooled to 70C and the diisocyanate was added to the mixture, care being exercised to exclude moisture which would react with isocyanate in the mixture.
To test the bonding strength of the adhesive system, the two components of the adhesive were mixed to-gether in a volume ratio of 3.36 to 1 of base component to hardener component. The adhesive immediately a~ter being 5 mixed was applied as a thin coat to opposed surfaces of two FRP panels (produced from Derakane~790 vînylester com-pound manufactured by Dow Chemical Company) along an edge bonding zone 2.54 centimeters in width, the bondiny sur-faces previously having been primed with a primer comprised of one part by weight of p,p',p"-triphenylmethane tri-isocyanate to five parts by weight of methylene chloride.
The two F~P panels were clamped together with the bonding zones coated with adhesive in face-to-face contact. The adhesive set within about ten minutes forming a bonded lap seam 2.54 centimeters wide between the two FRP panelsO The bond was aged at 25C for 24 hours, heated at 135C. for 30 minutes, and tested at 25C. for shear strength by the procedure described in ASTM Designation No. D1002-53T.
The shear strength results listed in Table I are the average result of six test samples:
TABLE _ Shear Str~ngth Test Co dition in kgf/cm Initial 63.91 After 14 days ~ 93C 62.36 After 24 hours immersed 64.27 in boiling water After 90 days @ 37C in 65.61 98~ relative humidity 3G After 3 hours @ 138C 61.58 EXAMPLE II
The adhesive system of Example I was used to prepare lap bonded specimens comprised o~ a FRP panel and a cold rolled steel panel. The prepared specimens were aged at 25C for 24 hours, hea~ed for 30 minutes at 135C~
TRADEMARK
The use of the monomeric nitrogen containing polyol with from 3 to 6 hydroxyls suggested as a component of the FRP adhesive system described in U.S. Patent 3,812,003 is not used in the adhesive system of the present invention because of the presence of the para-phenylene diamine or ortho-phenylene diamine in the adhesive system hexein des-cribed, since the combination would produce an adhesive material that has an objectionably short gel or set time once the adhesive components are mixed together.
In the use of the adhesive sys-tem of the present invention, the surfaces of the FRP panels to be bonded together first are "wiped" or sprayed with an FRP primer, such as a solvent solution of an organic polyisocyanate.
The two components of the adhesive system (i.e., the "hardener component" and the "base component") are mixed together (desirably by feeding the two components to a portable hand-held mixing head) to form a reaction mixture comprised of (a) 100 parts by weight of a polyester triol or a polyether triol having a molecular weiyht between about 400 and 1000, (b) an aromatic diisocyanate having a functionality o from about 2.3 to 2.7 and an equivalent weight of about 85 to 150, said isocyanate being present in an amount in excess of the amount to stoichoimetrically react with the polyester triol or polyether triol in the mixture, (c) sufficient para-phenylene diamine or ortho-phenylene diamine or a mixture thereof to produce a desired flow resistance in the reaction mixture, (d) sufficient tin compound catalyst to achieve setting of the reaction mixture within 15 minutes after the two components of the adhesive system are mixed together, and ~e) suEficient amount of polyol free of nitrogen groups to provide fllnctional hydroxyl groups to stoichiometrically react with at least essentially all of the excess reactive isocyana~e groups in the reaction mixture. A thin film of the reaction mixture is spread on one or both of the surfaces of the FRP panels to be ;23~
bonded together and the two panels are clamped together until the adhesive mixture sets. Setting of the adhesive mixture can be accelerated by heating the assembly (desir-ably, to a temperature between 100C. to 175C.).
Although the adhesive system has been described for bonding two FRP panels together, the system also can be used for FRP-to-metal bonding and for metal-to-metal bonding.
The invention will be more fully understood from the following examples.
EXAMPLE I
A two-part adhesive system comprised of a "hard-ener component" and a "base component" was formed according to the following formulations:
Hardener_Component MaterialParts by Wei~ht Polyether triol (Pluracol TP440*) 100.0 1,4-Butanediol 7.4 Tetrol (Pluracol PEP450**) 20 3 Para-Phenylenediamine 3.19 Dibutyltin dilaurate 07 Total130.96 *Reaction product of trimethylolpropane and propylene oxide having a molecular weight of about 425, a viscosity of 600 cps at 25C., and an apparent pH
of 6.5, produced by BASF Wyandotte Corporation.
**Reaction product of pentaerythritol and propylene oxide with an equivaIent weight of about 100, sold by Wyandotte Chemical Company. (Pluracol is a trade mark.) ~2341~l The ~Ihardener component" was formed by mixing the ingredi ents together in a reactor a-k 100C at a pressure of less than 100 millimeters (mm) of merc~lry for one and one half hours .
Base Component Material Parts by Weight Polyol (Pluracol 220*) 100.0 Polyether triol (Pluracol TP440**) - 9.4 Limestone filler 75.0 Aromatic diisocyanate (PAPI 901***) 107.0 Total 291.4 *Polyol having a molecular weight of about 2600, a viscosity of 1200 cps at 25C, and an apparent pH of 6.5, manufactured by BASF ~yandotte Corporation.
**Reaction product of trlmethylolpropane and propylene oxide having a molecular weight of about 425, a vis-cosity of 600 cps at 25C., and an apparent pH of 605J
produced by BASF Wyandotte Corporation.
***A polymethylene polyphenylene isocyanate having a functionality of 2.3, an isocyanate equivalent of 133, and a viscosity of 80 cps at 25C, manufactured by Upjohn Polymer Chemicals.
The functional hydroxyl groups of the polyols in the l'base component" react with aromatic diisocyanate which provides a composition having a desirable viscosity. The limestone filler improves of the compatibility of the polyol and diisocyanate components.
In the preparation of the "base component"~ the ingredients (with the exception of the diisocyanate) were mixed together and degassed in a reactor at 100C
under a vacuum o~ less than 100 mm of mercury for three hours. The degass~d mixture was cooled to 70C and the diisocyanate was added to the mixture, care being exercised to exclude moisture which would react with isocyanate in the mixture.
To test the bonding strength of the adhesive system, the two components of the adhesive were mixed to-gether in a volume ratio of 3.36 to 1 of base component to hardener component. The adhesive immediately a~ter being 5 mixed was applied as a thin coat to opposed surfaces of two FRP panels (produced from Derakane~790 vînylester com-pound manufactured by Dow Chemical Company) along an edge bonding zone 2.54 centimeters in width, the bondiny sur-faces previously having been primed with a primer comprised of one part by weight of p,p',p"-triphenylmethane tri-isocyanate to five parts by weight of methylene chloride.
The two F~P panels were clamped together with the bonding zones coated with adhesive in face-to-face contact. The adhesive set within about ten minutes forming a bonded lap seam 2.54 centimeters wide between the two FRP panelsO The bond was aged at 25C for 24 hours, heated at 135C. for 30 minutes, and tested at 25C. for shear strength by the procedure described in ASTM Designation No. D1002-53T.
The shear strength results listed in Table I are the average result of six test samples:
TABLE _ Shear Str~ngth Test Co dition in kgf/cm Initial 63.91 After 14 days ~ 93C 62.36 After 24 hours immersed 64.27 in boiling water After 90 days @ 37C in 65.61 98~ relative humidity 3G After 3 hours @ 138C 61.58 EXAMPLE II
The adhesive system of Example I was used to prepare lap bonded specimens comprised o~ a FRP panel and a cold rolled steel panel. The prepared specimens were aged at 25C for 24 hours, hea~ed for 30 minutes at 135C~
TRADEMARK
3~
and tested at 25C. for shear strength by the procedure described in ~STM Designation Mo. D1002-53T. The shear strength results listed in Table II are the average result of six test samples:
TABLE II
Shear Stren~th Test Condition in kgf/c~
Initial 74.37 ~fter 14 days ~ 93C 70. 84 10 ~fter 24 hours immersed83.64 in boiling water ~fter 38 days @ 37~C in75.08 98% relative humidity After 3 hours @ 138C. 80.95 EXAMPLE III
A two-part adhesive system was formed using the "base component" described in Example I and a "hardener com-ponent" formed according to the following formulation:
Hardener Component MaterialParts by Weight Polyester triol (RUCO 2015-200*) 100.0 1,4-Butanediol 10.2 Para-phenylene diamine 3.01 25 Trimethylol propane 20.0 Dibutyl tin dilaurate .0605 Red dye 035 Total133.055 *Polyester triol with a functionality of 2.8, a molec-ular weight of 785, and a viscosity of 8000 cps, manufacturec~ by Hooker Chemical Corporation.
: The adhesive was mixed as descri.bed in Example I
and test samples for bonded lap strength tests were pre~
pared as described in Example I.
The specimens were tested for shear strength ~923~L
within one day after bonding and at the specified temper-atures by the procedure described in ASTM Designation No.
D1002-S3T. The shear strength results listed in Table III
are the average .result of five test samples:
TABLE III
Shear Stren~th Test TemPerature in kgf/cm _ -40C. 50.20 25C. 46.03 82C. 35.92 121C. 20.93 200C. 7.21 EXAMP E_ V
~ dditional F~P lap-bonded samples were prepared using the adhesive system described in Example III with a 1.25 cm bonding zone and quick set at the temperatures and for the times listed in Table IV. Immediately after set-ting and while still warm they were impacted on their edgein an impact tester and the force to break the bond was recorded. The results listed in Table IV are the average result of two test samples.
TABLE IV
Set Time Set TempexatureXmpact~ m ) 3 minutes 110C. 21.9 5 minutes 110C. 44.9 3 minutes 116C. 23.0 5 minutes 116C. 4301 3 minutes 121C. 28.2 5 minutes 121C. 43.1 EX~P~E V
Two-part adhesive ~ystems were formed using the "base component" ~escribed in Example I and "hardener components" according to the following formulations:
~3tZ3~9~
Hardener_C_ ponent Material Parts By Weight Composition_A Composition B
Polyether triol 100.0 100.0 (Pluracol TP440) Tetrol 124.0 100.0 (Pluracol PEP450) ortho-phenylene 5.56 12.5 diamine Dibutyl tin 0.0490.049 dilaurate -Total 229.609212.549 The adhesive was mixed as described in Example I and test samples for bonded lap strength tests were pre-pared as described in Example I. The samples were tested by the test procedure referenced in Example I. The test results are listed in Table V:
. TABLE V
Initial Shear Strength Adhesive System in kgf/cm2 _ With Composition A as 64.5 hardener component With Composition B as 66.5 hardener component
and tested at 25C. for shear strength by the procedure described in ~STM Designation Mo. D1002-53T. The shear strength results listed in Table II are the average result of six test samples:
TABLE II
Shear Stren~th Test Condition in kgf/c~
Initial 74.37 ~fter 14 days ~ 93C 70. 84 10 ~fter 24 hours immersed83.64 in boiling water ~fter 38 days @ 37~C in75.08 98% relative humidity After 3 hours @ 138C. 80.95 EXAMPLE III
A two-part adhesive system was formed using the "base component" described in Example I and a "hardener com-ponent" formed according to the following formulation:
Hardener Component MaterialParts by Weight Polyester triol (RUCO 2015-200*) 100.0 1,4-Butanediol 10.2 Para-phenylene diamine 3.01 25 Trimethylol propane 20.0 Dibutyl tin dilaurate .0605 Red dye 035 Total133.055 *Polyester triol with a functionality of 2.8, a molec-ular weight of 785, and a viscosity of 8000 cps, manufacturec~ by Hooker Chemical Corporation.
: The adhesive was mixed as descri.bed in Example I
and test samples for bonded lap strength tests were pre~
pared as described in Example I.
The specimens were tested for shear strength ~923~L
within one day after bonding and at the specified temper-atures by the procedure described in ASTM Designation No.
D1002-S3T. The shear strength results listed in Table III
are the average .result of five test samples:
TABLE III
Shear Stren~th Test TemPerature in kgf/cm _ -40C. 50.20 25C. 46.03 82C. 35.92 121C. 20.93 200C. 7.21 EXAMP E_ V
~ dditional F~P lap-bonded samples were prepared using the adhesive system described in Example III with a 1.25 cm bonding zone and quick set at the temperatures and for the times listed in Table IV. Immediately after set-ting and while still warm they were impacted on their edgein an impact tester and the force to break the bond was recorded. The results listed in Table IV are the average result of two test samples.
TABLE IV
Set Time Set TempexatureXmpact~ m ) 3 minutes 110C. 21.9 5 minutes 110C. 44.9 3 minutes 116C. 23.0 5 minutes 116C. 4301 3 minutes 121C. 28.2 5 minutes 121C. 43.1 EX~P~E V
Two-part adhesive ~ystems were formed using the "base component" ~escribed in Example I and "hardener components" according to the following formulations:
~3tZ3~9~
Hardener_C_ ponent Material Parts By Weight Composition_A Composition B
Polyether triol 100.0 100.0 (Pluracol TP440) Tetrol 124.0 100.0 (Pluracol PEP450) ortho-phenylene 5.56 12.5 diamine Dibutyl tin 0.0490.049 dilaurate -Total 229.609212.549 The adhesive was mixed as described in Example I and test samples for bonded lap strength tests were pre-pared as described in Example I. The samples were tested by the test procedure referenced in Example I. The test results are listed in Table V:
. TABLE V
Initial Shear Strength Adhesive System in kgf/cm2 _ With Composition A as 64.5 hardener component With Composition B as 66.5 hardener component
Claims (8)
1. A two part adhesive system which produce when intermixed a reaction mixture comprised of:
(a) 100 parts by weight of a polyester triol or polyether triol having a molecular weight of about 400 to 1000, (b) an aromatic diisocyanate having a functionality of from about 2.3 -to 2.7 and an equivalent weight of from about 85 to 150, said aromatic diisocyanate being present in an amount in excess of the amount necessary to stoichiometri-cally react with the polyester triol or polyether triol in said reaction mixture, (c) sufficient para-phenylene diamine or ortho-phenylene diamine or a mixture thereof to produce adequate resistance to flow in the reaction mixture, (d) sufficient tin compound catalyst to cause the reaction mixture to set within 15 minutes at the ambient temperature, and (e) sufficient additional polyol free of nitrogen groups to provide functional hydroxyl groups essentially equivalent to the isocyanate groups in excess of the necessary isocyanate groups to stoichiometrically react with said polyester triol or polyether triol.
(a) 100 parts by weight of a polyester triol or polyether triol having a molecular weight of about 400 to 1000, (b) an aromatic diisocyanate having a functionality of from about 2.3 -to 2.7 and an equivalent weight of from about 85 to 150, said aromatic diisocyanate being present in an amount in excess of the amount necessary to stoichiometri-cally react with the polyester triol or polyether triol in said reaction mixture, (c) sufficient para-phenylene diamine or ortho-phenylene diamine or a mixture thereof to produce adequate resistance to flow in the reaction mixture, (d) sufficient tin compound catalyst to cause the reaction mixture to set within 15 minutes at the ambient temperature, and (e) sufficient additional polyol free of nitrogen groups to provide functional hydroxyl groups essentially equivalent to the isocyanate groups in excess of the necessary isocyanate groups to stoichiometrically react with said polyester triol or polyether triol.
2. The adhesive system of claim 1 wherein said adhesive system includes from 20 to 100 parts by weight of an inert powdery filler.
3. The adhesive system of claim 1 wherein one part of the said two-part system is a component comprised of:
(a) said 100 parts by weight polyester triol or polyether triol, (b) said para-phenylene diamine or ortho-phenylene diamine or mixture thereof, and (c) said tin compound catalyst, and which has a viscosity of from 800 to 4,000 cps at 25°C, and wherein said second part of the two-part system is a component comprised of said aromatic diisocyanate and which has a viscosity of from 20,000 to 55,000 cps at 25°C.
(a) said 100 parts by weight polyester triol or polyether triol, (b) said para-phenylene diamine or ortho-phenylene diamine or mixture thereof, and (c) said tin compound catalyst, and which has a viscosity of from 800 to 4,000 cps at 25°C, and wherein said second part of the two-part system is a component comprised of said aromatic diisocyanate and which has a viscosity of from 20,000 to 55,000 cps at 25°C.
4. The adhesive system of claims 1 or 2 wherein said adhesive mixture contains from 1.8 to 3.0 parts by weight of para-phenylene diamine or ortho-phenylene diamine or mixture thereof per 100 parts by weight of said poly-ester triol or polyether triol in said adhesive mixture.
5. The adhesive system of claims 1 or 2 wherein the said diamine in the adhesive mixture is para-phenylene diamine.
6. The adhesive system of claims 1 or 2 wherein said adhesive mixture contains from 0.01 to 0.2 parts by weight of said tin compound catalyst per 100 parts by weight of said polyester triol or polyether triol in said adhesive mixture.
7. The adhesive system of claim 1 wherein said tin compound catalyst is dibutyl tin dilaurate.
8. A laminate comprised of two panels of fiberglass reinforced polyester adhered together with an adhesive comprising a reaction product of a reactive mixture of:
(a) 100 parts by weight of a polyester triol or polyether triol having a molecular weight of about 400 to 1000, (b) an aromatic diisocyanate having a functionality of from about 2.3 to 2.7 and an equivalent weight of from about 85 to 150, said aromatic diisocyanate being present in an amount in excess of the amount necessary to stoichiomet-trically react with the polyester triol or polyether triol in said reaction mixture, (c) sufficient para-phenylene diamine or ortho-phenylene diamine or a mixture thereof to produce adequate resistance to flow in said reactive mixture, (d) sufficient tin compound catalyst to cause said reactive mixture to set within 15 minutes of the ambient tem-perature, and (e) sufficient additional polyol free of nitrogen groups to provide functional hydroxyl groups essentially equivalent to the isocyanate groups in excess of the necessary isocyanate groups to stoichiometrically react with said polyester triol or polyether triol.
(a) 100 parts by weight of a polyester triol or polyether triol having a molecular weight of about 400 to 1000, (b) an aromatic diisocyanate having a functionality of from about 2.3 to 2.7 and an equivalent weight of from about 85 to 150, said aromatic diisocyanate being present in an amount in excess of the amount necessary to stoichiomet-trically react with the polyester triol or polyether triol in said reaction mixture, (c) sufficient para-phenylene diamine or ortho-phenylene diamine or a mixture thereof to produce adequate resistance to flow in said reactive mixture, (d) sufficient tin compound catalyst to cause said reactive mixture to set within 15 minutes of the ambient tem-perature, and (e) sufficient additional polyol free of nitrogen groups to provide functional hydroxyl groups essentially equivalent to the isocyanate groups in excess of the necessary isocyanate groups to stoichiometrically react with said polyester triol or polyether triol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US273,133 | 1981-06-12 | ||
| US06/273,133 US4336298A (en) | 1981-06-12 | 1981-06-12 | Adhesive composition and composite made therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1192341A true CA1192341A (en) | 1985-08-20 |
Family
ID=23042675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000403884A Expired CA1192341A (en) | 1981-06-12 | 1982-05-27 | Adhesive composition and composite made therewith |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4336298A (en) |
| EP (1) | EP0068209B1 (en) |
| JP (1) | JPS57207667A (en) |
| CA (1) | CA1192341A (en) |
| DE (1) | DE3262634D1 (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853267A (en) * | 1984-02-09 | 1989-08-01 | Minnesota Mining And Manufacturing Company | Easy open closure system |
| JPS61228075A (en) * | 1985-04-02 | 1986-10-11 | Meisei Kogyo Kk | Adhesive composition |
| CA1279249C (en) * | 1986-05-30 | 1991-01-22 | Randall C. Rains | Two component polyurethane adhesive |
| US4954199A (en) * | 1986-05-30 | 1990-09-04 | Mobay Corporation | Two component polyurethane adhesive |
| JPS63150364A (en) * | 1986-12-12 | 1988-06-23 | Honda Motor Co Ltd | Structural outer panel made of synthetic resin |
| DE3727847A1 (en) | 1987-08-20 | 1989-03-02 | Fuller H B Co | MELT ADHESIVE AND METHOD FOR ITS PRODUCTION AND PROCESSING |
| US4876308A (en) * | 1988-02-18 | 1989-10-24 | Gencorp Inc. | Polyurethane adhesive for a surface treatment-free fiber reinforced plastic |
| US5231147A (en) * | 1989-04-10 | 1993-07-27 | Rheox, Inc. | Thermosetting polyurethane structural adhesive compositions and processes for producing the same |
| DE3919697A1 (en) * | 1989-06-16 | 1990-12-20 | Bayer Ag | SINGLE-COMPONENT REACTIVE ADHESIVES BASED ON POLYURETHANE |
| US4994540A (en) * | 1990-01-16 | 1991-02-19 | Mobay Corporation | Sag resistant, unfilled, low viscosity urethane structural adhesive |
| US5204439A (en) * | 1990-01-16 | 1993-04-20 | Miles Inc. | Two-component polyurethane adhesive |
| US5164473A (en) * | 1990-01-16 | 1992-11-17 | Miles Inc. | Two-component polyurethane adhesive |
| JPH03283354A (en) * | 1990-03-30 | 1991-12-13 | Shin Kobe Electric Mach Co Ltd | Sealed lead-acid battery |
| DE4033221A1 (en) * | 1990-10-19 | 1992-04-23 | Bayer Ag | TWO-COMPONENT POLYURETHANE ADHESIVES |
| US5308657A (en) * | 1991-09-11 | 1994-05-03 | Miles Inc. | Protection of furniture edging |
| DE4138246A1 (en) * | 1991-11-21 | 1993-05-27 | Bayer Ag | TWO-COMPONENT POLYURETHANE REACTIVE MATERIALS |
| US5175228A (en) * | 1991-12-09 | 1992-12-29 | Gencorp Inc. | Two-component primerless urethane-isocyanurate adhesive compositions having high temperature resistance |
| US5340901A (en) * | 1991-12-09 | 1994-08-23 | Gencorp Inc. | Two-component, primerless, organic phosphorus containing polyurethane adhesive |
| US6746626B2 (en) * | 1994-06-20 | 2004-06-08 | Sgl Technic Inc. | Graphite polymers and methods of use |
| US6001248A (en) * | 1994-08-25 | 1999-12-14 | The University Of Iowa Research Foundation | Gradient interface magnetic composites and systems therefor |
| US5606003A (en) * | 1994-09-01 | 1997-02-25 | Gencorp Inc. | Primerless urethane adhesive compositions |
| US5668211A (en) * | 1996-12-18 | 1997-09-16 | Bayer Corporation | Two-component polyurethane adhesive |
| US5719252A (en) * | 1996-12-18 | 1998-02-17 | Bayer Corporation | Unfilled two-component polyurethane adhesive |
| US6423810B1 (en) | 2001-02-05 | 2002-07-23 | Lord Corporation | High strength, long-open time structural polyurethane adhesive and method of use thereof |
| US6866743B2 (en) | 2001-04-12 | 2005-03-15 | Air Products And Chemicals, Inc. | Controlled structure polyurethane prepolymers for polyurethane structural adhesives |
| US8431058B2 (en) * | 2007-03-19 | 2013-04-30 | Basf Se | Polyurethane systems for production of polyurethane sandwich components |
| DE102009046739B4 (en) * | 2009-11-16 | 2020-03-05 | Saint-Gobain Isover G+H Ag | Two-component adhesive and sealant system |
| WO2011057896A1 (en) * | 2009-11-16 | 2011-05-19 | Saint-Gobain Isover | Adhesive and sealant system |
| CN103189410B (en) * | 2010-11-03 | 2016-07-06 | 汉高股份有限及两合公司 | There is the two component polyurethane adhesive of thixotropic effect |
| EP2468789A1 (en) | 2010-12-24 | 2012-06-27 | Sika Technology AG | Adhesive for wind turbine rotor blades |
| MX2019006130A (en) | 2016-12-28 | 2019-08-14 | Henkel Ag & Co Kgaa | Two-component polyurethane adhesive. |
| JP7004090B2 (en) * | 2018-12-21 | 2022-01-21 | Dic株式会社 | Adhesives, laminated films, and methods for manufacturing laminated films |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248371A (en) * | 1961-03-10 | 1966-04-26 | Wyandotte Chemicals Corp | Cross-linking blocked two-step prepolymer polyurethane coating compositions |
| US3812003A (en) * | 1970-02-11 | 1974-05-21 | Goodyear Tire & Rubber | Polyurethane composition and laminates made therewith |
| JPS53141345A (en) * | 1977-05-17 | 1978-12-09 | Sumitomo Bakelite Co Ltd | Adhesive composition |
| US4247676A (en) * | 1979-08-13 | 1981-01-27 | The Goodyear Tire & Rubber Company | Storable flowable polyurethane adhesive composition |
| US4296212A (en) * | 1980-08-27 | 1981-10-20 | The Upjohn Company | Elastomeric polyurethane-polyurea polymer prepared from an organic polyisocyanate a polyol and an aromatic diamine having at least one of the ortho positions to each amine lower alkyl |
-
1981
- 1981-06-12 US US06/273,133 patent/US4336298A/en not_active Expired - Fee Related
-
1982
- 1982-05-27 CA CA000403884A patent/CA1192341A/en not_active Expired
- 1982-05-27 JP JP57088965A patent/JPS57207667A/en active Granted
- 1982-06-09 EP EP82105060A patent/EP0068209B1/en not_active Expired
- 1982-06-09 DE DE8282105060T patent/DE3262634D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4336298A (en) | 1982-06-22 |
| EP0068209B1 (en) | 1985-03-20 |
| EP0068209A1 (en) | 1983-01-05 |
| DE3262634D1 (en) | 1985-04-25 |
| JPS57207667A (en) | 1982-12-20 |
| JPH0252669B2 (en) | 1990-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1192341A (en) | Adhesive composition and composite made therewith | |
| EP0304083B1 (en) | Primerless adhesive for fiberglass reinforced polyester substrates | |
| US4728710A (en) | Sag resistant urethane adhesives with improved antifoaming property | |
| EP0126297B1 (en) | Method for adhering two different surfaces by means of water dispersible polyurethane adhesive compostitions | |
| EP0777695B2 (en) | Polyurethane compositions having a low content of monomer diisocyanates | |
| US4985535A (en) | Moisture-curable hot-melt adhesive composition | |
| EP0280775B1 (en) | Sag resistant, two component urethane adhesives | |
| CA1278640C (en) | Moisture curable polyurethane polymers | |
| EP0115245B1 (en) | A sag resistant two component adhesive and sealant | |
| EP1517971B1 (en) | Silane based moisture curing hot-melt adhesives | |
| DE60212894T2 (en) | The use of controlled structure polyurethane prepolymers for polyurethane structural adhesives | |
| EP0417540A2 (en) | Masses of reactive polyurethane adhesives comprising finely dispersed polymers | |
| EP3240830B1 (en) | Crash durable epoxy adhesive compositions having improved low-temperature impact resistance and wash off resistance | |
| JP2004518791A (en) | High strength, long opening time structural polyurethane adhesives and methods of using same | |
| EP0464483B1 (en) | Use of adhesives on the basis of polyols and polyisocyanates | |
| JPH05105863A (en) | Adhesive composition | |
| DE3122693A1 (en) | METHOD FOR SOLIDIFYING STONES AND / OR COAL WITH ITSELF OR OTHER GEOLOGICAL FORMATIONS | |
| EP0371370A1 (en) | Process for the preparation and use of moisture-curable hot melt adhesive masses | |
| AU673373B2 (en) | Intumescent one-component sealant | |
| WO1997031046A1 (en) | Solid, adhesive material which peels off smoothly | |
| EP0063534A2 (en) | A sag resistant two component adhesive | |
| JP3479589B2 (en) | Adhesive compositions based on polyurethane and polyamine suspensions, their preparation and use | |
| EP0402728B1 (en) | One-component reactive adhesive based on polyurethane | |
| DE60224974T3 (en) | Moisture-curing adhesives | |
| JP2008521979A (en) | Two-component polyurethane adhesive, additive for the two-component polyurethane adhesive and use of the additive |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |