WO1991004999A1 - Composition de resine epoxyde durcissable a deux composants - Google Patents

Composition de resine epoxyde durcissable a deux composants Download PDF

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Publication number
WO1991004999A1
WO1991004999A1 PCT/GB1990/001500 GB9001500W WO9104999A1 WO 1991004999 A1 WO1991004999 A1 WO 1991004999A1 GB 9001500 W GB9001500 W GB 9001500W WO 9104999 A1 WO9104999 A1 WO 9104999A1
Authority
WO
WIPO (PCT)
Prior art keywords
kit
component
epoxy resin
curing agent
epoxy
Prior art date
Application number
PCT/GB1990/001500
Other languages
English (en)
Inventor
Pak Keung Pang
Original Assignee
Cookson Group Plc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cookson Group Plc filed Critical Cookson Group Plc
Publication of WO1991004999A1 publication Critical patent/WO1991004999A1/fr

Links

Classifications

    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines

Definitions

  • the invention relates to a two-pack curable epoxy resin composition.
  • it relates to such a composition in which the first and second components of the two-pack can be present in equal amounts either by weight or by volume.
  • compositions it is generally preferred to arrange the ingredients so that the first component containing the epoxy resin and the second component containing the curing agent are present in approximately equal amounts by volume or by weight depending on whether they are to be dispensed by a volume mechanism or a weighing mechanism. This is important because it is easy for mistakes in mixing the composition to occur if the user has to measure out different quantities of the two components. For example, an operator might weigh out 60 wt.% of the first component and 40 wt.% of the second when the instructions for use in fact state that he should be weighing out 40 wt.% of the first component and 60 wt.% of the second.
  • Typical bulking agents are plasticizers such as the phthalates.
  • these additives can have a detrimental effect on the properties of the cured composition. For example, the phthalates lower the overall physical strength of the cured composition and they also reduce the glass transition temperature of that composition.
  • a kit which comprises first and second components for a curable epoxy resin composition the first component comprising a first epoxy compound curable by a non-acidic curing agent and the second component comprising a non-acidic curing agent for the first epoxy compound and in which the first component is stored separately from the second component characterised in that the second component includes a second epoxy compound which is not curable by the non-acidic curing agent.
  • a non-acidic curing agent is meant a curing agent which does not contain acid groups or groups which can produce acid groups under storgae-conditions e.g. carboxylates and anhydrides.
  • non-acidic curing agents include certain polya ines, polyamides, aromatic amines, amine/epoxy adducts and imidazoles.
  • Various non-acidic curing agents may be selected according to the length of shelf life required in the particular application. Aromatic amine and i idazole curing agents are to be preferred when a substantial (for example 3 months or more) length of shelf life is required.
  • Such a two-pack composition is stable prior to mixing because the second epoxy compound does not react with the non-acidic curing agent.
  • the second epoxy compound is simply a bulking agent which increases the weight or volume of the second component so that compositions having equal volume or equal weight proportions of the first component and the second component can be formulated.
  • the second component contains epoxide groups it behaves very differently on curing of the composition from prior art bulking agents.
  • the composition may include- metallic particles, for example silver, in the first component, the second component or both.
  • metallic particle-filled epoxy resin compositions are now of great commercial
  • the present invention includes a printed circuit having conductive pathways formed from a cured epoxy resin
  • composition produced by mixing equal amounts by weight or by volume of the first and second components of a kit as described herein and then curing the mixture.
  • non-acidic curing agent are those in which the epoxy function is provided as a cyclohexane-3,4-epoxide group. While such epoxide groups can react with acidic curing agents such as acids or anhydrides they are not cured at any appreciable rate by non-acidic
  • Cyclopentane-2,3-epoxide group-containing compounds react similarly and may also be employed in the present invention.
  • cycloaliphatic epoxides will contain more than one cyclohexane or cyclopentane epoxy group per molecule so that they can polymerise.
  • Such compounds are generally prepared by epoxidizing unsaturated aromatic
  • hydrocarbon compounds such as cyclo-olefins, using hydrogen peroxide or peracids such as peracetic acid or perbenzoic acid.
  • R is -CH 2 OOC- or -CH 2 00C(CH 2 ) COO- and R' is hydrogen, methyl, ethyl, propyl, butyl or benzyl.
  • Another property of the second epoxy compounds which can be significant and should be considered when selecting which epoxy compound to include in a particular composition is its viscosity. So that it is not difficult to mix the first and second components the viscosity of the second epoxy compound should not be too high.
  • the viscosity will be no more than 800 centipoise at 25°C, preferably no more than 500 centipoise.
  • Examples of cyclohexane-3,4-epoxide compounds having viscosities in these ranges are 3,4-epoxycyclohexylmethyl- 3,4-epoxy cyclohexane carboxylate having the following structure
  • dicyclopentadiene dioxide having the following structure
  • the curing agent may be an
  • SUBSTITUTESHEET amine an amide, an i idazole or a modified amine. While aromatic amines may be employed as well as aliphatic amines they tend to have higher acidity as measured by their pKa values and so second components containing them with cycloaliphatic epoxides are sometimes a little less stable than if an aliphatic amine had been employed. However, second components containing aromatic amines are often sufficiently stable for practical purposes.
  • curing agents which may be employed in the second component of the present invention depending on the length of shelf life required, in the second component of the present invention are diethylenetriamine, triethylenetetramine, hexamethylenediamine, piperadine, benzyldimethylamine, diaminodimethylmethane, diaminodiphenylsulphone, dicyandiamide, an a ine-epoxy resin adduct, an amine-glycidyl adduct, an amine-ethylene oxide adduct, and a cyanoethylation product.
  • imidazole curing agents which may be employed in the second component of the present invention when a relatively lengthy shelf life is desired are 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, l-cyanoethyl-2-phenylimidazole-trimellitate, 2- ( ⁇ -(2'- ethylimidazoyl-(1') ) )-ethyl-4 ,6- diamino-5-triazine, l-cyanoethyl-2-phenyl- ,5- di (cyanoethoxymethyl) imidazole and l-benzyl-2-methylimidazole.
  • Any conventional epoxy compound may be employed as the first epoxy compound but two which are particularly preferred because their properties are well known is Bi ⁇ phenol A epoxy resin and Bisphenol F epoxy resin.
  • the kit of the present invention which is a two-pack epoxy resin composition it is possible to produce the epoxy resin by using equal amounts of the first epoxy compound and the second epoxy compound.
  • the composition may be arranged so that the first and second components are present in equal amounts by weight or in equal amounts by volume depending on whether it is desired to dispense the composition by weight measuring mechanism or a volume measuring mechanism.
  • the kit of the present invention may be formulated to produce a metal-filled epoxy composition.
  • the first and second components will generally be made up as follws: first component, first epoxy compound in an amount of 6 to 11 wt. %, reactive diluent in an amount of 0 to 5 wt. %, wetting agent in an amount of 0 to 0.5 wt. %, and silver powder in an amount of 32 to 42.5 wt. %; second component, cycloaliphatic epoxide in an amount of 6 to 11 wt. %, curing agent in an amount of 0.5 to 15 wt. %, wetting agent in an amount of 0 to 5 wt. % and silver powder in an amount of 32 to 42.5 wt. %.
  • Component A was prepared in a 30cm 3 polypropylene container cleaned in methanol and air dried. All the liquid components were weighed into the container and a stainless steel blade palette knife was used to stir the mixture for 5 minutes. The silver powder was than added and the material mixed until all the silver powder was dispersed uniformly into the liquid. The screw top was put on the container and sealed using polyvinylchloride tape adhesive.
  • Component B was prepared in the same way as Component A. Once prepared the two components were stored in a refrigerator until they were to be used.
  • Bond Strength Tests Samples were then prepared by mixing equal amounts by weight of Component A and Component B for each formulation and stirring. The samples were applied to copper coupons and cured before bond strength was measured using a lap shear strength test.
  • a 2.54 cm by 2.54 cm square area of a copper coupon 2.54 cm wide by 10.4 cm long by 0.162 cm thick was etched by dipping it into concentrated nitric acid for 3 to 5 seconds then washed and dried immediately in hot air.
  • the adhesive was immediately applied to the etched area and a Sheen paint film thickness gauge glided over the adhesive to produce a film with a constant thickness of 0.01 cm.
  • Two coupons made by the same method were then brought together and a slight pressure was used to ensure that there were no air bubbles trapped in the joint. Excess adhesive on the outside of the joint was removed using a palette knife. Masking tape was used to hold the coupons in position whilst the sample was being cured but was removed before the bond strength test. The samples were each cured at 150°C for 30 minutes. Five samples prepared by the same method were used for each test.
  • the lap shear strength of each sample was then measured using an Instron tensile testing machine, model no. 6025, load cell 100 kilo newtons.
  • the two ends of the cured sample were inserted into a pair of wedge grips and a cross head speed of 1.3 mm/minute was used. The force required to cause bond failure for each sample was recorded.
  • a series of formulations of epoxy resin with certain specific curing agents was prepared according to the following method. 10 grams of epoxy resin was weighed into a 30cm 3 polypropylene container, cleaned in methanol and air dried. 1 gram of diethylementria ine curing agent was added and the contents stirred using a glass rod for 5 minutes to achieve a uniform mixture. A screw top was put onto the container and sealed using polyvinyl- chloride tape adhesive.
  • the sealed containers were stored at room temperature and the shelf lives of the mixtures were monitored daily for the first 14 days and then week by week thereafter.
  • the gel time was used to indicate the end of shelf life of the mixtures.
  • Epoxy resin Diethylenetriamine 100:10
  • Epoxy resin Hexamethylenetria ine 100:30
  • Epoxy resin Isophoronedia ine 100:30
  • Epoxy resin N-aminoethylpiperizine 100:30
  • Epoxy resin Polyetheramine ⁇ 100:30
  • Epoxy resin Polyamides 100:70
  • Epoxy resin Amine epoxy adducts 100:25 Epoxy resin : Imidazoles 100:10
  • the cycloaliphatic epoxide used was 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Jeu comprenant un premier et un deuxième composants destinés à une composition de résine époxyde durcissable. Le premier composant comprend un premier composé époxyde pouvant être durci par un durcisseur sans acide, et le deuxième composant comprend un durcisseur sans acide destiné au premier composé époxyde. Le premier composant est stocké séparément du deuxième composant caractérisé en ce qu'il comprend un deuxième composé époxyde qui ne peut pas être durci par le durcisseur sans acide.
PCT/GB1990/001500 1989-10-02 1990-10-01 Composition de resine epoxyde durcissable a deux composants WO1991004999A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8922177.4 1989-10-02
GB898922177A GB8922177D0 (en) 1989-10-02 1989-10-02 Two-pack curable epoxy resin composition

Publications (1)

Publication Number Publication Date
WO1991004999A1 true WO1991004999A1 (fr) 1991-04-18

Family

ID=10663935

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1990/001500 WO1991004999A1 (fr) 1989-10-02 1990-10-01 Composition de resine epoxyde durcissable a deux composants

Country Status (2)

Country Link
GB (1) GB8922177D0 (fr)
WO (1) WO1991004999A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1701690A2 (fr) * 2003-12-18 2006-09-20 Ashland Inc. Composition adhesive de resine epoxyde, son procede de preparation et d'utilisation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4581158A (en) * 1984-09-26 1986-04-08 W. R. Grace & Co. Conductive thermosetting compositions and process for using same
EP0304503A1 (fr) * 1987-08-26 1989-03-01 Asahi Kasei Kogyo Kabushiki Kaisha Durcisseur pour système de résine époxyde en un seul emballage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4581158A (en) * 1984-09-26 1986-04-08 W. R. Grace & Co. Conductive thermosetting compositions and process for using same
EP0304503A1 (fr) * 1987-08-26 1989-03-01 Asahi Kasei Kogyo Kabushiki Kaisha Durcisseur pour système de résine époxyde en un seul emballage

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1701690A2 (fr) * 2003-12-18 2006-09-20 Ashland Inc. Composition adhesive de resine epoxyde, son procede de preparation et d'utilisation
EP1701690A4 (fr) * 2003-12-18 2007-10-10 Ashland Licensing & Intellectu Composition adhesive de resine epoxyde, son procede de preparation et d'utilisation

Also Published As

Publication number Publication date
GB8922177D0 (en) 1989-11-15

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