CA1184757A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- CA1184757A CA1184757A CA000402492A CA402492A CA1184757A CA 1184757 A CA1184757 A CA 1184757A CA 000402492 A CA000402492 A CA 000402492A CA 402492 A CA402492 A CA 402492A CA 1184757 A CA1184757 A CA 1184757A
- Authority
- CA
- Canada
- Prior art keywords
- paste
- epoxy compound
- adduct
- paste according
- dialkylamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
- H01L23/4827—Materials
- H01L23/4828—Conductive organic material or pastes, e.g. conductive adhesives, inks
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Abstract of the Disclosure An electroconductive paste comprising (a) an electroconductive filler, (b) a reactive solvent, and (c) a hardener comprising (c-1) an epoxy resin, (c-2) a latent hardener, and (c-3) an epoxy compound-dialkylamine adduct, the percent by weight of (a), (b) and (c) being 95 to 50, 1 to 20 and 4 to 30, respectively, and the weight ratio of (c-1) : (c-2) : (c-3) being 100 : 0 to 30 : 0.1 to 40.
The paste is useful for bonding electronic elements to metal lead frames and/or substrates.
The paste is useful for bonding electronic elements to metal lead frames and/or substrates.
Description
5 ~
~ he present invention relates to a conductive paste, particularly suitable for the bonding of electro.nic parts.
For the bon~ing of electronic elements (herein-after called chips) such as semiconductor integrated circuits light-emitting diodesj etc. to metal lead ~rames and/or substratesS electroconductive pastes are becomin~
to be used more and moreO
The chip~bonding is carried out by a process which comprises drop-feeding the electroconductive paste on the place o~ the metal lead ~rame or substrate to which the chip should be fixed, the~ press-mounting the chip on the dropped paste~ and fi~ally subjecting the bonded chips collected into a suitable number to hardening treat-ment i~ a heating furnace. The chip-bonded metal lead frame or ~ubstr~te is further subjected to wire-bonding and then resiu-molded or cap~sealed to obtain a final product.
~ he electroconductive pastes usable for such purpose~ are required to have the following p.roperties, .in consideration of the above-me~tioned chip-bonding proce 8g Ir (A) the usable duration (so~called "pot life") should be as long as possible 9 (B) the time necessary ~or hardening should be as short a~ possible, (~) the quantity of released gas upon hardening should be as little as pos~ible~ a~d ths ~as should not be harmful, particularl~ to semico~ductor elements, and ~ ~ :
s~
(D) tihe resin after hardening should have excellent heat resistance.
~ y the usable duration is meant a time spa~ from the moment of the drop-feed of the paste up to the time at which the paste, after standing at room temperature, loses its chip-bonding ability.
In the chip-bonding process, there are cases ~here a long time is necessary from the moment of paste drop-~eed up to chip mounting, so that too short a usable duration will cause a bad operability and a fluctuation in chip-bondin~ strength after hardening.
~ he electroconductive pastes usable for the above-mentio~ed purposes comprises an electroconductive filler, a thermosetting resln such as epvxy resin, a hardener and a solvent, etc~
As the hardener, for example, an acid anh~dride, boron tri~luoride-amine complex, amine compound 9 and the 1`
like are usuall~ used. However, in the case o~ usi~g acid j~' anh~dride or boron tri~luoride amine complex 9 the usuable ~, ¦
duratio~ is lo~g, but a hi~h temperature a~d a long time are neoessary ~or hardening, whereas in case of using the amine compounds, the hardening time becomes short but the usable duration becomes also short. ~herefor~
it has been difficult to satisr~ both properties (A) and (B) at the same time by conventional hardeners.
As the solvents which are used for regulating a great increase of the viscosity when the electroconduc-tive filler is incorporated, there are reactive ones a~d non-reactive ones. Since reactive solvents such as epoxy compounds have a low molecular weig~t, they have
~ he present invention relates to a conductive paste, particularly suitable for the bonding of electro.nic parts.
For the bon~ing of electronic elements (herein-after called chips) such as semiconductor integrated circuits light-emitting diodesj etc. to metal lead ~rames and/or substratesS electroconductive pastes are becomin~
to be used more and moreO
The chip~bonding is carried out by a process which comprises drop-feeding the electroconductive paste on the place o~ the metal lead ~rame or substrate to which the chip should be fixed, the~ press-mounting the chip on the dropped paste~ and fi~ally subjecting the bonded chips collected into a suitable number to hardening treat-ment i~ a heating furnace. The chip-bonded metal lead frame or ~ubstr~te is further subjected to wire-bonding and then resiu-molded or cap~sealed to obtain a final product.
~ he electroconductive pastes usable for such purpose~ are required to have the following p.roperties, .in consideration of the above-me~tioned chip-bonding proce 8g Ir (A) the usable duration (so~called "pot life") should be as long as possible 9 (B) the time necessary ~or hardening should be as short a~ possible, (~) the quantity of released gas upon hardening should be as little as pos~ible~ a~d ths ~as should not be harmful, particularl~ to semico~ductor elements, and ~ ~ :
s~
(D) tihe resin after hardening should have excellent heat resistance.
~ y the usable duration is meant a time spa~ from the moment of the drop-feed of the paste up to the time at which the paste, after standing at room temperature, loses its chip-bonding ability.
In the chip-bonding process, there are cases ~here a long time is necessary from the moment of paste drop-~eed up to chip mounting, so that too short a usable duration will cause a bad operability and a fluctuation in chip-bondin~ strength after hardening.
~ he electroconductive pastes usable for the above-mentio~ed purposes comprises an electroconductive filler, a thermosetting resln such as epvxy resin, a hardener and a solvent, etc~
As the hardener, for example, an acid anh~dride, boron tri~luoride-amine complex, amine compound 9 and the 1`
like are usuall~ used. However, in the case o~ usi~g acid j~' anh~dride or boron tri~luoride amine complex 9 the usuable ~, ¦
duratio~ is lo~g, but a hi~h temperature a~d a long time are neoessary ~or hardening, whereas in case of using the amine compounds, the hardening time becomes short but the usable duration becomes also short. ~herefor~
it has been difficult to satisr~ both properties (A) and (B) at the same time by conventional hardeners.
As the solvents which are used for regulating a great increase of the viscosity when the electroconduc-tive filler is incorporated, there are reactive ones a~d non-reactive ones. Since reactive solvents such as epoxy compounds have a low molecular weig~t, they have
- 2 ~
5~ `
a defect such that the heat resistance of the resin after hardening is lowered. ~or this reason, in order to maintain a good heat resistance~ non-reactive ~ol-vents are used in most cases~ But in such a case, since the olvent evaporates almost completely at the time of hardening, the quantity of released ~as becomes very large.
The present inventors have studied to improve the drawbacks of con~entional electroconductive paste~
and provide an electrodonductive paste having all of the properties (A), (B), (C) and (D), and attained to the present invention. I
~he present invention pro~ides an ~lectrocon_ L
ductive paste comprising l:
(a) an electroconductive filler, (b) a reactive 301vent, and (c) a hardening compound comprisin~
(c-l) an epox~ resin, (c-2) a late~t hardener~ and (c-3) an epoxy compound-dialkylamine adduct, the percent by weight of (a), ~b) and (c) being 95 to 50, 1 to 20 and 4 to 30, respectively, and the weight ratio of (c~ (c-2) ; (c-3) being 100 : 0 to 30 : 0.1 to 40.
~he present invention is explained in detail in the following, ~he electroconductive filler (a) usable in the present i~vention may be any electroco~ductive fine powder made of a noble metal suc~ as gold1 silver, pla-tinum, etc. a base metal such as nickel, aluminum, etcO
5~ `
a defect such that the heat resistance of the resin after hardening is lowered. ~or this reason, in order to maintain a good heat resistance~ non-reactive ~ol-vents are used in most cases~ But in such a case, since the olvent evaporates almost completely at the time of hardening, the quantity of released ~as becomes very large.
The present inventors have studied to improve the drawbacks of con~entional electroconductive paste~
and provide an electrodonductive paste having all of the properties (A), (B), (C) and (D), and attained to the present invention. I
~he present invention pro~ides an ~lectrocon_ L
ductive paste comprising l:
(a) an electroconductive filler, (b) a reactive 301vent, and (c) a hardening compound comprisin~
(c-l) an epox~ resin, (c-2) a late~t hardener~ and (c-3) an epoxy compound-dialkylamine adduct, the percent by weight of (a), ~b) and (c) being 95 to 50, 1 to 20 and 4 to 30, respectively, and the weight ratio of (c~ (c-2) ; (c-3) being 100 : 0 to 30 : 0.1 to 40.
~he present invention is explained in detail in the following, ~he electroconductive filler (a) usable in the present i~vention may be any electroco~ductive fine powder made of a noble metal suc~ as gold1 silver, pla-tinum, etc. a base metal such as nickel, aluminum, etcO
3 --7~
and no~metal such as carbon. The powder may be made of an alloy or in a mixture of two or more of the powders~ Usuallys the powder ha~ a particle diameter of about 0.1 to 10 ~m. The powder i~ flake form is preferable in respect of electroconductivity.
~he qua~tity of the electroconducti~e filler ma~ be altered depending on the specific gravity of the powder to be used and ran~es from 50 thI~ough 95 % by weight based on the weight of the paste. A quantity less than 50 % by weight will ~ot make the harde~ed product electroconducti~e. Whe~eas, if the quantity exceeds ¦.
95 % by ~veight, the ratio of the epoxy resin becomes too low, which will results in insufficienc~ of adhesive strength.
As the reactiYe solvents, suitable are epoxy compounds such as phenylglycidyl ether, butylglycidyl ether, neopentyl glycol glycidyl ether, etc. Since the reactive solvent is used for the regulation of the ~iSC08it~ of the paste, it should be limited to a necessary minimum. With the increase in the quantity added, the ~uantity of released gas increases and the heat resis-tJa~ce of the resi~ after hardening lowers. For this reason, the suitable quantity to be added ranges from 1 through 20 % by weight~ I~ the qu~ntity is less than 1 % by weight, the viscosity of the composition becomes too high. If the quantit~ exceeds 20 % by weight, the quantity of released gas upon harde~ing becomes too much or the charac~eristics of the hardened product will be lmpalred, ~ 7S ~
As the epoxy resin usable for the hardening component, an~ can be used which has two or more epoxy groups per molecule. Such epoxy resins include~ for example, polyglycidyl ethers produced by the reactiou betwee~ a polyh~dric phenol (e.gO bisphenol A, bisphenol F, catechol, resorcin, etc.) or a pol~hydric alcohol (e.g. glycerinl polyethylene glycol~ etc~) and epichlo-rohydrin; polygl~cidyl ether esters produced by the .:
reaction be~ween a hydrox~carbox~lic acid (e.g. p-ox~benzoic acid, beta-oxynaphthoic acid, etc.) aud epichlorohydrin; polyglycidyl esters obtained from a polycarboxylic acid (e.g. phthalic acid, terephthalic acid, etcO); glycidylamine compounds obtained from 4,4'- :
dlaminodiphenyl methan~, m-aminophenol, etc.; epoxydized novolac~ and epox~dized polyolefins.
As the latent hardener, there can be used those known latent hardeners such as urea, guanidine, hydrazine, hydra3ide, amidine~ triazine, azo compounds, etc. Co~crete example~ of these compounds includ~
acetylmethyl urea, benz~lurea, thiourea, 3-(substituted or u~ubstituted)phenyl~ di~ alkylurea (e.g. 3-phenyl~ dimethylurea, 3-(4-chlorophenyl)~ di-methylurea, 3-(3,4-dichlorophenyl~ dimethylurea, 3-phenyl~ dibutylurea, etc.), acetylsemicarbazide, acetaldehyde semicarbazone, asetone semicarbazone, ~
N,N'-diphenylguanidi~e, methylguanidine, biguanide, .
dicyandiamide, sebacic acid dihydrazide, succinic acid ~.
dihydrazide, adipic acid dihydrazide 9 tartaric acid dihydrazid~, dicyandiamidine, hydrazobenzene, acet-aldehyde phenylhydrazone, ben ophenone phenylhydrazone 9 ', benzamidine, melamine~ azobenzene,. diaminoazobe.nze~e, -- 5 ~
7~
etc. The quantity to be used is 0 to 30 parts by weight based on 100 parts by weight of the epoxy resin. If the quantity is more than 30 parts by weight, it is impossible to obtain stable properties after hardening.
The epoxy compound-dialkylamine adduct usable for the hardening component functions as a hardening promotor. mhe dialkylamine usable for the preparation of the adduct, which alkyl may be unsubstituted or substi-tuted, includes dimethylamine, dipropylamine, N-methyl-ethylamine 9 N-ethylisopropylamine, diallylamine, diben-zylamine or the like, and N-ethylethanolamine, diethanol-amine or the like. The epoxy compound includes, ~or example, monoepoxy compounds represented by butylglycidyl ether and phenylglycidyl ether, epoxy resins obtained from the above-exemplified polyhydric phenols, polycarbo-xylic acids and amines.
At least one member of the epoxy compounds and an excess quantity of the dialky]amine are mixed in a solvent and allowed to react under heating. After completion of the , reaction, the unreacted amine and solven-t are removed by distillation to obtain the epoxy compound-dialkylamine adduct having a desired softening point.
~ s such solvents, those which are capable of dis-solving the epoxy compound and have a boiling point above 50C. are suitable. They include, for example, tetrahydro-furan, dioxane, acetone, methyl ethyl ketone, toluene, monochlorobenæene, methylcellosolve, ethylcellosolve, etc. L' Of these, ethylcellosolve and toluene are preferable.
The adducts thus obtained are pulverized by an atmizer or the like and are used in the form of powder in ~4~7~7 the present invention. The powder may be further surface-treated with an acidic substance. The sur~ace-treated adduct is preferable in view of the storage stabili-ty of the electroconductive pastes.
rrhe surface treatment of the adduct may be carried ou-t by exposing the adduct to a gaseous acid or dispersing it in a dilute solution of the acidic substance, followed by drying. :
The acidic substances used for the surface treat-ment are gaseous or liquid inorganic or organic acids.
They include, for example, sulfur dioxide, hydrochloric .
acid, carbon dioxides, sulfuric acid, phosphoric acid, boric acid, formic acid, oxalic acid, acetic acid, pro-pionic acid, lactic acid, caproic acid, salicylic acid, tartaric acid, succinic acid, adipic acid, sebacic acid, p-toluene sulfonic acid, phenol, phyrogallol, tannic acid, rosin, polyacrylic acid, polymethacrylic acid, alginic acid, phenol resin, resorcin resin, etc.
The acidic subs-tances may be used in an amount ~ , :
enough to neutralize the amino groups exposed on the surface s 1':
of the adduc-t powder. Too much a ouantity may lower the hardening promotin~ effect of -the resin. Therefore, it is preferable to decide the necessary quantity, for example, by a quantitative analysis of the amine.
The adduct compound accelerates the action of i the latent hardener J and also act singly as a hardener. -The quantity of the adduct to be used is 0.1 to 40 parts by weight based on 100 parts by weight of the epoxy resin.
With the increase of the quantity of the adduct, the ratio of the latent hardener may be lowered. A quantity less 7 _ than 0.1 part by weight fails to harden the resin suffi-ciently. The quantity of the adduct may be increased to use no latent hardener. ~owever, if the quantity exceeds 40 parts by weight, the hardened product is discolored ~, . . !' and its characteristics are rather deteriorated.
- The sum of the quantities of the hardening component comprising the epoxy resin, latent hardener and epoxy compound-dialkylamine adduct is 4 to 30 ~ by weight of the total weight of the above mentioned (a), (b) and (c). The quan-tities of the hardening component and the i;
electroconductive filler are complementary with each other.
If the quantity of the hardening component is too large, the electroconductivity will be lost, whereas it is too small, -the strength of the hardened product will be made insufficient.
The electroconductive paste of the present inven~
tion can be easily obtained by weighing out the above men-tioned ingredients and kneading them with a three roll mill or the like. , Insufficiency in the degree of dispersion of the hardener will cause a fluctuation of the adhesive strength, e~c. when the resulting paste is used with extremely small quantities of drop-feeds, so that it is more prefer-able that the epoxy resin, latent hardener and epoxy com-pound-dialkylamine adduct are sufficiently mixed to form the hardening component.
The electroconductive paste thus obtained has a long pot life, hardens rapidly when heated at a high temperature, releases a small quantity of gas upon harden-ing, and has excellent characteristics (especially heat resistance), and there~ore it is particularly suitable for 5~
the bonding of electronic parts.
The electroconductive resin paste according to the present invention may contain another solvent, vis-cosity regulating agent, filler, coloring agent, e-tc.
as far as no adverse effect is produced on the storage stability, hardening properties, etc.
The above explanation has referred to the case of chip bonding of semiconductor elements according to the drop-feed method, but the electroconductive resin paste of the present invention may be used for screen-printing, the formation of electroconductive circuits on a plastic plate, or the like~.
The present invention is explained in more detail with reference to the following Examples.
Examples Using as electroconductive filler mainly flaky ~
silver powder, as the reactive solvent mainly phenylgly-cidyl ether (hereinafter abbreviated as PGE), and as the t epoxy resin in all cases a bisphenol A-type epoxy resin (hereinafter abbreviated as BPA Epoxy), and ln combination with various hardeners, electroconductive pastes were pro-duced, and their characteristics were measured. The com-positions of the pastes are shown in the Table, wherein ¦;
BPA Epoxy is Sumiepoxy ELA-128 tthe trade name of a bis-phenol A-type epoxy resin produced by Sumitomo Chemical Company, Limited; its epoxy e~uivalent is 190 g/equiv.).
As the solvent in Experiment No. 3 only, butylglycidyl ether (hereinafter abbreviated as BG~) was used. The hardener in Experiment No. 1 was Sumicure P-725 (the trade name o~
`:
_ 9 _ ~ 7~
a polyamide resin produced by Sumitomo Chemical Company, ~imited; its amine value is 300 mg KOH/g), and this product is widely used as a hardener for usual epoxy resins.
As the latent hardener, dicyandiamide (herein-after abbreviated as DICY), 3-(4-chlorophenyl)-1?1-dimethyl-urea (hereinafter abbreviated as p-urea) and 3-(3 9 4-dichloro- !`
phenyl)-l,l-dimethylurea (hereinafter abbreviated as 3-urea) were used. As the epoxy compound-dialkylamine adduct, which is the hardening promoter, there was used the reac-tion product of ~umiepoxy ESCN-220 ~ (the trade name of a cresol-novolac-type epoxy resin produced by Sumitomo .. ..
Chemical Company, ~imited; softening point 70C.; epoxy equivalent 215 g/equiv.) with dimethylamine, the reaction product being abbreuiated as N-amine hereinafter.
~he "N-amine" in Experiment No. 3 is the reaction product of Sumiepoxy ESCN-220 HH (the trade name of a cresol-novolac-type epoxy resin produced by Sumitomo Chemical Company ?
~imited; epoxy equi~alent ~20 g/equiv.) with dimethylamine.
The adduct in Experiment No. 5 is the reaction product of Sumiepoxy ESCN-220 ~ wi-th dibutylamine, the reaction pro-duct being abbreviated as N'-amine, hereinafter. The adduct in ~xperiment No. 7 is the reaction product of an equal weight mixture of Sumiepoxy ESCN-220 ~ and Sumiepoxy ESA-011 (the trade name of a bisphenol A t~pe epoxy resin produced by Sumitomo Chemical Company, ~imited; softening point 69C.;
epoxy equivalent 490 g/equiv.) with dimethylamine, the reac tion product being abbreviated as NA-amine, hereinafter.
~he adduct in Experiment No. 8 is produced by surface-neutra- i lizing the said NA-amine with acetic acid, the adduct being 1~
'75~ ,~
.
, .
abbreviated as neutralized NA-amine.
The electroconductive paste was produced by thoroughly mixing the epoxy resin and hardener, then adding the electroconductive filler and solvent~ and sufficiently kneadin`g the mixture by three roll mill. IL
The characteristics of the paste thus produced were measured as follows: i;
Usable duration (pot life) j.
The resin i9 drop-fed onto an alumina substrate, using a quantitative drop-feeding appliance (dispenser).
On the drop-fed paste, Si-chips of a 1.5 mm sqLuare are placed~one by one with the passage of time. The time I (number of day) at which the chip does not adhere is ~i determined as the pot li~e.
Quantity of released gas i:
As soon as the paste is drop-fed onto the alumina substrate a Si chip is adhered. By using a thermobalance, the quantity of` released gas when the paste is hardened at 7 .
150C. for 30 minutes, is determined as the quantity of weight reduction.
Adhesion stren~th and strenJth after heating __~___ __ The adhesion strength between the resin and Si chip is measured for the sample hardened in the preceding para-graph. The adhesion strength after heating at 350C. for 30 seconds is also measured. The adhesion strength and strength after heating are shown by the pushing pressure when the Si chip, pushed by a jlg at its side, comes off. r Sheet resistance The paste is printed on an alumina substrate to form a pattern 2.5 mm wide and 5.0 mm long, and the printed ~4t7~;j.7 paste is hardened at 150C. for 30 minutes. ~he resistance between the two ends in the lengthwise direction of the hardened film is measured, and it is expressed as the sheet resistance. (In this case, the sheét resistance is 1/2 of the total resistance.) These characteristic values are shown in the succeeding Table. b' ~ he paste of Experiment No. 1 has too short a pot li~e and is unsuitable. ~he pastes of Experiment No. 2 and No. 6 have too low an adhesion strength. This is :
because with only the latent hardener the hardening tem-perature 150C. is too low for sufficient hardening.
In Experiment Nos. 3, 4, 5, 7 and 8? hardening was accelerated by the presence of the epoxy compound-dialkylamine adduct, and the characteristic values were satisfactory enough. Especially, the result of Experiment No. 3 shows that, if the amine adduct is added in a suf-ficient quantity there is no problem, even withou-t addition of any latent hardener.
Experiment No. 9 to No. 13 show the case where the ratios of the resin and hardener components in the paste were varied~ In Experiment No. 9, the resin component was too little to give a sufficient adhesion strength9 and on the con-trary in Experiment No. 13, the resin component was too much for giving a good electroconducti~itvv.
In ~xperiment No. 14 to No. 16, the electroconduc-tivé filler was gold, copper or aluminum powder. ~11 of them gave satisfactory results.
p ~ I , o o o o ~ o ~ o ~: o o o ~ o a) h h h h a~ h O
o ~ o ~ a) o H ~ 1~4 ~ H
cr O O O O O O O
a) ~ r ~ ~ (:10 1~ 0 0 N U~ 1 E ~ 1~ N N ~ N
tlO S~
h ~l ~~ O 1~ 0 Is~
~ r~ ~ ~ r~l h ~ ~ t~
C~
,S O h ~ bi) CO Ll-\ ~J N N 0; ) r ~ D ,Y r-l r a~ , o c . ~ . ~ t- ~ ~ O
N N N r-i N N N
C3 ~ ~
~ LO
-~0 ~ ~ O L~
h O Ir~
P~ h ~! t[~ ~ t~
3 h ~ ~ ~ :~ ::~
h ~ , ~ F~ L ~ r--NI~ a.) t ~ ~J
~ ~ ~1 O O a) O ~ O O F' O u~ ~3 r~l ~ r~ ~ r--1 r-l r--1 r--1 r-l r~ ~ ~ . ~ ~ . ~~~ ~;~o ~ ~ `b~
h h ~ r~ Lf~ ~ L~ t~ ~:) L~ ) I Lt~ Lr~ V I
t~ Pl O _ O r-l r~l I N H ~ Fl 5:~ ~I H r~l I ~ ~1 F~ Fl o~ F~ ~D F~l r~l ~ ~ ~ ~~
o.a~ ~0 ~0 c~ ~ ~ O c~ o ~o ~o U~ ~ ~~ F4 r-l P-~ r~l ~:q 00P~ r~l P~ rl ` F4 rl f 4 r-l h ~ h h ~h ~r h h h h r~ ~ r~ H r--l ~ H r--l r~l r-l .~ ~rl Lr~ ~1 L~\ ~1 CO ~1 Lr~ 1 L~ ~rl L~
X O ¦ H N S~ ~t L~
~13-5~7 o o o ~ o ~ o ~, o o o ~ o h ~ h a) S::
a~ o ~ ~ o ~d ,C a~
o O ~ 0~
N ~i ~ N L
O
A
a) L~
r~
~D N N ~D L~
" V Lr` ~ ~ cr~ O
N ~ ~ ~* t~
+' N O O N ~ r i N
C~ ~
. _~
Lr~ ~ ~ L~
., '~ "
E~ Lf~ L~ L~ L~ L~ Lr~ L
h.~ ~ ~ ~ h ~ h Q~ ~ r-l F2~N P~ r-l Q~ ~4rN~
ô $:~ o o o a) ô a) o q, O o O ~
r~l~ r r-l ~ ~-1 ' ~ rl ~ r-l t~R
H ~ N L~ V ~:\1 H I ~0 H I U~ N H I t~ H I r-l ~2; r-l R ~ ; ~ Z Fl ~ Z
O ~ C~ C~ O C~ Lr~ ~ O ~ O
r-l F4 r-l 1:4 ~ P~ H P1 r-l p I ~ P~ r~l h h h h h h r-l r-l H H H H r~
~rl L~ 0 ~l L~ r~ O ~rl LO
o r-l r1 r-l r I vl r I
3~7 ~;
~ O ~ o H +' E~
O O
Lr~ t N
~ ~t t--,, ~ OD
. .
- N N
o , C) : _, a~ ~ u~
a~
h ::~
P~N ~N
.~ .~vl o a~ o ~1 ~ ~ ~
~1 ~ ~ ~ . ~æ
H I ~I H I r1 1~
O p~ O
h I -O L~
C~ ~ ¢ ~ r-~ ~D
and no~metal such as carbon. The powder may be made of an alloy or in a mixture of two or more of the powders~ Usuallys the powder ha~ a particle diameter of about 0.1 to 10 ~m. The powder i~ flake form is preferable in respect of electroconductivity.
~he qua~tity of the electroconducti~e filler ma~ be altered depending on the specific gravity of the powder to be used and ran~es from 50 thI~ough 95 % by weight based on the weight of the paste. A quantity less than 50 % by weight will ~ot make the harde~ed product electroconducti~e. Whe~eas, if the quantity exceeds ¦.
95 % by ~veight, the ratio of the epoxy resin becomes too low, which will results in insufficienc~ of adhesive strength.
As the reactiYe solvents, suitable are epoxy compounds such as phenylglycidyl ether, butylglycidyl ether, neopentyl glycol glycidyl ether, etc. Since the reactive solvent is used for the regulation of the ~iSC08it~ of the paste, it should be limited to a necessary minimum. With the increase in the quantity added, the ~uantity of released gas increases and the heat resis-tJa~ce of the resi~ after hardening lowers. For this reason, the suitable quantity to be added ranges from 1 through 20 % by weight~ I~ the qu~ntity is less than 1 % by weight, the viscosity of the composition becomes too high. If the quantit~ exceeds 20 % by weight, the quantity of released gas upon harde~ing becomes too much or the charac~eristics of the hardened product will be lmpalred, ~ 7S ~
As the epoxy resin usable for the hardening component, an~ can be used which has two or more epoxy groups per molecule. Such epoxy resins include~ for example, polyglycidyl ethers produced by the reactiou betwee~ a polyh~dric phenol (e.gO bisphenol A, bisphenol F, catechol, resorcin, etc.) or a pol~hydric alcohol (e.g. glycerinl polyethylene glycol~ etc~) and epichlo-rohydrin; polygl~cidyl ether esters produced by the .:
reaction be~ween a hydrox~carbox~lic acid (e.g. p-ox~benzoic acid, beta-oxynaphthoic acid, etc.) aud epichlorohydrin; polyglycidyl esters obtained from a polycarboxylic acid (e.g. phthalic acid, terephthalic acid, etcO); glycidylamine compounds obtained from 4,4'- :
dlaminodiphenyl methan~, m-aminophenol, etc.; epoxydized novolac~ and epox~dized polyolefins.
As the latent hardener, there can be used those known latent hardeners such as urea, guanidine, hydrazine, hydra3ide, amidine~ triazine, azo compounds, etc. Co~crete example~ of these compounds includ~
acetylmethyl urea, benz~lurea, thiourea, 3-(substituted or u~ubstituted)phenyl~ di~ alkylurea (e.g. 3-phenyl~ dimethylurea, 3-(4-chlorophenyl)~ di-methylurea, 3-(3,4-dichlorophenyl~ dimethylurea, 3-phenyl~ dibutylurea, etc.), acetylsemicarbazide, acetaldehyde semicarbazone, asetone semicarbazone, ~
N,N'-diphenylguanidi~e, methylguanidine, biguanide, .
dicyandiamide, sebacic acid dihydrazide, succinic acid ~.
dihydrazide, adipic acid dihydrazide 9 tartaric acid dihydrazid~, dicyandiamidine, hydrazobenzene, acet-aldehyde phenylhydrazone, ben ophenone phenylhydrazone 9 ', benzamidine, melamine~ azobenzene,. diaminoazobe.nze~e, -- 5 ~
7~
etc. The quantity to be used is 0 to 30 parts by weight based on 100 parts by weight of the epoxy resin. If the quantity is more than 30 parts by weight, it is impossible to obtain stable properties after hardening.
The epoxy compound-dialkylamine adduct usable for the hardening component functions as a hardening promotor. mhe dialkylamine usable for the preparation of the adduct, which alkyl may be unsubstituted or substi-tuted, includes dimethylamine, dipropylamine, N-methyl-ethylamine 9 N-ethylisopropylamine, diallylamine, diben-zylamine or the like, and N-ethylethanolamine, diethanol-amine or the like. The epoxy compound includes, ~or example, monoepoxy compounds represented by butylglycidyl ether and phenylglycidyl ether, epoxy resins obtained from the above-exemplified polyhydric phenols, polycarbo-xylic acids and amines.
At least one member of the epoxy compounds and an excess quantity of the dialky]amine are mixed in a solvent and allowed to react under heating. After completion of the , reaction, the unreacted amine and solven-t are removed by distillation to obtain the epoxy compound-dialkylamine adduct having a desired softening point.
~ s such solvents, those which are capable of dis-solving the epoxy compound and have a boiling point above 50C. are suitable. They include, for example, tetrahydro-furan, dioxane, acetone, methyl ethyl ketone, toluene, monochlorobenæene, methylcellosolve, ethylcellosolve, etc. L' Of these, ethylcellosolve and toluene are preferable.
The adducts thus obtained are pulverized by an atmizer or the like and are used in the form of powder in ~4~7~7 the present invention. The powder may be further surface-treated with an acidic substance. The sur~ace-treated adduct is preferable in view of the storage stabili-ty of the electroconductive pastes.
rrhe surface treatment of the adduct may be carried ou-t by exposing the adduct to a gaseous acid or dispersing it in a dilute solution of the acidic substance, followed by drying. :
The acidic substances used for the surface treat-ment are gaseous or liquid inorganic or organic acids.
They include, for example, sulfur dioxide, hydrochloric .
acid, carbon dioxides, sulfuric acid, phosphoric acid, boric acid, formic acid, oxalic acid, acetic acid, pro-pionic acid, lactic acid, caproic acid, salicylic acid, tartaric acid, succinic acid, adipic acid, sebacic acid, p-toluene sulfonic acid, phenol, phyrogallol, tannic acid, rosin, polyacrylic acid, polymethacrylic acid, alginic acid, phenol resin, resorcin resin, etc.
The acidic subs-tances may be used in an amount ~ , :
enough to neutralize the amino groups exposed on the surface s 1':
of the adduc-t powder. Too much a ouantity may lower the hardening promotin~ effect of -the resin. Therefore, it is preferable to decide the necessary quantity, for example, by a quantitative analysis of the amine.
The adduct compound accelerates the action of i the latent hardener J and also act singly as a hardener. -The quantity of the adduct to be used is 0.1 to 40 parts by weight based on 100 parts by weight of the epoxy resin.
With the increase of the quantity of the adduct, the ratio of the latent hardener may be lowered. A quantity less 7 _ than 0.1 part by weight fails to harden the resin suffi-ciently. The quantity of the adduct may be increased to use no latent hardener. ~owever, if the quantity exceeds 40 parts by weight, the hardened product is discolored ~, . . !' and its characteristics are rather deteriorated.
- The sum of the quantities of the hardening component comprising the epoxy resin, latent hardener and epoxy compound-dialkylamine adduct is 4 to 30 ~ by weight of the total weight of the above mentioned (a), (b) and (c). The quan-tities of the hardening component and the i;
electroconductive filler are complementary with each other.
If the quantity of the hardening component is too large, the electroconductivity will be lost, whereas it is too small, -the strength of the hardened product will be made insufficient.
The electroconductive paste of the present inven~
tion can be easily obtained by weighing out the above men-tioned ingredients and kneading them with a three roll mill or the like. , Insufficiency in the degree of dispersion of the hardener will cause a fluctuation of the adhesive strength, e~c. when the resulting paste is used with extremely small quantities of drop-feeds, so that it is more prefer-able that the epoxy resin, latent hardener and epoxy com-pound-dialkylamine adduct are sufficiently mixed to form the hardening component.
The electroconductive paste thus obtained has a long pot life, hardens rapidly when heated at a high temperature, releases a small quantity of gas upon harden-ing, and has excellent characteristics (especially heat resistance), and there~ore it is particularly suitable for 5~
the bonding of electronic parts.
The electroconductive resin paste according to the present invention may contain another solvent, vis-cosity regulating agent, filler, coloring agent, e-tc.
as far as no adverse effect is produced on the storage stability, hardening properties, etc.
The above explanation has referred to the case of chip bonding of semiconductor elements according to the drop-feed method, but the electroconductive resin paste of the present invention may be used for screen-printing, the formation of electroconductive circuits on a plastic plate, or the like~.
The present invention is explained in more detail with reference to the following Examples.
Examples Using as electroconductive filler mainly flaky ~
silver powder, as the reactive solvent mainly phenylgly-cidyl ether (hereinafter abbreviated as PGE), and as the t epoxy resin in all cases a bisphenol A-type epoxy resin (hereinafter abbreviated as BPA Epoxy), and ln combination with various hardeners, electroconductive pastes were pro-duced, and their characteristics were measured. The com-positions of the pastes are shown in the Table, wherein ¦;
BPA Epoxy is Sumiepoxy ELA-128 tthe trade name of a bis-phenol A-type epoxy resin produced by Sumitomo Chemical Company, Limited; its epoxy e~uivalent is 190 g/equiv.).
As the solvent in Experiment No. 3 only, butylglycidyl ether (hereinafter abbreviated as BG~) was used. The hardener in Experiment No. 1 was Sumicure P-725 (the trade name o~
`:
_ 9 _ ~ 7~
a polyamide resin produced by Sumitomo Chemical Company, ~imited; its amine value is 300 mg KOH/g), and this product is widely used as a hardener for usual epoxy resins.
As the latent hardener, dicyandiamide (herein-after abbreviated as DICY), 3-(4-chlorophenyl)-1?1-dimethyl-urea (hereinafter abbreviated as p-urea) and 3-(3 9 4-dichloro- !`
phenyl)-l,l-dimethylurea (hereinafter abbreviated as 3-urea) were used. As the epoxy compound-dialkylamine adduct, which is the hardening promoter, there was used the reac-tion product of ~umiepoxy ESCN-220 ~ (the trade name of a cresol-novolac-type epoxy resin produced by Sumitomo .. ..
Chemical Company, ~imited; softening point 70C.; epoxy equivalent 215 g/equiv.) with dimethylamine, the reaction product being abbreuiated as N-amine hereinafter.
~he "N-amine" in Experiment No. 3 is the reaction product of Sumiepoxy ESCN-220 HH (the trade name of a cresol-novolac-type epoxy resin produced by Sumitomo Chemical Company ?
~imited; epoxy equi~alent ~20 g/equiv.) with dimethylamine.
The adduct in Experiment No. 5 is the reaction product of Sumiepoxy ESCN-220 ~ wi-th dibutylamine, the reaction pro-duct being abbreviated as N'-amine, hereinafter. The adduct in ~xperiment No. 7 is the reaction product of an equal weight mixture of Sumiepoxy ESCN-220 ~ and Sumiepoxy ESA-011 (the trade name of a bisphenol A t~pe epoxy resin produced by Sumitomo Chemical Company, ~imited; softening point 69C.;
epoxy equivalent 490 g/equiv.) with dimethylamine, the reac tion product being abbreviated as NA-amine, hereinafter.
~he adduct in Experiment No. 8 is produced by surface-neutra- i lizing the said NA-amine with acetic acid, the adduct being 1~
'75~ ,~
.
, .
abbreviated as neutralized NA-amine.
The electroconductive paste was produced by thoroughly mixing the epoxy resin and hardener, then adding the electroconductive filler and solvent~ and sufficiently kneadin`g the mixture by three roll mill. IL
The characteristics of the paste thus produced were measured as follows: i;
Usable duration (pot life) j.
The resin i9 drop-fed onto an alumina substrate, using a quantitative drop-feeding appliance (dispenser).
On the drop-fed paste, Si-chips of a 1.5 mm sqLuare are placed~one by one with the passage of time. The time I (number of day) at which the chip does not adhere is ~i determined as the pot li~e.
Quantity of released gas i:
As soon as the paste is drop-fed onto the alumina substrate a Si chip is adhered. By using a thermobalance, the quantity of` released gas when the paste is hardened at 7 .
150C. for 30 minutes, is determined as the quantity of weight reduction.
Adhesion stren~th and strenJth after heating __~___ __ The adhesion strength between the resin and Si chip is measured for the sample hardened in the preceding para-graph. The adhesion strength after heating at 350C. for 30 seconds is also measured. The adhesion strength and strength after heating are shown by the pushing pressure when the Si chip, pushed by a jlg at its side, comes off. r Sheet resistance The paste is printed on an alumina substrate to form a pattern 2.5 mm wide and 5.0 mm long, and the printed ~4t7~;j.7 paste is hardened at 150C. for 30 minutes. ~he resistance between the two ends in the lengthwise direction of the hardened film is measured, and it is expressed as the sheet resistance. (In this case, the sheét resistance is 1/2 of the total resistance.) These characteristic values are shown in the succeeding Table. b' ~ he paste of Experiment No. 1 has too short a pot li~e and is unsuitable. ~he pastes of Experiment No. 2 and No. 6 have too low an adhesion strength. This is :
because with only the latent hardener the hardening tem-perature 150C. is too low for sufficient hardening.
In Experiment Nos. 3, 4, 5, 7 and 8? hardening was accelerated by the presence of the epoxy compound-dialkylamine adduct, and the characteristic values were satisfactory enough. Especially, the result of Experiment No. 3 shows that, if the amine adduct is added in a suf-ficient quantity there is no problem, even withou-t addition of any latent hardener.
Experiment No. 9 to No. 13 show the case where the ratios of the resin and hardener components in the paste were varied~ In Experiment No. 9, the resin component was too little to give a sufficient adhesion strength9 and on the con-trary in Experiment No. 13, the resin component was too much for giving a good electroconducti~itvv.
In ~xperiment No. 14 to No. 16, the electroconduc-tivé filler was gold, copper or aluminum powder. ~11 of them gave satisfactory results.
p ~ I , o o o o ~ o ~ o ~: o o o ~ o a) h h h h a~ h O
o ~ o ~ a) o H ~ 1~4 ~ H
cr O O O O O O O
a) ~ r ~ ~ (:10 1~ 0 0 N U~ 1 E ~ 1~ N N ~ N
tlO S~
h ~l ~~ O 1~ 0 Is~
~ r~ ~ ~ r~l h ~ ~ t~
C~
,S O h ~ bi) CO Ll-\ ~J N N 0; ) r ~ D ,Y r-l r a~ , o c . ~ . ~ t- ~ ~ O
N N N r-i N N N
C3 ~ ~
~ LO
-~0 ~ ~ O L~
h O Ir~
P~ h ~! t[~ ~ t~
3 h ~ ~ ~ :~ ::~
h ~ , ~ F~ L ~ r--NI~ a.) t ~ ~J
~ ~ ~1 O O a) O ~ O O F' O u~ ~3 r~l ~ r~ ~ r--1 r-l r--1 r--1 r-l r~ ~ ~ . ~ ~ . ~~~ ~;~o ~ ~ `b~
h h ~ r~ Lf~ ~ L~ t~ ~:) L~ ) I Lt~ Lr~ V I
t~ Pl O _ O r-l r~l I N H ~ Fl 5:~ ~I H r~l I ~ ~1 F~ Fl o~ F~ ~D F~l r~l ~ ~ ~ ~~
o.a~ ~0 ~0 c~ ~ ~ O c~ o ~o ~o U~ ~ ~~ F4 r-l P-~ r~l ~:q 00P~ r~l P~ rl ` F4 rl f 4 r-l h ~ h h ~h ~r h h h h r~ ~ r~ H r--l ~ H r--l r~l r-l .~ ~rl Lr~ ~1 L~\ ~1 CO ~1 Lr~ 1 L~ ~rl L~
X O ¦ H N S~ ~t L~
~13-5~7 o o o ~ o ~ o ~, o o o ~ o h ~ h a) S::
a~ o ~ ~ o ~d ,C a~
o O ~ 0~
N ~i ~ N L
O
A
a) L~
r~
~D N N ~D L~
" V Lr` ~ ~ cr~ O
N ~ ~ ~* t~
+' N O O N ~ r i N
C~ ~
. _~
Lr~ ~ ~ L~
., '~ "
E~ Lf~ L~ L~ L~ L~ Lr~ L
h.~ ~ ~ ~ h ~ h Q~ ~ r-l F2~N P~ r-l Q~ ~4rN~
ô $:~ o o o a) ô a) o q, O o O ~
r~l~ r r-l ~ ~-1 ' ~ rl ~ r-l t~R
H ~ N L~ V ~:\1 H I ~0 H I U~ N H I t~ H I r-l ~2; r-l R ~ ; ~ Z Fl ~ Z
O ~ C~ C~ O C~ Lr~ ~ O ~ O
r-l F4 r-l 1:4 ~ P~ H P1 r-l p I ~ P~ r~l h h h h h h r-l r-l H H H H r~
~rl L~ 0 ~l L~ r~ O ~rl LO
o r-l r1 r-l r I vl r I
3~7 ~;
~ O ~ o H +' E~
O O
Lr~ t N
~ ~t t--,, ~ OD
. .
- N N
o , C) : _, a~ ~ u~
a~
h ::~
P~N ~N
.~ .~vl o a~ o ~1 ~ ~ ~
~1 ~ ~ ~ . ~æ
H I ~I H I r1 1~
O p~ O
h I -O L~
C~ ~ ¢ ~ r-~ ~D
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An electroconductive paste comprising:
(a) an electroconductive filler;
(b) a reactive solvent; and (c) a hardener comprising, (c-1) an epoxy resin, (c-2) a latent hardener, and (c-3) an epoxy compound-dialkylamine adduct, the percent by weight of (a), (b) and (c) being 95 to 50, 1 to 20 and 4 to 30, respectively, and the weight ratio of (c-1) : (c-2) . (c-3) being 100 : 0 to 30 : 0.1 to 40.
(a) an electroconductive filler;
(b) a reactive solvent; and (c) a hardener comprising, (c-1) an epoxy resin, (c-2) a latent hardener, and (c-3) an epoxy compound-dialkylamine adduct, the percent by weight of (a), (b) and (c) being 95 to 50, 1 to 20 and 4 to 30, respectively, and the weight ratio of (c-1) : (c-2) . (c-3) being 100 : 0 to 30 : 0.1 to 40.
2. The paste according to claim 1, wherein the electro-conductive filler is a powder made of noble metals, base metals or non-metals.
3. The paste according to claim 1, wherein the reactive solvent is phenylglycidyl ether, butylglycidyl ether or neopentylglycol glycidyl ether.
4. The paste according to claim 1, wherein the epoxy compound is at least one member selected from polyglycidyl ethers, polyglycidyl ether esters, polyglycidyl esters, glycidylamine compounds, epoxydized novolacs and epoxydized polyolefins.
5. The paste according to claim 1, wherein the latent hardener is at least one member selected from urea, guanidine, hydrazine, hydrazide, amidine, triazine and azo compounds.
6. The paste according to claim 5, wherein the latent hardener is at least one member selected from acetylmethyl urea, benzylurea, thiourea, 3-(substituted or unsubstituted) phenyl-1,1-di-C1-C4 alkylureas, acetylsemicarbazide, acetal-dehyde semicarbazone, acetone semicarbazone, N,N'-diphenyl, guanidine, methylguanidine, biguanide, dicyandiamide, sebacic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, tartaric acid dihydrazide, dicyandiamidine, hydrazobenzene, acetaldehyde phenylhydrazone, benzophenone phenylhydrazone, benzamidine, melamine, azobenzene and diaminoazobenzene.
7. The paste according to claim 1, wherein the dialkyl-amine is a member selected from dimethylamine, dipropylamine, N-methylethylamine, N-ethylisobutylamine, diallylamine, dibenzylamine, N-ethylethanolamine and diethanolamine.
8. The paste according to claim 1, wherein the epoxy compound-dialkylamine adduct is the one produced by heating an epoxy compound and an excess amount of dialkylamine in a solvent.
9. The paste according to claim 1, wherein the epoxy compound-dialkylamine adduct is the one produced by heating an epoxy compound and an excess amount of dialkylamine to obtain the epoxy compound-dialkylamine adduct, and then treating the surface of the resulting adduct with a acidic substance.
10. Electronic parts produced by using the paste of claim 1 for bonding elements.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP71168/81 | 1981-05-11 | ||
JP56071168A JPS57185316A (en) | 1981-05-11 | 1981-05-11 | Electrically conductive resin paste |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1184757A true CA1184757A (en) | 1985-04-02 |
Family
ID=13452849
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000402492A Expired CA1184757A (en) | 1981-05-11 | 1982-05-07 | Conductive paste |
Country Status (6)
Country | Link |
---|---|
US (1) | US4410457A (en) |
JP (1) | JPS57185316A (en) |
CA (1) | CA1184757A (en) |
DE (1) | DE3217723A1 (en) |
FR (1) | FR2505543A1 (en) |
GB (1) | GB2102004B (en) |
Families Citing this family (66)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0110285A3 (en) * | 1982-11-27 | 1985-11-21 | Prutec Limited | Interconnection of integrated circuits |
JPS59195837A (en) * | 1983-04-21 | 1984-11-07 | Sharp Corp | Chip bonding method for large-scale integrated circuit |
US4535012A (en) * | 1983-09-30 | 1985-08-13 | Electro Materials Corp. Of America | Fast curing solderable conductor |
US4564563A (en) * | 1983-09-30 | 1986-01-14 | Electro Materials Corp. Of America | Solderable conductor |
US4575432A (en) * | 1984-07-09 | 1986-03-11 | W. R. Grace & Co. | Conductive thermosetting compositions and process for using same |
US4595606A (en) * | 1984-07-18 | 1986-06-17 | Rohm And Haas Company | Solderable conductive compositions having high adhesive strength |
US4595604A (en) * | 1984-07-18 | 1986-06-17 | Rohm And Haas Company | Conductive compositions that are directly solderable and flexible and that can be bonded directly to substrates |
US4581158A (en) * | 1984-09-26 | 1986-04-08 | W. R. Grace & Co. | Conductive thermosetting compositions and process for using same |
US4747968A (en) * | 1985-05-08 | 1988-05-31 | Sheldahl, Inc. | Low temperature cure having single component conductive adhesive |
EP0205686A1 (en) * | 1985-06-13 | 1986-12-30 | Kidd, Inc. | Die-bonding electroconductive paste |
US4695508A (en) * | 1985-09-06 | 1987-09-22 | The Yokohama Rubber Co., Ltd. | Adhesive composition |
DE3533993A1 (en) * | 1985-09-24 | 1987-04-02 | Borg Instr Gmbh | METHOD FOR CONTACTING ON PATHWAYS, DEVICE FOR EXERCISING THE METHOD, AND LIQUID CRYSTAL CELL WITH BONDED CHIP |
US4732702A (en) * | 1986-02-13 | 1988-03-22 | Hitachi Chemical Company, Ltd. | Electroconductive resin paste |
US4780371A (en) * | 1986-02-24 | 1988-10-25 | International Business Machines Corporation | Electrically conductive composition and use thereof |
US4859268A (en) * | 1986-02-24 | 1989-08-22 | International Business Machines Corporation | Method of using electrically conductive composition |
US4880570A (en) * | 1986-03-31 | 1989-11-14 | Harris Corporation | Electroconductive adhesive |
US4695404A (en) * | 1986-04-07 | 1987-09-22 | Amerasia International Technology, Inc. | Hyperconductive filled polymers |
US4960614A (en) * | 1987-02-06 | 1990-10-02 | Key-Tech, Inc. | Printed circuit board |
US4786524A (en) * | 1987-07-08 | 1988-11-22 | The United States Of America As Represented By The United States Department Of Energy | Coating formulation and method for refinishing the surface of surface-damaged graphite articles |
JPH0628269B2 (en) * | 1987-07-15 | 1994-04-13 | 株式会社巴川製紙所 | Adhesive tape for die bonding |
DE3809331C1 (en) * | 1988-03-19 | 1989-04-27 | Degussa Ag, 6000 Frankfurt, De | |
DE3824139A1 (en) * | 1988-07-15 | 1990-01-25 | Siemens Ag | Electrodes for piezoceramics |
US5001542A (en) * | 1988-12-05 | 1991-03-19 | Hitachi Chemical Company | Composition for circuit connection, method for connection using the same, and connected structure of semiconductor chips |
JP2833111B2 (en) * | 1989-03-09 | 1998-12-09 | 日立化成工業株式会社 | Circuit connection method and adhesive film used therefor |
US5075034A (en) * | 1989-09-08 | 1991-12-24 | The Dexter Corporation | Induction curable two-component structural adhesive with improved process ability |
US5183593A (en) * | 1989-11-14 | 1993-02-02 | Poly-Flex Circuits, Inc. | Electrically conductive cement |
GB2239244B (en) * | 1989-11-14 | 1994-06-01 | David Durand | Moisture resistant electrically conductive cements and methods for making and using same |
US5180523A (en) * | 1989-11-14 | 1993-01-19 | Poly-Flex Circuits, Inc. | Electrically conductive cement containing agglomerate, flake and powder metal fillers |
US5056706A (en) * | 1989-11-20 | 1991-10-15 | Microelectronics And Computer Technology Corporation | Liquid metal paste for thermal and electrical connections |
US5043102A (en) * | 1989-11-29 | 1991-08-27 | Advanced Products, Inc. | Conductive adhesive useful for bonding a semiconductor die to a conductive support base |
US5376403A (en) * | 1990-02-09 | 1994-12-27 | Capote; Miguel A. | Electrically conductive compositions and methods for the preparation and use thereof |
JPH0412595A (en) * | 1990-05-02 | 1992-01-17 | Mitsubishi Petrochem Co Ltd | Conductive paste composition |
EP0481228A3 (en) * | 1990-10-17 | 1992-09-02 | American Cyanamid Company | Induction curing electro-coatable seam filler |
US5170930A (en) * | 1991-11-14 | 1992-12-15 | Microelectronics And Computer Technology Corporation | Liquid metal paste for thermal and electrical connections |
US5354392A (en) * | 1992-01-24 | 1994-10-11 | Matsushita Electric Industrial Co., Ltd. | Method for connecting a wiring arranged on a sheet with another wiring arranged on another sheet by ultrasonic waves |
US5445308A (en) * | 1993-03-29 | 1995-08-29 | Nelson; Richard D. | Thermally conductive connection with matrix material and randomly dispersed filler containing liquid metal |
US5328087A (en) * | 1993-03-29 | 1994-07-12 | Microelectronics And Computer Technology Corporation | Thermally and electrically conductive adhesive material and method of bonding with same |
US5464910A (en) * | 1993-12-22 | 1995-11-07 | Shikoku Chemicals Corporation | Epoxy resin adduct combined with a borate ester and phenolic compound |
JPH09324107A (en) * | 1996-06-07 | 1997-12-16 | Matsushita Electric Ind Co Ltd | Electrically conductive filler composition |
JP2915379B2 (en) * | 1996-06-18 | 1999-07-05 | レイセオン・カンパニー | Conductive adhesive resistant to drop impact |
US6338809B1 (en) | 1997-02-24 | 2002-01-15 | Superior Micropowders Llc | Aerosol method and apparatus, particulate products, and electronic devices made therefrom |
EP1007308B1 (en) * | 1997-02-24 | 2003-11-12 | Superior Micropowders LLC | Aerosol method and apparatus, particulate products, and electronic devices made therefrom |
US6830823B1 (en) | 1997-02-24 | 2004-12-14 | Superior Micropowders Llc | Gold powders, methods for producing powders and devices fabricated from same |
US6297564B1 (en) | 1998-04-24 | 2001-10-02 | Amerasia International Technology, Inc. | Electronic devices employing adhesive interconnections including plated particles |
GB2338481B (en) * | 1998-06-16 | 2002-09-11 | Atraverda Ltd | Electrochemical curable resin compositions |
US6451127B1 (en) | 1999-06-01 | 2002-09-17 | Motorola, Inc. | Conductive paste and semiconductor component having conductive bumps made from the conductive paste |
EP1226742B1 (en) | 1999-11-03 | 2006-12-27 | Nexicor, LLC | Hand held induction tool |
WO2001046289A1 (en) * | 1999-12-21 | 2001-06-28 | Atraverda Limited | Electrochemical curable resin compositions |
US7081214B2 (en) * | 2000-10-25 | 2006-07-25 | Harima Chemicals, Inc. | Electroconductive metal paste and method for production thereof |
CN1500278A (en) * | 2001-03-28 | 2004-05-26 | E・I・内穆尔杜帮公司 | Compsn. for filling through-holes in printed wiring boards |
US20040094751A1 (en) * | 2002-03-25 | 2004-05-20 | Toshiaki Ogiwara | Composition for filling through-holes in printed wiring boards |
US7438969B2 (en) * | 2002-07-10 | 2008-10-21 | Ngk Spark Plug Co., Ltd. | Filling material, multilayer wiring board, and process of producing multilayer wiring board |
US20040226620A1 (en) * | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
US7141617B2 (en) * | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
US7956102B2 (en) * | 2007-04-09 | 2011-06-07 | The Board Of Trustees Of The University Of Illinois | Sol-gel inks |
US20100009153A1 (en) * | 2008-06-12 | 2010-01-14 | Nanomas Technologies, Inc. | Conductive inks and pastes |
US7922939B2 (en) * | 2008-10-03 | 2011-04-12 | The Board Of Trustees Of The University Of Illinois | Metal nanoparticle inks |
US8187500B2 (en) * | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
US8642709B2 (en) | 2010-03-23 | 2014-02-04 | Henkel Ag & Co. Kgaa | Epoxy resin composition with reduced toxicity |
DE102010028586A1 (en) * | 2010-05-05 | 2011-11-10 | Henkel Ag & Co. Kgaa | 1K epoxy resin composition with reduced toxicity |
DE102010020882A1 (en) * | 2010-05-18 | 2011-11-24 | Alzchem Trostberg Gmbh | Semicarbazone for curing epoxy resins |
SG189275A1 (en) * | 2010-10-05 | 2013-05-31 | Ferro Corp | Single component, low temperature curable polymeric composition and related method |
JP5741809B2 (en) * | 2011-02-22 | 2015-07-01 | 三菱マテリアル株式会社 | Bonding paste and method for bonding semiconductor element and substrate |
DE102011118501A1 (en) * | 2011-11-15 | 2013-05-16 | Alzchem Ag | Alkyl or dialkyl semicarbazones as hardeners for epoxy resins |
DE102011118760A1 (en) | 2011-11-15 | 2013-05-16 | Alzchem Ag | Use of N, N '(-dimethyl) -units and methods for curing epoxy resin compositions |
CA2969328A1 (en) * | 2015-01-16 | 2016-07-21 | Halliburton Energy Services, Inc. | Hydrazide-based curing agents for use in subterranean operations |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE510201A (en) * | 1949-10-25 | 1900-01-01 | ||
BE617618A (en) * | 1961-05-16 | |||
FR1355543A (en) * | 1961-10-16 | 1964-03-20 | Pittsburgh Plate Glass Co | Electrically conductive coating compositions |
DE1520821A1 (en) * | 1963-07-20 | 1970-04-02 | Siemens Ag | Process for hardening solvent-free epoxy resins |
FR1533642A (en) * | 1966-08-05 | 1968-07-19 | Hysol Corp | New resinous conductive compositions |
FR1538385A (en) * | 1967-06-22 | 1968-09-06 | Nii R I Latexnykh Izdely | Method of making an electrical contact |
DE2131929C3 (en) * | 1970-06-12 | 1978-07-13 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Heat-curable, thickened epoxy resin compounds |
US3998779A (en) * | 1973-05-21 | 1976-12-21 | Chromalloy American Corporation | Coating method and composition for the sacrificial protection of metal substrates |
DE2546568A1 (en) * | 1975-10-17 | 1977-04-21 | Ted Bildplatten | Electrically conductive adhesives - comprises epoxy resin polysulphide plasticiser and gold particles |
DE2731335A1 (en) * | 1977-07-12 | 1979-01-25 | Veba Chemie Ag | METHOD FOR BONDING MATERIALS |
US4155896A (en) * | 1977-07-27 | 1979-05-22 | Rockwell International Corporation | Organic coatings and paints having unique electrical properties |
US4312793A (en) * | 1978-03-03 | 1982-01-26 | Charneski Mitchell D | Electrical joint compound |
US4210704A (en) * | 1978-08-04 | 1980-07-01 | Bell Telephone Laboratories, Incorporated | Electrical devices employing a conductive epoxy resin formulation as a bonding medium |
GB2028828B (en) * | 1978-08-04 | 1982-09-22 | Western Electric Co | Conductive adhesive system including a conductivity enhancer |
EP0018949B1 (en) * | 1979-05-08 | 1984-04-11 | Ciba-Geigy Ag | Curable epoxy resin mixtures and curing accelerators therefore |
-
1981
- 1981-05-11 JP JP56071168A patent/JPS57185316A/en active Granted
-
1982
- 1982-05-05 US US06/375,096 patent/US4410457A/en not_active Expired - Fee Related
- 1982-05-07 CA CA000402492A patent/CA1184757A/en not_active Expired
- 1982-05-10 GB GB08213512A patent/GB2102004B/en not_active Expired
- 1982-05-10 FR FR8208088A patent/FR2505543A1/en active Granted
- 1982-05-11 DE DE19823217723 patent/DE3217723A1/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
GB2102004B (en) | 1984-12-05 |
JPH0134545B2 (en) | 1989-07-19 |
FR2505543A1 (en) | 1982-11-12 |
US4410457A (en) | 1983-10-18 |
GB2102004A (en) | 1983-01-26 |
DE3217723A1 (en) | 1982-12-02 |
FR2505543B1 (en) | 1984-11-30 |
JPS57185316A (en) | 1982-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1184757A (en) | Conductive paste | |
KR0170415B1 (en) | Conductive adhesive useful for bonding a semiconductor die to a conductive support base | |
EP0304503B1 (en) | Hardener for curable one-package epoxy resin system | |
CN107709502B (en) | Composition for bonding heat dissipating material, heat dissipating material with adhesive, embedded substrate, and method for producing embedded substrate | |
US5458978A (en) | Epoxy resin systems containing glycidylated aromatic amines, phosphorus epoxies and metal salts | |
EP0928825B1 (en) | Resin composition for use in sealant and liquid sealant using the resin composition | |
US3948849A (en) | Adhesive compositions | |
CN114292384A (en) | Epoxy resin composition, cured epoxy resin composition, paste, method for producing the same, and electrode | |
US20060014924A1 (en) | Reworkable adhesives containing thermally labile groups | |
JPS6063223A (en) | Synthetic resin containing basic nitrogen group and manufacture | |
JPS59206459A (en) | Electrically conductive paste | |
EP0385745A2 (en) | Powder coating composition | |
JPH0511364B2 (en) | ||
KR100681565B1 (en) | Die-attaching paste and semiconductor device | |
US3036975A (en) | Rapid-curing epoxy resin compositions and method of making | |
JP2002194057A (en) | Thermosetting resin composition | |
US3677995A (en) | Epoxy resin cement | |
US4592959A (en) | Silicone encapsulated devices | |
US4810768A (en) | Method and formulation for extending shelf life of a silicone resin | |
JPS62131078A (en) | Binder of cathodic electrodeposition painting | |
JPH07138549A (en) | Conductive adhesive | |
JP2568593B2 (en) | Conductive resin composition | |
IE57889B1 (en) | Polyfunctional phenolic reaction product,process for its preparation and its use | |
JP3200251B2 (en) | Semiconductor device and epoxy resin composition used therefor | |
US5075379A (en) | Rubber/diamine blends for use in curing epoxy resins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKEC | Expiry (correction) | ||
MKEX | Expiry |