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
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/10—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/44—Polyester-amides
• • 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
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • 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
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • 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
  • 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
  • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
  • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
  • C09J177/12—Polyester-amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
  • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
• • 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

Definitions

• the present invention surprisingly and unexpectedly provides an adhesive which addresses the above-described problems and shortcomings in the art.
• an adhesive which is a reaction product as described hereinafter.
• the initial reaction provides for linking the acid terminating groups of a high molecular weight thermoplastic polyamide to those of a high molecular weight thermoplastic polyester with an aziridine component to provide for amide linkage sites between the two components in addition to those already present in the polyamide.
• a second reaction is carried out by reacting the polyamide/aziridine/polyester sites and the already inco ⁇ orated polyamide sites ofthe polyamide component with an epoxy, such as bis epi epoxy, thus forming a block copolymer of long segments of polyamide polyester/polyamide in which the polyamide and polyamide/polyester sites are reacted with epoxy in a parallel fashion.
• a third reaction carried out is that of a glycidoxyalkoxysilane, which is inco ⁇ orated as a bond enhancer, with the amide and formed polyamide aziridine/polyester linkages to provide for the adhesive ofthe present invention.
• the first reaction is accomplished at room temperature, while the second and third steps are carried out at temperatures of 300° to 350°F to achieve full cure.
• a cast or coated film, to which the adhesive ofthe present invention has been applied can be stored at room temperature while awaiting processing into the final desired laminate or coverlay configuration.
• another aspect ofthe present invention is directed to a process of making the adhesive ofthe present invention which comprises linking a high molecular weight acid terminated thermoplastic polyamide resin with a high molecular weight polyester resin via an aziridine which forms polyamide and polyamide/aziridine/polyester linkages, then reacting with an epoxy and a silane via the amide groups in the polyamide and the formed polyamide/aziridine/polyester linkage.
• a further aspect ofthe present invention is an article having at least two surfaces bonded together by applying to said surfaces the adhesive ofthe present invention. Accordingly, the invention also encompasses composite or laminate articles having surfaces bonded together by the present adhesive.
• the adhesive ofthe present invention advantageously possesses excellent encapsulating properties with regard to circuit conductors while also unexpectedly providing virtually unmeasurable flow onto metal pads. Flow of adhesives onto pads requires manual cleaning with solvents which is very time consuming.
• the present adhesive advantageously avoids this costly step and thus advantageously speeds up the process of flexible circuit manufacturing.
• the adhesive ofthe present invention is thus su ⁇ risingly vastly superior to any other adhesive currently available for use in circuitry processing.
• An extremely high temperature resistant, flexible, and high bond strength adhesive is su ⁇ risingly provided by way ofthe present invention.
• the adhesive can be advantageously used to enhance the properties of polyester films such as polyethylene terephthalate and polyethylene naphthalate films for use in flexible and rigid board circuitry applications.
• the present invention also provides an excellent adhesive for films such as polyimide for the same applications. This allows the films to be used at temperatures which are capable of withstanding high temperatures, which to date has been limited by currently available adhesives. Along with being useful as a laminating adhesive, the adhesive is stable at room temperature and thus can be advantageously stored as a free film bond ply adhesive or coated on a film for future conversion into a laminate or coverlaying of electronic circuitry.
• the present invention provides an adhesive having excellent encapsulating and dimensional stability properties, which adhesive comprises a reaction product of a block copolymer of polyamide and polyamide/aziridine/polyester linkages with an epoxy and a silane.
• Dimensional Stability denotes the amount of shrinkage in the Machine and Transverse Direction of a film or substrate after being exposed to a given temperature for a given period of time, e.g., measurement ofthe film in both directions before and after exposure to 150°C for 30 minutes with log results in % change.
• a process of making the adhesive ofthe present invention comprises linking a high molecular weight polyamide component with a high molecular weight polyester component via aziridine as follows: H H
• a second step comprises reacting the polyamide linkage and the formed polyamide/aziridine/polyester linkage with an epoxy as follows:
• the third step for the process of making the present adhesive comprises reacting a silane, such as a glycidoxyalkoxysilane, e.g., glycidoxypropyltrimethoxysilane, with the high molecular weight polyamide and the formed linkage between the high molecular weight polyamide and the high molecular weight polyester by result ofthe aziridine reaction.
• a silane such as a glycidoxyalkoxysilane, e.g., glycidoxypropyltrimethoxysilane
• minor repeating unit constitutes from about 1% to about 5% ofthe total weight ofthe copolymer and the major repeating unit constitutes from about 95 to about 99% ofthe weight ofthe adhesive copolymer.
• R, R ⁇ X and Y are also defined as described previously.
• high molecular weight polyamide is meant a polyamide having a molecular weight of at least 5,000; particularly from about 5,000 to about 100,000; and more particularly from about 20,000 to about 50,000.
• high molecular weight polyester is meant a polyester having a molecular weight of at least 10,000; particularly from about 10,000 to about 200,000; and more particularly from about 20,000 to about 50,000.
• silanes examples include glycidoxyalkoxysilanes such as glycidoxypropylmethyldiethoxysilane and glycidoxypropyldimethylethoxysilane.
• Heptafluoroisopropoxyproplymethylcidhlorosilane is also suitable.
• Glycidoxypropyltrimethoxysilane is especially preferred.
• Non-limiting examples of suitable types of polyamides include: Versamid 744 Softening point of 125°C, Versamid 744 Softening point of
• the novel adhesive ofthe present invention preferably comprises a reaction product of an acid terminated thermoplastic polyamide component such as that sold by Henkel under the name of Versamid 972, a polyester/epoxy composition containing a glycidoxypropyltrimethoxysilane sold by Morton under the trade name of Adcote 76PI, and an aziridine component, such as that sold by EIT, Inc. under the trade name of XAMA 7.
• an acid terminated thermoplastic polyamide component such as that sold by Henkel under the name of Versamid 972
• an aziridine component such as that sold by EIT, Inc. under the trade name of XAMA 7.
• the adhesive ofthe present invention provides a fully crosslinked network without the evolution of volatile by-products to provide an advanced laminating, coverlay, and bond ply adhesive for film to film, foil to film, foil to foil, and hardboard to hardboard applications.
• the adhesive has excellent flexibility, superior bond strength, solder resistance, moisture and chemical resistance and superior Z-axis stability along with continuous and/or deferred processing capability.
• the adhesive can be stored for long periods of time, e.g., up to one year, prior to the implementation ofthe above-described curing process.
• the adhesive can be coated on an insulating film or release substrate by a continuous process and stored at room temperature indefinitely prior to further processing, or laminated in-line to various foils or films.
• the adhesive ofthe present invention can be advantageously cured without the evolution of volatile by-products to provide a flexible bond-ply with superior overall properties to any currently available system with the added advantage of excellent Z-axis stability.
• a mixture was prepared from the following components: A high molecular weight acid terminated thermoplastic polyamide resin at 20% solids in n-Propanol sold by Henkel under the trade name of Versamid 972, a mixture of high molecular weight polyester with residual acid functionality, bis-epi flexible epoxy, and glycidoxypropyltrimethoxysilane at 51% solids in methyl ethyl ketone sold by Morton under the trade name of Adcote 76P1 and a polyfunctional aziridine sold by EIT. Inc. under the trade name of XAMA 7. The mixture was then made by combining 88 parts by solids ofthe polyester/epoxy component to 9 parts by solids ofthe polyamide component.
• the mixture was then allowed to stand for 30 minutes at room temperature to assure a homogeneous solution.
• 3 parts by solids ofthe aziridine component was then allowed to stand for 30 minutes to allow for the onset ofthe aziridine reaction with both the acid groups of the polyamide and polyester components.
• the mixture was then bar coated to yield a one mil dry coat onto a sheet of 5 mil thick polyethylene-naphthalate film sold under the trade name of KALADEX by ICI Films, then dried for 10 minutes at 225°F to remove the solvents and allow for the onset ofthe epoxy and glycidoxypropyltrimethoxysilane reaction with the polyamide linkage and the formed linkage between the polyamide and polyester components by the aziridine component.
• the adhesive coated film was then placed over a sheet of 1 oz rolled annealed copper, placed between two 2 mil thick skived TFE press pads, then placed between two one-quarter inch thick stainless steel caul plates.
• the entire lay-up was then placed in a press at room temperature under 50 psi of pressure.
• the press was then heated to 350° F over a period of 14 minutes, allowed to remain at 350°F for 1 hour, then cooled to 200°F by running air through the press platens followed by water to cool the press to 150°F at which point the lay-up was removed.
• the subsequently formed laminate of polyethylenenaphthalate film/adhesive/copper was removed and allowed to condition at room temperature for 24 hours.
• the formed laminate was then tested in accordance with IPC-FC-241 procedures to yield the following properties: Initial Peel ⁇ to lO PLI
• EXAMPLE 2 The mixture from Example 1 was coated onto 2 mil thick polyimide film sold by UBE Industries of Japan under the trade name of UPILEX S, then dried and pressed under the same process as described in Example 1.
• EXAMPLE 4 A mixture was prepared consisting of 88 parts by solids of Morton 76 Pl and 9 parts by solids of Versamid 972 and allowed to stand at room temperature for 30 minutes. Three parts by solids of XAMA 7 was then added to the mixture and allowed to sit at room temperature for 30 minutes.
• Riston Lamination Processed normally when the Riston (photo-resist) was laminated to the copper side ofthe laminate at 140° to 145°F.
• Photo-exposure Processed normally Development: Processed normally Etching: The resulting circuit pattern was etched with cupric chloride at 130° to 135°F. Both the KALADEX and adhesive showed no attack in exposure to this etching process.
• the formed circuitry pattern was then coverlayed with a sheet of 50 micron KALADEX coated with the same mix of adhesive at 25 micron dry thickness in a press under 100 psi for 1 hour at 350°F.
• the coverlayed circuit was then critically examined under 100X magnification to determine how well the adhesive encapsulated the etched circuit conductors and to determine the amount of flow of adhesive onto exposed copper pads used for solder interconnects.
• the encapsulation was deemed exceptional and the flow onto the pads virtually unmeasurable, which was vastly superior to any other adhesive system used in circuitry processing currently available.
• the coverlayed circuitry was then exposed to hot oil leveling by submersion in hot oil for 20 seconds at 460°F. Upon removal from the hot oil, the circuitry was examined and determined to process as well as polyimide-based circuitry constructions from the criteria of lay-flat characteristics and other critical parameters.
• the circuitry was then punched from the laminate. Dimensional stability was deemed as excellent, as the pre-drilled registration holes fit very nicely onto the pins on the fixture used to hold the circuit in place during the punching process. In addition, the film and adhesive punched very cleanly, leaving no debris on the tool or in the punched holes.
• the circuitry was hand soldered using a solder iron with a tip temperature of 650°F with a Tin/Lead based solder composition. Neither the hot solder or direct contact with the solder iron tip had any adverse effect on the adhesive system.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)

Applications Claiming Priority (3)

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• 1997
  • 1997-02-21 EP EP97907743A patent/EP0882108A1/de not_active Withdrawn
  • 1997-02-21 KR KR1019980706586A patent/KR19990087191A/ko not_active Application Discontinuation
  • 1997-02-21 WO PCT/US1997/002701 patent/WO1997031078A1/en not_active Application Discontinuation
  • 1997-02-21 AU AU19662/97A patent/AU1966297A/en not_active Abandoned
  • 1997-02-21 JP JP53033197A patent/JP2001513115A/ja active Pending

Non-Patent Citations (1)

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