Electrically conductive adhesive agent, joined body, and joint

Abstract

This invention has an object to provide an electrically conductive adhesive agent which enables a thermosetting resin to cure in a short time. It contains electrically conductive metallic powder including Sn, the thermosetting resin; an acid-anhydride-based hardening agent and an organic acid. The electrically conductive metallic powder and the organic acid are reacted during a heating process to produce an organic acid metal salt which is used as hardening accelerator. It enables thermosetting resin to cure in a short time, for example, a time equivalent to a time that is required for the general reflow process.

Claims

1. A method of forming a joint, comprising: heating an electrically conductive adhesive agent, wherein the electrically conductive adhesive agent comprises an electrically conductive metallic powder including Sn, a thermosetting resin, an acid-anhydride-based hardening agent, and an organic acid, wherein the electrically conductive metallic powder contains Sn of 85 weight % or more based on 100 weight % of the electrically conductive metallic powder, wherein the electrically conductive adhesive agent contains 88 through 90 weight % of the electrically conductive metallic powder based on 100 weight % of the electrically conductive adhesive agent, wherein the electrically conductive adhesive agent is heated at a temperature of 150 degrees C. or more and less than a melting point of the electrically conductive metallic powder to cause the electrically conductive metallic powder and the organic acid to react and to produce a hardening accelerator comprised of an organic acid metal salt, wherein, prior to heating, the electrically conductive adhesive agent does not include a hardening accelerator, and wherein the joint is formed without melting the electrically conductive metallic powder.

2. The method according to claim 1, wherein the electrically conductive metallic powder further includes at least one of: Ag, Bi, Cu, Au, Ni, Sb or Pd; or an alloy consisting of any combination of Sn, Ag, Bi, Cu, Au, Ni, Sb and Pd.

3. The method according to claim 1, wherein the thermosetting resin is an epoxy resin having an aliphatic skeleton, wherein the epoxy resin has flexibility.

4. The method according to claim 1, wherein the acid-anhydride-based hardening agent is selected from the group consisting of: acetic acid anhydride, propionic anhydride, succinic anhydride, and maleic anhydride.

5. The method according to claim 1, wherein the electrically conductive adhesive agent contains 2 through 6 weight % of the organic acid.

6. The method according to claim 1, wherein a volume resistivity of the electrically conductive adhesive agent in the joint is less than 1*10.sup.3 cm.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is a graph showing a relationship between the filler content and volume resistivity.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

Composition Example of Electrically Conductive Adhesive Agent According to the Embodiment

(2) Electrically conductive adhesive agent of this invention contains electrically conductive metallic powder including Sn, thermosetting resin, a hardening agent and an organic acid.

(3) As curing resin, there is resin that is cured by heat, light, ultraviolet rays or the like. As the curing resin, epoxy-based resin, phenolic resin, polyimide-based resin, silicon resin, polyurethane resin, unsaturated polyester resin and the like are conceivable, but the thermosetting resin is used because in the resin that is cured by light or ultraviolet rays, it is impossible to cure any resin positioned under the electronic parts when mounting the parts. As the thermosetting resin, the epoxy resin is the optimal resin.

(4) As the epoxy resin, epoxy resin of bisphenol type is selected. As the bisphenol type, bisphenol A type, bisphenol AP type, bisphenol AF type, bisphenol B type, bisphenol BP type, bisphenol C type, bisphenol E type, bisphenol F type, bisphenol G type, bisphenol M type, bisphenol S type, bisphenol P type, bisphenol PH type, bisphenol TMC type, bisphenol Z type and the like are exemplified. Preferably, it is the bisphenol A type.

(5) It is said that the epoxy resin is excellent in electric and/or mechanical joining properties but is fragile and poor in drop impact characteristic. This is because when curing the epoxy resin, any peeling occurs at an electrode interface to raise a crack. The epoxy resin at which this phenomenon occurs is set to be standard resin.

(6) When using any flexible resin in which, for example, an aliphatic skeleton is given to the epoxy resin, both the flexibility and the toughness are reinforced so that it is possible to prevent any crack by surface peeling from occurring.

(7) Hardening agent is used to cure the epoxy resin. As the hardening agent, amine, an acid anhydride and the like can be used. When the amine is used, the reaction is progressed even if the refrigeration storage is performed, so that the epoxy resin is cured. Therefore, the acid anhydride is selected to perform the refrigeration storage thereof.

(8) As the acid anhydride, acetic acid anhydride, propionic anhydride, succinic anhydride, maleic anhydride and the like are exemplified. In this embodiment, the succinic anhydride is used.

(9) It takes a long time until the hardening merely by heating the epoxy resin and the acid anhydride. Therefore, the hardening accelerator is required. As the hardening accelerator, for example, phenolic compound, tertiary amine, quaternary ammonium salt, quaternary phosphonium salt, imidazole, organic acid metal salt, Lewis acid and the like are exemplified. In this embodiment, the organic acid metal salt is used.

(10) The metallic powder constituting the organic acid metal salt may be replaced by the electrically conductive metallic powder itself for joining which is added to resin for joining. In this case, it is required to separately add nothing in order to produce the organic acid metal salt. Of course, the electrically conductive metallic powder may be separately added to produce the organic acid metal salt.

(11) The organic acid metal salt produced by the reaction of the metallic powder and the organic acid during the heating process is utilized as the hardening accelerator. According to this method, since there is no hardening accelerator when it is stored, in other words, any hardening acceleration function is not operated, it is possible to perform the refrigeration storage, thereby enabling the storage stability to be improved.

(12) As the electrically conductive metallic powder, Sn, Ag, Bi, Cu, Au, Ni, Sb or Pd itself or one or two species or more of metal or/and alloy in alloy consisting of the metals selected from the metallic powder group are exemplified. Sn itself is preferably used or a mixture or an alloy including Sn is used.

(13) As the organic acid, any generic organic acid may be used. Low molecular organic acid is preferable. In this embodiment, glutaric acid is used.

Executed Examples

(14) The following will describe concrete examples in which the invention is applied to the electrically conductive adhesive agent in the executed examples. This invention, however, is not limited to the following concrete examples.

(15) FIG. 1 is a characteristic diagram showing a relationship between the content of the electrically conductive metallic powder and volume resistivity. The volume resistivity is obtained by (resistance value*cross section area/length). Its unit is cm. In this example, the printing was performed on a ceramic substrate using the electrically conductive adhesive agent containing Sn powder, the epoxy resin, the hardening agent and the organic acid so that it could have a length of 11.5 mm, a width of 1.5 mm and a thickness of 0.12 mm. After hardening, its resistance value and volume resistivity were obtained.

(16) As being clearly shown in FIG. 1, it is understood that when the electrically conductive metallic powder is contained in the adhesive agent so that its content is 88 through 90 weight % of the total 100 weight % of the adhesive agent, the volume resistivity of the adhesive agent suddenly falls down. When the content thereof becomes 90 weight %, the volume resistivity thereof falls down to 1*10.sup.4 cm so that conductive property required for the solder can be sufficiently endured.

(17) The following examination was performed to find out a combination of the electrically conductive metallic powder (metallic filler) and the organic acid and the contents thereof when the organic acid metal salt was produced. All of the executed examples and the comparison examples contained electrically conductive metallic powder, epoxy resin, a hardening agent and an organic acid. When the epoxy resin cures, any exothermic reaction is accompanied. Accordingly, the exothermic reaction was observed by a Differential Scanning calorimetry (DSC) and temperature when thermosetting occurred and the volume resistivity after the hardening were measured. Measurement conditions of DSC were within a range of 25 through 300 degrees C. and temperature rising rate was 10 degrees C./min. The result thereof is shown in Table 1. The electrically conductive metallic powder used Sn, Cu or Ni and the organic acid used glutaric acid.

(18) TABLE-US-00001 TABLE 1 Executed Executed Comparison Comparison Example 1 Example 2 Example 1 Example 2 Electrically Sn Sn Cu Ni Conductive Metallic Powder Organic 0.5 2 2 2 Acid (wt %) Peak 216 204 255 280 Temperature (Degrees C.) Volume 6*10.sup.3 3*10.sup.4 3*10.sup.3 3*10.sup.1 Resistivity (cm)

(19) Peak temperature of the exothermic reaction is changed also by an addition amount of organic acid. When adding the organic acid of 0.5 weight %, the peak temperature was 216 degrees C. but when adding the organic acid of 2 weight %, it was 204 degrees C. which were decreased by 12 degrees C. Therefore, it is understood that an amount of the organic acid allows curing speed of the thermosetting resin to be accelerated.

(20) As a result where the executed examples 1 and 2 were carried out with the amount of the organic acid being changed, there was difference between them in the volume resistivity. It is conceivable that the more the amount of the organic acid is, many organic acid metal salts are produced, so that the curing speed becomes faster, which enables pieces of Sn powder to be adhered more closely. In addition, it is conceivable that there is any action by the organic acid to remove any oxide film from the Sn surface.

(21) Sn reacts with an organic acid so as to be easy to produce organic acid metal salts and enables the epoxy resin to cure at lower temperature than that of other metal. Namely, it is said that Sn is preferable for curing at the lower temperature.

(22) Table 2 showed how a period of time when the epoxy resin cured was influenced by a relationship of a molar ratio between the epoxy resin and the hardening agent and presence/absence of the organic acid metal salt. As the organic acid metal salt, glutaric acid-Sn salt was produced and it was executed using a binder of the epoxy resin, the hardening agent and the organic acid metal salt. In the Table, a circle indicates curing; a triangle indicates semi-curing; and a cross indicates uncured.

(23) TABLE-US-00002 TABLE 2 Executed Comparison Comparison Example 3 Example 3 Example 4 Molar ratio of Epoxy Resin: 1:2 1:2 No Hardening Agent Hardening Agent Organic Acid Metal salt 2 2 Curing Curing Time: X X X Temperature: 3 min 150 degrees C. Curing Time: X X 6 min Curing Time: X X 9 min Curing Time: X X 12 min Curing Curing Time: X X Temperature: 3 min 200 degrees C. Curing Time: X 20 min

(24) As being clearly shown in the comparison example 4, it is understood that when there is no hardening agent even if the same epoxy resin is used, the curing does not advance. This is the same in a case where the curing temperature is 150 degrees C. or in a case where the curing temperature is 200 degrees C. below. In the comparison example 3, a semi-curing was seen when about twenty minutes elapsed at a case of the curing temperature of 200 degrees C. while the epoxy resin and the hardening agent were mixed at a molar ratio of 1:2.

(25) On the other hand, in the executed example 3, a semi-curing was seen when six minutes elapsed at a case of the curing temperature of 150 degrees C. below while the epoxy resin and the hardening agent were mixed at a molar ratio of 1:2 and the organic acid metal salts of 2 weight % was further mixed to this mixture. It completely cured when twelve minutes elapsed. Further, when setting the curing temperature to be 200 degrees C., it completely cured at only three minutes.

(26) Thus, by adding the organic acid metal salts to the mixture of the epoxy resin and the hardening agent with a molar ratio of 1:2, it is possible to accelerate the curing and even when the curing temperature is set to be at a relatively low curing temperature of 200 degrees C., it is also possible to completely cure at around three minutes. This enables the curing to be performed for a short time.

(27) Any flexibility was given to the epoxy resin and a drop impact test was performed to verify drop impact resistance characteristics. The drop impact test was performed as follows.

(28) The prepared electrically conductive adhesive agent was printed onto a substrate for module and LGS having a size of 12 mm*12 mm was mounted thereon to prepare a substrate for verification. Next, this substrate for verification was positioned at a position floated by 10 mm from a pedestal and both ends of this substrate were fixed using a dedicated jig. Under this state, impacts of acceleration of 1500 G were repeatedly given thereto following JEDEC standards. Times until LGA was released from the substrate for module were then measured and they were used as drop times. The samples used in the drop test were limited to only the samples in which the epoxy resin cured and the volume resistivity thereof was order of 10.sup.4 cm. They were tested.

(29) Table 3 is a table showing overall characteristics of the electrically conductive adhesive agent according to the invention. In the table, resins represented as flexible resin indicate the epoxy resins with flexibility, which have flexibility and toughness.

(30) As the epoxy resin of bisphenol A type in this executed example, EPICLON EXA-4816 (made by DIC Corporation) or the like is known. A binder is referred to as a mixture containing thermosetting resin, hardening agent, an organic acid and thixotropic agent.

(31) Further, the thixotropic agent is added to keep a shape when the electrically conductive adhesive agent has been applied to a circuit board and may be any compound that does not become soft nor be melted at heating temperature but gives a thixotropy.

(32) A composition rate of the organic acid and the thixotropic agent in Table 3 is weight % in the binder composition and a composition rate of the binder and the filler is weight % in the electrically conductive adhesive agent. The peak temperature is a peak temperature by the exothermic reaction when the epoxy resin cures based on the DSC measurement.

(33) TABLE-US-00003 TABLE 3 Executed Executed Executed Comparison Comparison Example 4 Example 5 Example 6 Example 5 Example 6 Epoxy Flexible Flexible Standard Flexible Flexible Resin of Resin Resin Resin Resin Resin Bisphenol A Type Molar Ratio 1:2 1:2 1:2 1:1 1:2 of Epoxy Resin: Hardening Agent Organic 4 2 4 4 0 Acid Thixotropic 1 1 1 1 0 Agent Binder: the 12 12 12 12 12 above Mixture Filler: Sn 88 88 88 88 88 powder Volume 2*10.sup.4 8*10.sup.4 3*10.sup.4 1*10.sup.2 Unmeasurable Resistivity (cm) Times until 100 or 100 or 1 Breaking by More More Drop Impact Peak Temp 160 190 162 164 (Degrees C.) Curing after Cured Cured Cured Cured Uncured 3 minutes elapsed at 200 degrees C.

(34) Even when using the flexible resin as the epoxy resin, it cured after the heating was added for three minutes at 200 degrees C. Its volume resistivity was an order of 10.sup.4 cm. In cases of the flexible resin in both of the executed examples 4 and 5, the times until the breaking by the drop impact were 100 times or more. It is thus understood that using the flexible resin is more preferable on the drop impact characteristic than using the standard resin as the epoxy resin in the executed example 6.

(35) By comparing a case in which the molar ratio of the epoxy resin and the hardening agent is a mixture equivalent of mole in the comparison example 5 with a case in which it is 1:2 mixture wherein the hardening agent is much added like the executed example 4, there occurred a difference in the volume resistivity. This is because the epoxy resin cannot perfectly react in the state where the hardening agent is within the mixture equivalent of mole, so that degree of adhesion in Sn powder is deteriorated.

(36) Further, it is determined that, even when the molar ratio is 1:2 like the comparison example 6, any volume resistivity as shown in each of the executed examples 4 through 6 cannot be obtained at all if any organic acid is not included.

(37) Although these executed examples have used Sn powder as the electrically conductive metallic powder, there is a high probability that this invention can be performed in an alloy containing metal other than Sn such as, for example, Sn-1Cu alloy. Accordingly, Table 4 shows a result of test in which it was executed with alloys other than Sn powder. Regarding the binder, the same composition thereof as that of the executed example 4 was used.

(38) In the executed example 10, an ally 1, Sn-3.4ag-0.7Cu-2Bi-5Sb-0.04Ni, was used as the electrically conductive metallic powder. Other alloys used pieces of the electrically conductive metallic powder shown in Table 4. The peak temperature is a peak temperature by the exothermic reaction when the epoxy resin cures based on the DSC measurement.

(39) TABLE-US-00004 TABLE 4 Executed Executed Executed Executed Comparison Executed Example 7 Example 8 Example 9 Example 10 Example 7 Example 8 Electrically Sn3.0Ag0.5Cu Sn5Sb Sn10Sb Alloy 1 Sn30Cu Sn77Cu conductive Metallic Powder Peak Temp 164 156 160 157 165 240 (Degrees C.) Volume 3*10.sup.4 4*10.sup.4 5*10.sup.4 9*10.sup.4 1*10.sup.2 8*10.sup.5 Resistivity (cm)

(40) From the executed examples 7 through 10, it is understood that even when the electrically conductive metallic powder is any of the alloys other than Sn powder, an effect can be obtained. In the comparison example 7, the epoxy resin could start curing at the low temperature but its volume resistivity was 1*10.sup.2 cm which was increased. In the comparison example 8, the epoxy resin did not start curing at 200 degrees C. or less.

(41) The invention contains the electrically conductive metallic powder including Sn, the thermosetting resin, the acid anhydride hardening agent, the organic acid and the thixotropic agent, wherein the electrically conductive metallic powder reacts with the organic acid during the heating process to produce the organic acid metal salts which is the hardening accelerator. Therefore, it is applicable to any electrically conductive joining agent containing the electrically conductive metallic powder including Sn, the thermosetting resin, the acid anhydride hardening agent and the organic acid, without limiting to the above-mentioned electrically conductive adhesive agents. Further, it is also applicable to any joining when any electrical conductivity is required other than an object to join various kinds of electronic circuits onto a circuit board.

INDUSTRIAL APPLICABILITY

(42) This invention is applicable to the joining of the parts by the electrically conductive adhesive agent, the soldering by solder paste containing the thermosetting resin and a joined body, a joint and the like joined by the adhesive agent.