CA2133839A1 - A high performance epoxy based laminating adhesive - Google Patents
A high performance epoxy based laminating adhesiveInfo
- Publication number
- CA2133839A1 CA2133839A1 CA002133839A CA2133839A CA2133839A1 CA 2133839 A1 CA2133839 A1 CA 2133839A1 CA 002133839 A CA002133839 A CA 002133839A CA 2133839 A CA2133839 A CA 2133839A CA 2133839 A1 CA2133839 A1 CA 2133839A1
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- adhesive material
- substrates
- polyfunctional
- epoxies
- 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
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—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
-
- 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
- C09J175/06—Polyurethanes from polyesters
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Abstract
A process for producing an improved three-dimensional polymeric adhesive material comprises: (1) reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product; and (2) reacting the adduct product with a polyelectrophile to generate a three-dimensional polymeric adhesive material. Preferably, the starting polymer is a high molecular weight polyester, the polyfunctional nucleophile is a polyisocyanate, and the polyelectrophile is at least one polyepoxide. The present invention also encompasses processes for bonding at least two substrates by generating the adhesive material between them, as well as the adhesive material itself. The invention is particularly suitable for bonding electronic components such as printed circuit boards.
Description
~093/20123 2 1 3 3 8 3 9 PCT/US93/02677 ,~ .; , .
A HIGH PERFORMANCE EPOXY BASED LAMINATING ADHESIVE
t . ~! .; ., CROSS-R~FERENCES
This application is a continuation-in-part of Application Serial No. 07/483,266, by Thomas F. Gardeski and Diane G. No~ak, filed February 15, 1990, which is, in turn, a con~inuation of Application Serial No.
5 07/153,141, by Thomas F. Gardeski and Diane G. Novak, filed February 8, 1988, and now abandoned, both of which are also entitled "A High Performance Epoxy Based aminating Adhesive." These two applications are hereby incorporated in their entirety by this reference.
BACKGRO~N~ OF THE INVENTION
This invention is direted to three-dimensional :
~ polymeric adhesive materials and m~thods for producing .
~ 15~ uch materials.
, During the past quarter century, the rapid growth of~the electronic circui~s industry has resulted in the de~elopment of higher performance construction :
materials. However, ~he development of high performance :' adhesive materials and systems to bond the construction materials together has not kept pace. This lack of higher performance adhesive materials is particularly :
2133`83~
WOg3/20123 PCT/US93/02677 felt in the assembly of electronic components for use in se~ere environmental conditions, such as under-the-hood automotive and military applications. Adhesive materials and~systems that are currently available mee~ some of the requirements for such properties as peel strength, chemical resistance, moisture resistance, high temperature stability, dimensional stability, especially in the Z-axis direction, and ease of processing.
~; ~ However, these~materials and systems typically fail to 10- meet one or more of these requirements. Therefore, a need exists for an adhesive material that meets all of ; ~ the rèquirements~for use under severe environmental conditions while;~retaining ease of application.
; We have~developed a three-dimensional adhesi~e terial~;and a process~for preparlng it that meets these needs and provides~an improved adhesi~e for use under 20~ se~ere~en~ironment;al~conditions, particularly in the assembly~of electronic components.
~ ~ :
One aspect of the present invention is a process~for produclng a three-dimensional polymeric adhesive material.~ The process comprises:
reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional ~ ~ucleophile to form an adduct product; and :;` ~:: :
~ ~0~3/201~3 ~13 ~B.~ Q . . PCT/US93/02677 (2) reacting the adduct product with a polyelectrophile ~o generate a three-dimensional polymeric adhesive material.
The starting polymer can contain an active hydrogen and ha~e a maximum acid ~alue of 2. Such a starting polymer can be selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, : 10 and mixtures thereof. Preferably, in this alternative, the starting polymer is a high molecular weight polyester.
~ Alternatively, the starting polymer can be a : 15 po~y~unctional hydroxy-containing polymer having a hydroxy number o~:at least 10. Preferably, the polyfunctional hydro~y-containing polymer is selected from the group consisting of polyols, polyesters, :
. : polyurethanes, and mixtures thereof.
: 20 ~ ~
; ~ Preferably, the polyfunctional nucleophile is a ;~ polyfunctional~nitrogen-containing compound. More ~, preferably, the polyfunc~ional nitrogen-containing compound is æelected from the group consisting of 25 ~ polyamines, polyazir1dines, polyisocyanates, and mixtures thereof. Most preferably, the polyfunctional nitxogen-: containing co~pound is a polyisocyanate.
~ .
~; , W O 93/20123 ~ ~ ~ PC~r/US93/~2677 `
Preferably, the polyelectrophile comprises at : least one polyepoxide~ More preferably, the polyepoxide is selected from the group consisting of bisphenol A-~ ~ epichlorohydrin epoxies, novolac epoxies, and mixtures ; 5 thereof. Most preferably, the polyexpoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies and novolac epoxies.
Preferably, when the polyelectrophile comprises at least:one~polyepoxide, the step of reacting the adduct : product with ~:he at least one polyepoxide comprises heating a mixture of the adduct product and the at least o~e polyepoxide~to;a~temperature between about 250F and about 400~F.
;` Preferably~ when a high molecular weight polyéster:and~at~least~one:polyepoxide are uæed to form the~three-dimen~ional~polymeric material, the high ; molecular~weight~polyester~comprlses fr~m about 50- to 2a ;~ about~90~ by~weight:~of:the~three-dimensional polymeric ::adhesive:material~and~the polyepoxide comprises from about~10% to~.~about~50% by weisht of the three-dimensional : . polymeric adhesive material.
25 ~: Another aspect~of:the~:present invention is a process for bonding at least two substrates. The process comprises the steps of:
(1) reacting a starting polymer containing an ~$o 93/~123 ~ g~ PCT/US93/02~77 active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product;
(2) mixing the adduct product with a polyelectrophile to generate a bonding precursor;
A HIGH PERFORMANCE EPOXY BASED LAMINATING ADHESIVE
t . ~! .; ., CROSS-R~FERENCES
This application is a continuation-in-part of Application Serial No. 07/483,266, by Thomas F. Gardeski and Diane G. No~ak, filed February 15, 1990, which is, in turn, a con~inuation of Application Serial No.
5 07/153,141, by Thomas F. Gardeski and Diane G. Novak, filed February 8, 1988, and now abandoned, both of which are also entitled "A High Performance Epoxy Based aminating Adhesive." These two applications are hereby incorporated in their entirety by this reference.
BACKGRO~N~ OF THE INVENTION
This invention is direted to three-dimensional :
~ polymeric adhesive materials and m~thods for producing .
~ 15~ uch materials.
, During the past quarter century, the rapid growth of~the electronic circui~s industry has resulted in the de~elopment of higher performance construction :
materials. However, ~he development of high performance :' adhesive materials and systems to bond the construction materials together has not kept pace. This lack of higher performance adhesive materials is particularly :
2133`83~
WOg3/20123 PCT/US93/02677 felt in the assembly of electronic components for use in se~ere environmental conditions, such as under-the-hood automotive and military applications. Adhesive materials and~systems that are currently available mee~ some of the requirements for such properties as peel strength, chemical resistance, moisture resistance, high temperature stability, dimensional stability, especially in the Z-axis direction, and ease of processing.
~; ~ However, these~materials and systems typically fail to 10- meet one or more of these requirements. Therefore, a need exists for an adhesive material that meets all of ; ~ the rèquirements~for use under severe environmental conditions while;~retaining ease of application.
; We have~developed a three-dimensional adhesi~e terial~;and a process~for preparlng it that meets these needs and provides~an improved adhesi~e for use under 20~ se~ere~en~ironment;al~conditions, particularly in the assembly~of electronic components.
~ ~ :
One aspect of the present invention is a process~for produclng a three-dimensional polymeric adhesive material.~ The process comprises:
reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional ~ ~ucleophile to form an adduct product; and :;` ~:: :
~ ~0~3/201~3 ~13 ~B.~ Q . . PCT/US93/02677 (2) reacting the adduct product with a polyelectrophile ~o generate a three-dimensional polymeric adhesive material.
The starting polymer can contain an active hydrogen and ha~e a maximum acid ~alue of 2. Such a starting polymer can be selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, : 10 and mixtures thereof. Preferably, in this alternative, the starting polymer is a high molecular weight polyester.
~ Alternatively, the starting polymer can be a : 15 po~y~unctional hydroxy-containing polymer having a hydroxy number o~:at least 10. Preferably, the polyfunctional hydro~y-containing polymer is selected from the group consisting of polyols, polyesters, :
. : polyurethanes, and mixtures thereof.
: 20 ~ ~
; ~ Preferably, the polyfunctional nucleophile is a ;~ polyfunctional~nitrogen-containing compound. More ~, preferably, the polyfunc~ional nitrogen-containing compound is æelected from the group consisting of 25 ~ polyamines, polyazir1dines, polyisocyanates, and mixtures thereof. Most preferably, the polyfunctional nitxogen-: containing co~pound is a polyisocyanate.
~ .
~; , W O 93/20123 ~ ~ ~ PC~r/US93/~2677 `
Preferably, the polyelectrophile comprises at : least one polyepoxide~ More preferably, the polyepoxide is selected from the group consisting of bisphenol A-~ ~ epichlorohydrin epoxies, novolac epoxies, and mixtures ; 5 thereof. Most preferably, the polyexpoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies and novolac epoxies.
Preferably, when the polyelectrophile comprises at least:one~polyepoxide, the step of reacting the adduct : product with ~:he at least one polyepoxide comprises heating a mixture of the adduct product and the at least o~e polyepoxide~to;a~temperature between about 250F and about 400~F.
;` Preferably~ when a high molecular weight polyéster:and~at~least~one:polyepoxide are uæed to form the~three-dimen~ional~polymeric material, the high ; molecular~weight~polyester~comprlses fr~m about 50- to 2a ;~ about~90~ by~weight:~of:the~three-dimensional polymeric ::adhesive:material~and~the polyepoxide comprises from about~10% to~.~about~50% by weisht of the three-dimensional : . polymeric adhesive material.
25 ~: Another aspect~of:the~:present invention is a process for bonding at least two substrates. The process comprises the steps of:
(1) reacting a starting polymer containing an ~$o 93/~123 ~ g~ PCT/US93/02~77 active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product;
(2) mixing the adduct product with a polyelectrophile to generate a bonding precursor;
(3) applying the bonding precursor between ~he substrates prior to the reaction between the adduct product and the polyel ctrophile; and (4) reacting the adduct product with the polyelectrophile to generate a three-dimensional polymer adhesive material between the substrates, thereby bonding the substrates.
Typically, ~he substrates are selected from the group consisting of film substrates, foil substrates, and : 15 ~ hardboard ~ubstrates.
Another aspect of the present in~ention is a three-dimensional;adhesive produced by the process described above~. In general, the adhesive comprises:
2~ at least two linear:polymer moieties, each , moiety cornprising a~polymer containing nucleophilic nitrogen at~ms capable of react1on with an electrophile and (2) cross-l~inks between the nitrogens of the polymer moieties; each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties :~ through reaction o~ an electrophile with the nitrogen : atoms.
WO 93/20123 ~3~39 PCT/US93/02677 Preferably, the linear polymer moieties are selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, : polyfunctional phenolic resins, and mixtures thereof.
Preferably, the linear polymer moieties are ~; formed by reac~ion of a hydroxy-containing polymer with a polyfunctional nitrogen-containing nucleophile.
: ~ ' Preferably, the polyfunctional nitrogen-containing nucleophile:is selected from the group consisting of polyamines, polyaziridines, : : :
polyisocyanates, and mixtures thereof.
:15 One preferred versio~ of the three-dimensional polymeric adhesive of:~he present in~ention comprises:
at least two linear urethane linked polymer moieti~es, each moiety comprlsing a hydroxy-termina~ed polyester linked in urethane linkage by an ::: :~ : :
~ 20 aromatic isocyanate; and - : :
(2) ~ross-links between ~he ~itrogens of the ; urethane linked polymer moieties, each cross-link comprising a phenyl-containing polymer linked to the : : nltrogen at~ms of the urethane linkages by -CH2-CHOH-, :25 linkages, with ~he methylene groups of the linkages being : bonded directly to the nitrogen atoms such that the ross-links form a three-dimensional polymeric structure.
:
-- , 0 g3/20123 ~ P~/~JS93/iD2677 In this version, the cross--links preferably comprise at teast one polyepoxide selected f rom the group consisting of bisphenol A--epichlorohydrin epoxies, novolac epoxies, ~nd mixtures thereof.
s More preferab.y, the polyepoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies having the formula CH2--CH--CH2~0~¢~0CH2--CH--CH230~¢~-ocH2--CH--CH2 ~ ~ ~ and novolac epoxies having the formula :~ /o\
15 ~ :CH2--CH--CH2 o~CH2 ~ CH2~o--CH2--CH--CH2 wherein n is an inte~er from 1 to about 20, n being ~:: :
independently chosen for the bispheno~ A-epichlorohydrin :
epoxies and: ~or the novolac epoxies.
The adhesive material of the present invention can be used to bond at lecst two substrates, thereby ' forming a ~omposite structure. A composite structure formed cccording to the invention comprises:
:~ :
: : 25 (l ) :at least two bondable substrates; and (2) a three-dimensional polymeric adhesive material in adhesive contact with each o~ the substrates such that each of the substrates is bonded to at least SUBSTITUTE SHEET
W093/20123 b~3~ PCT/US93/02677 one other substrate by the adhesi~e material, the adhesive material comprising:
(a) at least two linear polymer moieties, each moiety comprising a polymer con~aining nucleophilic nitrogen atoms capable of reaction with an electrophile;
and (b) cross-links between the nitrogens of ~ the polymer moieties, each cross-link comprising a : polymer linked to the nitrogen atoms of the polymer : 10 moieties through reaction of an electrophile with the nitrogen atoms.
, .
DESCRIPTION
`15 I. The Adhesive Production Process i ::
One aspect of the present inv~ntion is a process for producing~a three-dimensional polymexic adhesive material. The polymeric adhesive material produced by this~process has impro~ed peel strength, chemical reslstance, moisture resistance, high ; : temperature.stability, and dimensional stabili~y. It is easy to process and is particularly suitable for use with electronic construct1on materials, such as printed circuit boards. ~In general, this process comprises:
~, 1) reacting a starting polymer containing an active hydrogen function or hydroxy func~ion with a polyfunctional nucleophiIe to form an adduct product; and ,10g3~20123 ~ t ~ ~ PCT/US~3/02677 f.J ~ ~ ~ V d ~
~ 2) reacting the adduct product with a polyelectrophile to generate a three-dim~nsional polymeric adhesive material.
S The starting polymer can contain an active hydrogen, with a maximum acid value of 2. Such polymers can be polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, or mixtures : thereof.
Alternatively, the starting polymer can be a polyfunctional hydroxy-containing polymer having a hydroxy number of at least 10. The poly~unctional hydroxy-containing pol~mer can be a polyol, a polyester, :
a polyurethane, or a mixture thexeof.
Preferably, the:starting polymer is a high : molecular weight polyester with hydroxyl end-yroup fun~tionality of the alcohol type.
20;
: The~ polyfunctional nucleophile can be a ~: polyfunctional nitrogen-containing:compound. Such :' compounds include polyamines, polyaziridines, polyisocyanates, and mixtures thereof. Preferably, the polyfunc~io~al nitrogen-containing:compound is a :
polyisoGyaLnate~
A particularly suitable starting polymer is a ::
:
WO93/2~123 } ~ 3g P~T/VS93~2677 polyester resin such as DuPont 49002 base. A
particularly suitable polyelectrophile is a polyfunctional isocyanate sold by Mobay Chemical Corp., Pittsburgh, Pennsylvania, under the name of Mondur MRS, which is a polymethylene polyphenylene ester of isocyanic acid.
Carbon atoms of alkyl and/or aryl moieties within the starting polymer or polyfunctional nucleophile can be optionally substituted with methyl and/or C2-C5 : : :
alkyl. The terms "starting polymer" and "polyfunctional nuc~eophile", as used herein, include compounds optionally substituted with methyl and/or C2-C5 alkyl.
The rea~tion of the starting polymer with the ~: , :
po~yfunctional nucleophile takes place slowly at room temperature and takes place more rapldly at about 250F.
Typically, this: reaction is performed in a solvent, such as a 90~:10~ mixture of methylene chloride:cyclohexanone.
: :
~ ~ .
The;second~stage of the process comprised is reacting the adduct product with a polyelectrophile to generate the three-dimensional polymeric adhesi~e material. The polyelectrophile is preferably a 25 ~ polyepoxide. More preferably, it is a polyepoxide selected from the group consisting of bisphenol A-epichlorohydrln epoxies, novolac epoxies, or a mixture thereof. Most preferably, the polyelectrophile is a ' ::
~093/20123 ~ 3~9 P~/USg3/0~677 mixture of a bisphenol A-epichlorohydrin epoxy, such as Celanese Epi-Rez-5132, and a novolac epoxy, such as Dow DEN 438. The bisphenol A-epichlorohydrin epoxy has the following structure:
CH/2--\CH--CH2~0~C~OCH2--CIH-CH230~C~ocH2--CH--CH2 :: CH3 c~3 :
~: 10 wherein n is an integer fron~ 1 to about 20. The novolac epoxy has :the f ollowtng structure:
;, : : .
: OCH2--GH--CH2 /\
CH2--CH--CH2--0~cH2~cH2~0--CH2--CH--CH2 wherein n is an integer from 1 to about 20. The vaîues o~ n are~: independently chosen for the bis-epi and novolac epoxies.
: 2:0~
Preferably, when a high molecwlar weight polyester and at least one polyepoxide are used to form the three-dlmensional polymeric material, the high ~ .
molecular weight ~polyester comprises f rom about 5070 to 25 about 90% by weight of the three-dimensional polymeric `: adhesive rnaterial and the polyepoxide comprises ~rom ~ ::
about 10% to about 50% by weight of the three--dimensional polymeric adhesive material.
SUBSTITUTE StlE~ET
WO 93/20123 ~3g j PCI/US93/02677 The reactivn of the adduct product and the polyelectrophile preferably takes place at a temperature from about 250-F to about 400-F. The first ond second stage reactions are depicted below:
1 st Stage:
H(R)xH + OCN-[c6H4(cH2)]n-Nco . O
~O(R)x-o-cN-[c6H4(cH2)~n-Nco H
where R represents the ester repeat unit and x, represents the number of ester repeat units and :
n represents the number of organic aromatic repeat units in th~e isocyanate component.
Typically, ~he substrates are selected from the group consisting of film substrates, foil substrates, and : 15 ~ hardboard ~ubstrates.
Another aspect of the present in~ention is a three-dimensional;adhesive produced by the process described above~. In general, the adhesive comprises:
2~ at least two linear:polymer moieties, each , moiety cornprising a~polymer containing nucleophilic nitrogen at~ms capable of react1on with an electrophile and (2) cross-l~inks between the nitrogens of the polymer moieties; each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties :~ through reaction o~ an electrophile with the nitrogen : atoms.
WO 93/20123 ~3~39 PCT/US93/02677 Preferably, the linear polymer moieties are selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, : polyfunctional phenolic resins, and mixtures thereof.
Preferably, the linear polymer moieties are ~; formed by reac~ion of a hydroxy-containing polymer with a polyfunctional nitrogen-containing nucleophile.
: ~ ' Preferably, the polyfunctional nitrogen-containing nucleophile:is selected from the group consisting of polyamines, polyaziridines, : : :
polyisocyanates, and mixtures thereof.
:15 One preferred versio~ of the three-dimensional polymeric adhesive of:~he present in~ention comprises:
at least two linear urethane linked polymer moieti~es, each moiety comprlsing a hydroxy-termina~ed polyester linked in urethane linkage by an ::: :~ : :
~ 20 aromatic isocyanate; and - : :
(2) ~ross-links between ~he ~itrogens of the ; urethane linked polymer moieties, each cross-link comprising a phenyl-containing polymer linked to the : : nltrogen at~ms of the urethane linkages by -CH2-CHOH-, :25 linkages, with ~he methylene groups of the linkages being : bonded directly to the nitrogen atoms such that the ross-links form a three-dimensional polymeric structure.
:
-- , 0 g3/20123 ~ P~/~JS93/iD2677 In this version, the cross--links preferably comprise at teast one polyepoxide selected f rom the group consisting of bisphenol A--epichlorohydrin epoxies, novolac epoxies, ~nd mixtures thereof.
s More preferab.y, the polyepoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies having the formula CH2--CH--CH2~0~¢~0CH2--CH--CH230~¢~-ocH2--CH--CH2 ~ ~ ~ and novolac epoxies having the formula :~ /o\
15 ~ :CH2--CH--CH2 o~CH2 ~ CH2~o--CH2--CH--CH2 wherein n is an inte~er from 1 to about 20, n being ~:: :
independently chosen for the bispheno~ A-epichlorohydrin :
epoxies and: ~or the novolac epoxies.
The adhesive material of the present invention can be used to bond at lecst two substrates, thereby ' forming a ~omposite structure. A composite structure formed cccording to the invention comprises:
:~ :
: : 25 (l ) :at least two bondable substrates; and (2) a three-dimensional polymeric adhesive material in adhesive contact with each o~ the substrates such that each of the substrates is bonded to at least SUBSTITUTE SHEET
W093/20123 b~3~ PCT/US93/02677 one other substrate by the adhesi~e material, the adhesive material comprising:
(a) at least two linear polymer moieties, each moiety comprising a polymer con~aining nucleophilic nitrogen atoms capable of reaction with an electrophile;
and (b) cross-links between the nitrogens of ~ the polymer moieties, each cross-link comprising a : polymer linked to the nitrogen atoms of the polymer : 10 moieties through reaction of an electrophile with the nitrogen atoms.
, .
DESCRIPTION
`15 I. The Adhesive Production Process i ::
One aspect of the present inv~ntion is a process for producing~a three-dimensional polymexic adhesive material. The polymeric adhesive material produced by this~process has impro~ed peel strength, chemical reslstance, moisture resistance, high ; : temperature.stability, and dimensional stabili~y. It is easy to process and is particularly suitable for use with electronic construct1on materials, such as printed circuit boards. ~In general, this process comprises:
~, 1) reacting a starting polymer containing an active hydrogen function or hydroxy func~ion with a polyfunctional nucleophiIe to form an adduct product; and ,10g3~20123 ~ t ~ ~ PCT/US~3/02677 f.J ~ ~ ~ V d ~
~ 2) reacting the adduct product with a polyelectrophile to generate a three-dim~nsional polymeric adhesive material.
S The starting polymer can contain an active hydrogen, with a maximum acid value of 2. Such polymers can be polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, or mixtures : thereof.
Alternatively, the starting polymer can be a polyfunctional hydroxy-containing polymer having a hydroxy number of at least 10. The poly~unctional hydroxy-containing pol~mer can be a polyol, a polyester, :
a polyurethane, or a mixture thexeof.
Preferably, the:starting polymer is a high : molecular weight polyester with hydroxyl end-yroup fun~tionality of the alcohol type.
20;
: The~ polyfunctional nucleophile can be a ~: polyfunctional nitrogen-containing:compound. Such :' compounds include polyamines, polyaziridines, polyisocyanates, and mixtures thereof. Preferably, the polyfunc~io~al nitrogen-containing:compound is a :
polyisoGyaLnate~
A particularly suitable starting polymer is a ::
:
WO93/2~123 } ~ 3g P~T/VS93~2677 polyester resin such as DuPont 49002 base. A
particularly suitable polyelectrophile is a polyfunctional isocyanate sold by Mobay Chemical Corp., Pittsburgh, Pennsylvania, under the name of Mondur MRS, which is a polymethylene polyphenylene ester of isocyanic acid.
Carbon atoms of alkyl and/or aryl moieties within the starting polymer or polyfunctional nucleophile can be optionally substituted with methyl and/or C2-C5 : : :
alkyl. The terms "starting polymer" and "polyfunctional nuc~eophile", as used herein, include compounds optionally substituted with methyl and/or C2-C5 alkyl.
The rea~tion of the starting polymer with the ~: , :
po~yfunctional nucleophile takes place slowly at room temperature and takes place more rapldly at about 250F.
Typically, this: reaction is performed in a solvent, such as a 90~:10~ mixture of methylene chloride:cyclohexanone.
: :
~ ~ .
The;second~stage of the process comprised is reacting the adduct product with a polyelectrophile to generate the three-dimensional polymeric adhesi~e material. The polyelectrophile is preferably a 25 ~ polyepoxide. More preferably, it is a polyepoxide selected from the group consisting of bisphenol A-epichlorohydrln epoxies, novolac epoxies, or a mixture thereof. Most preferably, the polyelectrophile is a ' ::
~093/20123 ~ 3~9 P~/USg3/0~677 mixture of a bisphenol A-epichlorohydrin epoxy, such as Celanese Epi-Rez-5132, and a novolac epoxy, such as Dow DEN 438. The bisphenol A-epichlorohydrin epoxy has the following structure:
CH/2--\CH--CH2~0~C~OCH2--CIH-CH230~C~ocH2--CH--CH2 :: CH3 c~3 :
~: 10 wherein n is an integer fron~ 1 to about 20. The novolac epoxy has :the f ollowtng structure:
;, : : .
: OCH2--GH--CH2 /\
CH2--CH--CH2--0~cH2~cH2~0--CH2--CH--CH2 wherein n is an integer from 1 to about 20. The vaîues o~ n are~: independently chosen for the bis-epi and novolac epoxies.
: 2:0~
Preferably, when a high molecwlar weight polyester and at least one polyepoxide are used to form the three-dlmensional polymeric material, the high ~ .
molecular weight ~polyester comprises f rom about 5070 to 25 about 90% by weight of the three-dimensional polymeric `: adhesive rnaterial and the polyepoxide comprises ~rom ~ ::
about 10% to about 50% by weight of the three--dimensional polymeric adhesive material.
SUBSTITUTE StlE~ET
WO 93/20123 ~3g j PCI/US93/02677 The reactivn of the adduct product and the polyelectrophile preferably takes place at a temperature from about 250-F to about 400-F. The first ond second stage reactions are depicted below:
1 st Stage:
H(R)xH + OCN-[c6H4(cH2)]n-Nco . O
~O(R)x-o-cN-[c6H4(cH2)~n-Nco H
where R represents the ester repeat unit and x, represents the number of ester repeat units and :
n represents the number of organic aromatic repeat units in th~e isocyanate component.
5 ~ 2nd Stage: :
O(R)XO--CN~C6 H4(CH2 ) ~n ~ CI~/CH--R-CH\--CH2 epoxy t --O(R)xocN~c6H4(cH2)~n H-C--H
: H--C~H
H--C--OH
H--¢--H
O~R)xOC--N~C6H4(CH2)~n $lJlBS~lT~T~
~093/20123 ~1 3 3 ~ 3 9; I. PCT/US93~02677 The pxessure at which the reaction occurs is generally not critical. The reaCtion typically takes pla e at atmospheric pressure.
: 5 The reaction typically occurs in an aprotic, moderately polar solvent or a mixture of such solvents.
Exemplary solvents are~a mixture of:methylene chloride and cyclohexanone or methyl ethyl ketone, or a mixture of methylene chloride~and cyclohexanone together with methyl ethyl keto~e. However, suitable solvents are not to be limited to these combinations; the choice of solvent i5 generally:~not;~crltlcal.~ ~
~1};. U~e~of the Adhèsiy~for Bondinq The process~ of;~producing:the adhesive of the presént invention:~can:~be incorporat;ed into a process for bond:ing at least~two~substrates. In general, this ~ ;20~ b~ondin~process~compris~e~s of the steps of:
s~ reacting a~starting polymer with a polyfunGtional nucleophile 'co ~ forrn~ an adduct product, as :~ :
described above;
2)~ mixlng the adduct product with a Z5 ;~polyelectrophile to~generate a bonding precursor;
(3) applying the bonding precursor between the :substrates prior to~a reaction between the adduct product and the polyelectrophile; and ::: :
:: :
, ~
.
W O 93/20123 i l ' ' 9 14 P(~rIUS9~102677 (4) reacting the adduct product with the polyelectrophile to generate a three-dimensional polymeric adhesive material between the substrates, thereby bonding the substrates.
The substrates used for this procedure can be film æubstrates, foil substrates, or hardboard :
substrates. A typical example of a film substrate is polyimide film. The substrates can be of the same materials or different materiaIs. The substrates can be electronic circuit boards or other electronic structural components.
III. The Adhesive Compound Another aspect of the invention is an improved three-dimenslonal polymeric adhesive material comprising:
(l) at~least~two linear polymer moieties, each moiety~ comprising a polymer containing nucleophilic nit~rogen atoms cap~ble of reaction with an electrophile;
and ) cross-links between the nitrogens of the ~; polymer moieties, each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties through reaction of an electrophile with the nitrogen atoms.
~ ~ 1 3 3 ~ ~ ~
WO93/20123 - . PCTIUS93/02677 Preferably, the adhesive comprises:
(1) at least ~wo linear urethane linked polymer moieties, each moiety comprising a hydroxy-terminated polyester linked in urethane linkage by an aromatic îsocyanate; and (2) cross-links between the nitrogen of the urethane linked polymer moieties, each cross-link comprising a phenyl-containing polymer linked to the nitrogen atoms of the polyurethanes by -CH2-C~OH- linkages ~: : 10 with the CH2 moieties being located adjacent to the nitrogen atoms.
:
: ~:
As dis1Osed above, this adhesive material can be formed in_situ for bonding at least two substrates.
: 15: The substrates can bé film substrates, foil substrates, : or hardboard substrates.
When~;at least~two: or more substrates are bonded by the adhesi~e;of the present invention, a compo~ite material can ~e formed. The composite material : comprises: :
~ ~ .
(1) at least two bondable substrates, and ~2) the three-dimensional polymeric adhesive material o the:present in~ention ln adhesive contact ~ with each of the:substrates such that each of the : substra~es lS bonded to at least one other substrate by :~ the adhesive material.
~ ~:
.
W O 93/20123 ?,~ ` . P(~rJUS93/02677 ~ ~839 ~ 16 The invention is illustrated by the following example. The example is for illustrative purposes and is not to be construed as limiting the scope of the vention in any~manner.
; An example of the adhesive material of the present invention includes the following components:
10~ :(1) a~polyester resin having a solids content ~;~ of 1~7-20~ comprised of:Dupont 49002 bàse in a solvent mixture of 90~::10% ~(w/w) methylene chloride:
;cyclohexanone;~
2~ àn~epoxy~;novolac at~85~ sollds content l5;~ composed~of~Dow DEN 438-EK85 in~methyl ethyl ketone;
: (3)~ a~bis~-epi;epoxy~composed of Celanese Epi-Rez~ 5132 ~at :100~solids content; and 4)~ a~polyfunctional isocyanate used as a cu ~ tivé~co ~c ent~,~Mondur: ~ S~from Mobay Chem~ical Co The Gomponents can~be~:combined according to either~of the~following two procedures:
The~adhesive coating composition is made by adding:8~0~ by solids~:of the~polyester c~omponent, 10~
25~ by~solids~of~the~epoxy~novolac,;10~by solids of the bis-::;epi epoxy, and~1.2~ parts by weight~:of the~:isocyanate in an open container~wlthout agltation~. The composition is : : : then agi~tated well for 1 to 5 minutes. The container is ~-~"~
WO93/20123 2 1 3 3 8 3 ~ PCT/US~3/02677 then capped with an airtight lid for 30 minutes to allow for the onset of the isocyanate/polyester reaction.
(2) The polyester and isocyanate are combined, thoroughly mixed, and then allowed to stand at room temperature for a minimum of 30 minutes prior to the epoxy addition to allow onset of the isocyanate/polyester reaction.
; The adhes1ve coating composition is then applied by means of the reverse roll coating technique to a l mil polyimide film to yield a 1 mil dry coat weight.
Drying (i.e., remova1 of the sol~ents) is accomplished through a 75-foot, 3-zone oven at 212F and 25 feet per minute. The coated substrate is then positioned nex~ to the treated~side of~a l ounce copper foil, where the copper~foi1 surface i8 treated with Oak CMC-lIl compound to enhance bondability. The polyimide film and copper foil~are~heated~to~a temperature of 225F to 400F with an applied pres~ure of 80 psi (pounds/square inch) to 120 ZO ~psl through~a~coater/1aminator combining station as part of a continuous~operat1on. The resulting roll is brought onto a six inch~core, left at room temperature for l to 7 days, then post cured as follows: 2 hours at 150F, 2 hours at 275F, and 2 hours at 350F.
~ , : : :
A composite structure was prepared according to the first of the abov~ procedures. The resulting composite structure e~hibited the properties shown in :
WO93/20123 ~ 21~ 3 8 ~ 9 PCT/US93/02677 Table 1 when tested per A~SI/IPC-FC-232B and 241B
procedures:
PROPERTIES OF ADHESIVE COMPOSITE STRUCTURE
Initial Peel 20 plia Peel After Solder 21 pli Chemical Reslstance:
: Methyl Ethyl Ketone 21 pli Toluene 20 pli ~Isopropyl Alcohol 21 pli Trichloroethylene/Methylene Chloride 21 pli Solder~ Float : Pass Aging (96 hours at ~ ~o Bond 2~75F~in~:air circulating oven) Strength Change pli -~:pounds per~linear inch ADVANTAGES OF THE _~y~N~
, ::
The`present invention provides an adhesive system with extremely balanced properties and the added 5 :~ benefit of superior Z-axis stability through a unique :: :~ : : : :
curing mechanism. More specifically, the present in~ention provldes an epoxy-based laminating adhesive ~: that can be cqntinuously processed and cured without the :: :
~:
: :
3 1! ~ 1 ~ 3 ~ ~9 WO93/20123 rCT/US93/0~677 evolution of byproducts to pro~ide a flexible bond-ply with superior overall properties, including excellent Z-axis stability. The adhesi~e material is applicable to film substrates such as polyimide, foi~ substrates such as copper, and hardboard substrates, such as FR4 (fiberglass impregnated hardboard). The adhesive of the present invention also possesses superior peel strength, chemical resistance, moisture resistance, and temperature ~: stability. It is particularly suitable for use in the :.
~10 bonding of electronic construction materials, such as : those intended for use in severe en~ironmental conditions. In particular, the adhesive of the present inv-ntion is~suitabl~e~for use in under-the-hood automotive and military~appl1cations.
Although~the present invention has been described in~cons~iderable detail with reference to certa~in~preferred~versions thereof~, other versions are pQssib1e~ Therefore~the spirit~and scope of the pending 2~0~ :claims:~::shou1d not be limited to the description of the preferred versions contained~herein.
:~ :~ : :,
O(R)XO--CN~C6 H4(CH2 ) ~n ~ CI~/CH--R-CH\--CH2 epoxy t --O(R)xocN~c6H4(cH2)~n H-C--H
: H--C~H
H--C--OH
H--¢--H
O~R)xOC--N~C6H4(CH2)~n $lJlBS~lT~T~
~093/20123 ~1 3 3 ~ 3 9; I. PCT/US93~02677 The pxessure at which the reaction occurs is generally not critical. The reaCtion typically takes pla e at atmospheric pressure.
: 5 The reaction typically occurs in an aprotic, moderately polar solvent or a mixture of such solvents.
Exemplary solvents are~a mixture of:methylene chloride and cyclohexanone or methyl ethyl ketone, or a mixture of methylene chloride~and cyclohexanone together with methyl ethyl keto~e. However, suitable solvents are not to be limited to these combinations; the choice of solvent i5 generally:~not;~crltlcal.~ ~
~1};. U~e~of the Adhèsiy~for Bondinq The process~ of;~producing:the adhesive of the presént invention:~can:~be incorporat;ed into a process for bond:ing at least~two~substrates. In general, this ~ ;20~ b~ondin~process~compris~e~s of the steps of:
s~ reacting a~starting polymer with a polyfunGtional nucleophile 'co ~ forrn~ an adduct product, as :~ :
described above;
2)~ mixlng the adduct product with a Z5 ;~polyelectrophile to~generate a bonding precursor;
(3) applying the bonding precursor between the :substrates prior to~a reaction between the adduct product and the polyelectrophile; and ::: :
:: :
, ~
.
W O 93/20123 i l ' ' 9 14 P(~rIUS9~102677 (4) reacting the adduct product with the polyelectrophile to generate a three-dimensional polymeric adhesive material between the substrates, thereby bonding the substrates.
The substrates used for this procedure can be film æubstrates, foil substrates, or hardboard :
substrates. A typical example of a film substrate is polyimide film. The substrates can be of the same materials or different materiaIs. The substrates can be electronic circuit boards or other electronic structural components.
III. The Adhesive Compound Another aspect of the invention is an improved three-dimenslonal polymeric adhesive material comprising:
(l) at~least~two linear polymer moieties, each moiety~ comprising a polymer containing nucleophilic nit~rogen atoms cap~ble of reaction with an electrophile;
and ) cross-links between the nitrogens of the ~; polymer moieties, each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties through reaction of an electrophile with the nitrogen atoms.
~ ~ 1 3 3 ~ ~ ~
WO93/20123 - . PCTIUS93/02677 Preferably, the adhesive comprises:
(1) at least ~wo linear urethane linked polymer moieties, each moiety comprising a hydroxy-terminated polyester linked in urethane linkage by an aromatic îsocyanate; and (2) cross-links between the nitrogen of the urethane linked polymer moieties, each cross-link comprising a phenyl-containing polymer linked to the nitrogen atoms of the polyurethanes by -CH2-C~OH- linkages ~: : 10 with the CH2 moieties being located adjacent to the nitrogen atoms.
:
: ~:
As dis1Osed above, this adhesive material can be formed in_situ for bonding at least two substrates.
: 15: The substrates can bé film substrates, foil substrates, : or hardboard substrates.
When~;at least~two: or more substrates are bonded by the adhesi~e;of the present invention, a compo~ite material can ~e formed. The composite material : comprises: :
~ ~ .
(1) at least two bondable substrates, and ~2) the three-dimensional polymeric adhesive material o the:present in~ention ln adhesive contact ~ with each of the:substrates such that each of the : substra~es lS bonded to at least one other substrate by :~ the adhesive material.
~ ~:
.
W O 93/20123 ?,~ ` . P(~rJUS93/02677 ~ ~839 ~ 16 The invention is illustrated by the following example. The example is for illustrative purposes and is not to be construed as limiting the scope of the vention in any~manner.
; An example of the adhesive material of the present invention includes the following components:
10~ :(1) a~polyester resin having a solids content ~;~ of 1~7-20~ comprised of:Dupont 49002 bàse in a solvent mixture of 90~::10% ~(w/w) methylene chloride:
;cyclohexanone;~
2~ àn~epoxy~;novolac at~85~ sollds content l5;~ composed~of~Dow DEN 438-EK85 in~methyl ethyl ketone;
: (3)~ a~bis~-epi;epoxy~composed of Celanese Epi-Rez~ 5132 ~at :100~solids content; and 4)~ a~polyfunctional isocyanate used as a cu ~ tivé~co ~c ent~,~Mondur: ~ S~from Mobay Chem~ical Co The Gomponents can~be~:combined according to either~of the~following two procedures:
The~adhesive coating composition is made by adding:8~0~ by solids~:of the~polyester c~omponent, 10~
25~ by~solids~of~the~epoxy~novolac,;10~by solids of the bis-::;epi epoxy, and~1.2~ parts by weight~:of the~:isocyanate in an open container~wlthout agltation~. The composition is : : : then agi~tated well for 1 to 5 minutes. The container is ~-~"~
WO93/20123 2 1 3 3 8 3 ~ PCT/US~3/02677 then capped with an airtight lid for 30 minutes to allow for the onset of the isocyanate/polyester reaction.
(2) The polyester and isocyanate are combined, thoroughly mixed, and then allowed to stand at room temperature for a minimum of 30 minutes prior to the epoxy addition to allow onset of the isocyanate/polyester reaction.
; The adhes1ve coating composition is then applied by means of the reverse roll coating technique to a l mil polyimide film to yield a 1 mil dry coat weight.
Drying (i.e., remova1 of the sol~ents) is accomplished through a 75-foot, 3-zone oven at 212F and 25 feet per minute. The coated substrate is then positioned nex~ to the treated~side of~a l ounce copper foil, where the copper~foi1 surface i8 treated with Oak CMC-lIl compound to enhance bondability. The polyimide film and copper foil~are~heated~to~a temperature of 225F to 400F with an applied pres~ure of 80 psi (pounds/square inch) to 120 ZO ~psl through~a~coater/1aminator combining station as part of a continuous~operat1on. The resulting roll is brought onto a six inch~core, left at room temperature for l to 7 days, then post cured as follows: 2 hours at 150F, 2 hours at 275F, and 2 hours at 350F.
~ , : : :
A composite structure was prepared according to the first of the abov~ procedures. The resulting composite structure e~hibited the properties shown in :
WO93/20123 ~ 21~ 3 8 ~ 9 PCT/US93/02677 Table 1 when tested per A~SI/IPC-FC-232B and 241B
procedures:
PROPERTIES OF ADHESIVE COMPOSITE STRUCTURE
Initial Peel 20 plia Peel After Solder 21 pli Chemical Reslstance:
: Methyl Ethyl Ketone 21 pli Toluene 20 pli ~Isopropyl Alcohol 21 pli Trichloroethylene/Methylene Chloride 21 pli Solder~ Float : Pass Aging (96 hours at ~ ~o Bond 2~75F~in~:air circulating oven) Strength Change pli -~:pounds per~linear inch ADVANTAGES OF THE _~y~N~
, ::
The`present invention provides an adhesive system with extremely balanced properties and the added 5 :~ benefit of superior Z-axis stability through a unique :: :~ : : : :
curing mechanism. More specifically, the present in~ention provldes an epoxy-based laminating adhesive ~: that can be cqntinuously processed and cured without the :: :
~:
: :
3 1! ~ 1 ~ 3 ~ ~9 WO93/20123 rCT/US93/0~677 evolution of byproducts to pro~ide a flexible bond-ply with superior overall properties, including excellent Z-axis stability. The adhesi~e material is applicable to film substrates such as polyimide, foi~ substrates such as copper, and hardboard substrates, such as FR4 (fiberglass impregnated hardboard). The adhesive of the present invention also possesses superior peel strength, chemical resistance, moisture resistance, and temperature ~: stability. It is particularly suitable for use in the :.
~10 bonding of electronic construction materials, such as : those intended for use in severe en~ironmental conditions. In particular, the adhesive of the present inv-ntion is~suitabl~e~for use in under-the-hood automotive and military~appl1cations.
Although~the present invention has been described in~cons~iderable detail with reference to certa~in~preferred~versions thereof~, other versions are pQssib1e~ Therefore~the spirit~and scope of the pending 2~0~ :claims:~::shou1d not be limited to the description of the preferred versions contained~herein.
:~ :~ : :,
Claims (34)
1. A process for producing a three-dimensional polymeric adhesive material comprising:
(a) reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product; and (b) reacting the adduct product with a polyelectrophile to generate a three-dimensional polymeric adhesive material.
(a) reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product; and (b) reacting the adduct product with a polyelectrophile to generate a three-dimensional polymeric adhesive material.
2. The process of claim 1 wherein the starting polymer contains an active hydrogen and has a maximum acid value of 2.
3. The process of claim 2 wherein the starting polymer is selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, and mixtures thereof.
4. The process of claim 3 wherein the starting polymer comprises a high molecular weight polyester.
5. The process of claim 1 wherein the starting polymer is a polyfunctional hydroxy-containing polymer having a hydroxy number of at least 10.
6. The process of claim 5 where the polyfunctional hydroxy-containing polymer is selected from the group consisting of polyols, polyesters, polyurethanes, and mixtures thereof.
7. The process of claim 6 where the polyfunctional hydroxy-containing polymer is a polyester.
8. The process of claim 1 wherein the polyfunctional nucleophile is a polyfunctional nitrogen-containing compound.
9. The process of claim 8 wherein the polyfunctional nitrogen-containing compound is selected from the group consisting of polyamines, polyaziridines, polyisocyanates, and mixtures thereof.
10. The process of claim 9 wherein the polyfunctional nitrogen-containing compound is a polyisocyanate.
11. The process of claim 1 wherein the polyelectrophile comprises at least one polyepoxide.
12. The process of claim 11 wherein the polyepoxide is selected from the group consisting of bisphenol A-epichlorohydrin epoxies, novolac epoxies, and mixtures thereof.
13. The process of claim 12 wherein the polyexpoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies and novolac epoxies.
14. A process for producing a three-dimensional polymeric adhesive material comprising:
(a) reacting a starting polymer comprising a high molecular weight polyester with a polyisocyanate to form an adduct product; and (b) reacting the adduct product with at least one polyepoxide selected from the group consisting of bisphenol A-epichlorohydrin epoxies, novolac epoxies, and mixtures thereof, to generate a three-dimensional polymeric adhesive material.
(a) reacting a starting polymer comprising a high molecular weight polyester with a polyisocyanate to form an adduct product; and (b) reacting the adduct product with at least one polyepoxide selected from the group consisting of bisphenol A-epichlorohydrin epoxies, novolac epoxies, and mixtures thereof, to generate a three-dimensional polymeric adhesive material.
15. The process of claim 14 wherein the high molecular weight polyester comprises from about 50% to about 90% by weight of the three-dimensional polymeric adhesive material and the polyepoxide comprises from about 10% to about 50% by weight of the three dimensional polymeric adhesive material.
16. The process of claim 14 wherein the polyepoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies and novolac epoxies.
17. The process of claim 14 wherein the step of reacting the adduct product with the at least one polyepoxide comprises heating a mixture of the adduct product and the at least one polyepoxide to a temperature between about 250°F and about 400°F.
18. A process for bonding at least two substrates comprising the steps of:
(a) reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product;
(b) mixing the adduct product with a polyelectrophile to generate a bonding precursor;
(c) applying the bonding precursor between the substrates prior to the reaction between the adduct product and the polyelectrophile; and (d) reacting the adduct product with the polyelectrophile to generate a three-dimensional polymer adhesive material between the substrates, thereby bonding the substrates.
(a) reacting a starting polymer containing an active hydrogen or hydroxy function with a polyfunctional nucleophile to form an adduct product;
(b) mixing the adduct product with a polyelectrophile to generate a bonding precursor;
(c) applying the bonding precursor between the substrates prior to the reaction between the adduct product and the polyelectrophile; and (d) reacting the adduct product with the polyelectrophile to generate a three-dimensional polymer adhesive material between the substrates, thereby bonding the substrates.
19. The process of claim 18 wherein the substrates are selected from the group consisting of film substrates, foil substrates, and hardboard substrates.
20. The process of claim 18 wherein the starting polymer is selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, and mixtures thereof.
21. The process of claim 20 wherein the starting polymer comprises a high molecular weight polyester.
22. The process of claim 18 wherein the polyfunctional nucleophile is a polyfunctional nitrogen-containing compound selected from the group consisting of polyamines, polyaziridines, polyisocyanates, and mixtures thereof.
23. The process of claim 22 wherein the polyfunctional nitrogen-containing compound is a polyisocyanate.
24. The process of claim 18 wherein the polyelectrophile comprises at least one polyepoxide selected from the group consisting of bisphenol A-epichlorohydrin epoxies, novolac epoxies, and mixtures thereof.
25. The process of claim 24 wherein the polyepoxide comprises a mixture of bisphenol A
epichlorohydrin epoxies and novolac epoxies.
epichlorohydrin epoxies and novolac epoxies.
26. A three-dimensional polymeric adhesive material comprising:
(a) at least two linear urethane linked polymer moieties, each moiety comprising a hydroxy-terminated polyester linked in urethane linkage by an aromatic isocyanate; and (b) cross-links between the nitrogens of the urethane linked polymer moieties, each cross-link comprising a phenyl-containing polymer linked to the nitrogen atoms of the polyurethanes by -CH2-CHOH-linkages, with the methylene groups of the linkages being bonded directly to the nitrogen atoms such that the cross-links form a three-dimensional polymeric structure.
(a) at least two linear urethane linked polymer moieties, each moiety comprising a hydroxy-terminated polyester linked in urethane linkage by an aromatic isocyanate; and (b) cross-links between the nitrogens of the urethane linked polymer moieties, each cross-link comprising a phenyl-containing polymer linked to the nitrogen atoms of the polyurethanes by -CH2-CHOH-linkages, with the methylene groups of the linkages being bonded directly to the nitrogen atoms such that the cross-links form a three-dimensional polymeric structure.
27. The polymeric adhesive material of claim 26 wherein the cross-links comprise at least one polyepoxide selected from the group consisting of bisphenol A-epichlorohydrin epoxies, novolac epoxies, and mixtures thereof.
28. The polymeric adhesive material of claim 27 wherein the polyepoxide comprises a mixture of bisphenol A-epichlorohydrin epoxies having the formula and novolac epoxies having the formula wherein n is an integer from 1 to about 20, n being independently chosen for the bisphenol A-epichlorohydrin epoxies and for the novolac epoxies.
29. A three-dimensional polymeric adhesive material comprising:
(a) at least two linear polymer moieties, each moiety comprising a polymer containing nucleophilic nitrogen atoms: capable of reaction with an electrophile;
and (b) cross-links between the nitrogens of the polymer moieties, each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties through reaction of an electrophile with the nitrogen atoms.
(a) at least two linear polymer moieties, each moiety comprising a polymer containing nucleophilic nitrogen atoms: capable of reaction with an electrophile;
and (b) cross-links between the nitrogens of the polymer moieties, each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties through reaction of an electrophile with the nitrogen atoms.
30. The polymer adhesive material of claim 29 wherein the linear polymer moieties are selected from the group consisting of polycarboxylic acids, polyesters, polyamides, polyacrylics, polyfunctional phenolic resins, and mixtures thereof.
31. The polymer adhesive material of claim 30 wherein the linear polymer moieties are formed by reaction of a hydroxy-containing polymer with a polyfunctional nitrogen-containing nucleophile.
32. The polymer adhesive material of claim 31 wherein the polyfunctional nitrogen-containing nucleophile is selected from the group consisting of polyamines, polyaziridines, polyisocyanates, and mixtures thereof.
33. A composite structure comprising:
(a) at least two bondable substrates; and (b) a three-dimensional polymeric adhesive material in adhesive contact with each of the substrates such that each of the substrates is bonded to at least one other substrate by the adhesive material the adhesive material comprising:
(i) at least two linear polymer moieties, each moiety comprising a polymer containing nucleophilic nitrogen atoms capable of reaction with an electrophile and (ii) cross-links between the nitrogens of the polymer moieties, each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties through reaction of an electrophile with the nitrogen atoms.
(a) at least two bondable substrates; and (b) a three-dimensional polymeric adhesive material in adhesive contact with each of the substrates such that each of the substrates is bonded to at least one other substrate by the adhesive material the adhesive material comprising:
(i) at least two linear polymer moieties, each moiety comprising a polymer containing nucleophilic nitrogen atoms capable of reaction with an electrophile and (ii) cross-links between the nitrogens of the polymer moieties, each cross-link comprising a polymer linked to the nitrogen atoms of the polymer moieties through reaction of an electrophile with the nitrogen atoms.
34. The composite material of claim 33 wherein the bondable substrates are selected from the group consisting of film substrates, foil substrates, and hardboard substrates.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86298392A | 1992-04-06 | 1992-04-06 | |
| US07/862,983 | 1992-04-06 | ||
| PCT/US1993/002677 WO1993020123A1 (en) | 1992-04-06 | 1993-04-06 | A high performance epoxy based laminating adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2133839A1 true CA2133839A1 (en) | 1993-10-14 |
Family
ID=25339932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002133839A Abandoned CA2133839A1 (en) | 1992-04-06 | 1993-04-06 | A high performance epoxy based laminating adhesive |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0635035A4 (en) |
| JP (1) | JPH07509010A (en) |
| CA (1) | CA2133839A1 (en) |
| WO (1) | WO1993020123A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4423513B2 (en) * | 1997-10-20 | 2010-03-03 | 東洋紡績株式会社 | Adhesive resin composition and adhesive film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL134942C (en) * | 1965-06-14 | |||
| DE1720492B1 (en) * | 1966-08-04 | 1972-05-31 | Dow Chemical Co | METHOD OF MANUFACTURING MODIFIED EPOXY POLY ADDUCTS |
| IT1187748B (en) * | 1985-10-02 | 1987-12-23 | Resem Spa | SINGLE-COMPONENT POLYURETHANE ADHESIVE |
| DE3727847A1 (en) * | 1987-08-20 | 1989-03-02 | Fuller H B Co | MELT ADHESIVE AND METHOD FOR ITS PRODUCTION AND PROCESSING |
| US4835226A (en) * | 1988-06-06 | 1989-05-30 | Lord Corporation | Flock adhesive composition |
| CA2004130A1 (en) * | 1989-11-29 | 1991-05-29 | Thomas F. Gardeski | High performance epoxy based laminating adhesive |
-
1993
- 1993-04-06 EP EP93909150A patent/EP0635035A4/en not_active Withdrawn
- 1993-04-06 WO PCT/US1993/002677 patent/WO1993020123A1/en not_active Application Discontinuation
- 1993-04-06 JP JP5517523A patent/JPH07509010A/en active Pending
- 1993-04-06 CA CA002133839A patent/CA2133839A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07509010A (en) | 1995-10-05 |
| EP0635035A4 (en) | 1996-03-13 |
| WO1993020123A1 (en) | 1993-10-14 |
| EP0635035A1 (en) | 1995-01-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |