KR100929136B1 - Conductive paste and the manufacturing method thereof and the electric device comprising thereof - Google Patents

Abstract

PURPOSE: A conductive paste is provided to lower manufacturing costs and to ensure excellent electrical conductivity and adhesive force by replacing expensive metal powder with copper powder, or reducing the used amount of metal powder. CONSTITUTION: A conductive paste comprises: metal powder; low-melting-point alloy powder containing at least one selected from the group consisting of Sn/Bi, Sn/In and Sn/Pb; nanopowder containing at least one selected from the group consisting of Ag, Cu, Al, Ni, expanded graphite, carbon nanotube, carbon and grapheme; a first binder including a thermosetting resin; and a second binder including a rosin compound.

Description

A conductive adhesive, a method of manufacturing the same, and an electronic device including the same

The present invention relates to a conductive adhesive, a method of manufacturing the same, and an electronic device including the same. In particular, the present invention relates to a conductive adhesive having excellent electrical conductivity and adhesive strength and low manufacturing cost, and a method of manufacturing the same.

The conductive adhesive bonds the device and the electrode in the semiconductor device when the conductive circuit is formed on the printed circuit board, when the electrode or the integrated circuit (IC) chip is formed in the liquid crystal display (LCD), the plasma display panel (PDP), or the like. In the case of forming an electrode in a solar cell, it is widely used in the process of manufacturing various electronic devices.

Conventional conductive adhesives have been prepared by mainly adding a binder, an organic solvent, an additive, and the like to conductive powders such as gold (Au), silver (Ag), and carbon (C) to be mixed in a paste form. Especially in the field where high conductivity is required, gold powder, silver powder, palladium powder or alloy powder thereof has been mainly used. Among them, the conductive paste containing silver powder has good conductivity and has been mainly used for the formation of wiring layers (conductive layers) such as printed wiring boards and electronic components, or electrical circuits or electrodes of electronic components. When applied, an ion migration phenomenon occurs in an electric circuit or an electrode, which causes a problem in that an electrode or a wiring is shorted at an unwanted portion. In addition, in order to form a conductive adhesive having excellent conduction resistance in general, since silver powder should be included in an amount of about 70 to 90% by weight, the price of the conductive adhesive also increases due to the price of the silver powder. In particular, as the conductive adhesive is used in a variety of electronic devices, the amount of use is rapidly increased, thereby increasing the necessity of lowering the manufacturing cost by replacing the silver powder or reducing the amount of the silver powder. In addition, since the price of gold powder and palladium powder, which are conventionally used in addition to silver powder, is also expensive, a necessity of reducing the amount of use thereof is required.

To this end, attempts have been made to use copper as a conductive filler, which is much less expensive than silver powder. However, when copper is exposed to air, moisture, high temperature, or other oxidizing agents, copper oxide is formed, which causes a problem of sharply decreasing the electrical conductivity of the conductive adhesive.

The technical problem to be achieved by the present invention is to provide a conductive adhesive having excellent conductivity and adhesion, a method of manufacturing the same and a device including the same. In addition, to replace the expensive metal powder contained in the conductive adhesive with copper powder or to reduce the amount of expensive metal powder used to provide a low-cost manufacturing conductive adhesive and excellent electrical conductivity and adhesion.

Conductive adhesive according to the present invention for solving the above technical problem is a metal powder, Sn / Bi, Sn / In and a low melting point alloy powder containing a material selected from the group consisting of Sn / Pb, comprising a thermosetting resin It may include a first binder, and a second binder comprising a rosin compound.

The conductive adhesive according to the present invention for solving the above technical problem is a metal powder, Sn / Bi, Sn / In and Sn / Pb containing at least one material selected from the group consisting of Cu, Ag, Au, Ni and Al Low melting alloy powder containing at least one material selected from the group consisting of, Ag, Cu, Al, Ni, expanded graphite, carbon nanotubes (CNT), carbon, and nano containing at least one material selected from the group consisting of graphene Powder, a first binder comprising a thermosetting resin, and a rosin compound.

Method for producing a conductive adhesive according to the present invention for solving the above technical problem is at least one material selected from the group consisting of cast oil, siloxaneimide, liquid polybutadiene rubber, silica, acrylate hydrogenated in a thermosetting resin and a rosin compound Adding and modifying the mixture, and mixing the thermosetting resin and the rosin compound with a metal powder and a low melting alloy powder containing at least one material selected from the group consisting of Sn / Bi, Sn / In and Sn / Pb. Forming and dispersing the mixture.

An electronic device according to the present invention for solving the above technical problem is a low melting point alloy powder, Ag, Cu, Al containing at least one material selected from the group consisting of metal powder, Sn / Bi, Sn / In and Sn / Pb , Ni, expanded graphite, carbon nanotubes (CNT), carbon, and nano-powder comprising at least one material selected from the group consisting of graphene, a first binder comprising a thermosetting resin, and a second binder comprising a rosin compound It may include a conductive adhesive comprising a.

The conductive adhesive according to the present invention disperses the low melting point alloy powder and the nanopowder between the metal particles to exhibit excellent electrical conductivity and adhesion. In addition, the manufacturing method of the conductive adhesive according to the present invention can replace the expensive metal powder with copper powder or reduce the amount of expensive metal powder used to lower the manufacturing cost. In addition, the electronic device including the conductive adhesive according to the present invention can increase the reliability of the electronic device by using a conductive adhesive excellent in electrical conductivity and adhesion.

Hereinafter, a preferred embodiment of the present invention will be described in detail. The terms “first”, “second”, and the like are only used to distinguish various elements, and the elements of the present invention are not limited to the above terms. The terms are used only for the purpose of distinguishing one component from another. Terms such as "comprises" in the present application are intended to indicate that there is a feature or step described in the specification or a combination thereof, but in advance the possibility of the presence or addition of one or more other features or steps or a combination thereof. It should be understood that it does not exclude. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art.

Conductive adhesive

The conductive adhesive according to one embodiment of the present invention may include a metal powder, a low melting alloy powder, a nano powder, a first binder including a thermosetting resin, and a second binder including a rosin compound.

As the metal powder, each of copper (Cu) powder, silver (Ag) powder, gold (Au) powder, nickel (Ni) powder, and aluminum (Al) powder may be used, or one or more thereof may be mixed. For example, only copper powder may be used as the metal powder, or copper powder and silver powder may be used together.

As the low melting alloy powder, at least one of Sn / Bi, Sn / In, and Sn / Pb is used. That is, one of Sn / Bi, Sn / In, and Sn / Pb may be used, or two or more materials may be mixed and used. Melting | fusing point of the low melting point alloy powder is 138 degreeC-187 degreeC, More preferably, it is 130 degreeC-180 degreeC. The melting point of Sn / Bi is 137 ° C to 138 ° C, the melting point of Sn / Pb is 187 ° C, and the melting point of Sn / In is 148 ° C to 155 ° C. In an embodiment of the present invention, Sn / Bi-based alloy powder may be used, and in particular, it is preferable to use Sn42 / Bi58 which is inexpensive and has a low melting point. Sn42 / Bi58 is Sn 40% by weight, Bi means an alloy containing 58%.

As the nano powder, one or more materials of Ag, Cu, Al, Ni, expanded graphite, carbon nanotubes (CNT), carbon, and graphene may be used. In the present invention, the nanopowder means a fine powder having a particle size smaller than that of a metal powder or a low melting point alloy powder, and the nanopowder means a powder having a particle size of 10 nm to 100 nm. There is a slight difference between the particle sizes inside the powder, but the largest number of particles are distributed or the average particle size can be seen as the particle size of the powder.

The copper powder, the low melting point alloy powder, and the nanopowder may be spherical or flake shaped and needle shaped. Copper powder, low melting alloy powder, nano powder, etc. are generally spherical, but when each particle is not perfectly spherical, the particle size is defined as the average of the length of the longest line segment and the length of the shortest line segment. If each particle is close to a sphere, the particle size will be close to the diameter value of the sphere.

Copper powders, low melting point alloy powders, and nanopowders serve as conductive fillers, and there is no limitation on the particle size of each, but each particle size is a particle of a metal powder ≥ a particle of a low melting alloy powder ≥ a particle of a nano powder Or particles of low melting point alloy powder ≥ particles of metal powder ≥ particles of nanopowder, and having a relationship of particle size of copper powder ≥ particle size of low melting point alloy powder ≥ particle size of nano powder desirable.

The low melting point alloy powder, which has a smaller particle size than the copper particles, is dispersed between the copper particles, melted and liquefied at low temperature (for example, 138), and then permeates between the pores between the copper particles to bond the copper particles to each other. It is because adhesive force can be improved. In addition, since the low melting alloy powder may be thermally cured in a short time and may not sufficiently penetrate between the pores of the copper particles, the nano powder having a smaller particle size than the copper particles or the low melting alloy particles fills the remaining voids between the copper particles. Humidity and oxygen in the outside can be pushed out to suppress the corrosion of metal powder and the deterioration of polymer, and to increase the adhesion and electrical conductivity.

In the conductive adhesive according to an embodiment of the present invention, the particle size of the copper powder may be 0.05 μm to 10 μm, and more preferably 0.1 μm. If the particle size of the copper powder is 0.05μm or less, the dispersibility is not good, and if the particle size is 10μm or more, the porosity is increased to reduce the contact point between the particles, thereby lowering the electrical conductivity. In addition, the particle size of the low melting point alloy powder may be 0.05μm ~ 10μm, more preferably 0.1μm, the particle size of the nanopowder may be 10nm ~ 100nm, more preferably 50nm. Nano powder is smaller in particle size than copper powder and low melting powder.

As the first binder, a thermosetting resin is used. Thermosetting resins include epoxy resins, phenolics, melamine resins, urea resins, unsaturated polyester resins, unsaturated polyesters, silicones, and polyurethanes One or more materials of polyurethane, allyl resin and thermosetting acrylic resin, phenol-melamine polycondensation resin, urea melamine polycondensation resin may be used. Thermosetting resins play the most important role in improving conductivity by minimizing the gap between copper powders with strong adhesion.

As the second binder, a rosin compound is used. Rosin compounds include gum rosin, rosin esters, polymerized rosin esters, hydrogenated rosin esters, disproportionated rosin esters, and dibasic acid denatured. One or more of the materials may be used as the dibasic acid modified rosin esters, the phenol-modified rosin esters, the phthalene phenol copolymer resin, the maleic acid modified resin and the acrylic modified hydrogenated resin. Rosin is a natural resin obtained by distilling rosin. It contains abiotic acid as a main component and contains resinous acids such as neo-abietic acid, repopimaric acid, hydroavietic acid, pimaric acid and dextonic acid. Means. The rosin compound is mixed with an active agent and used as a flux to activate soldering of low melting alloy powder. Rosin compounds also improve wettability.

When the conductive adhesive according to an embodiment of the present invention is applied to the contact surface and then thermally cured, the low melting alloy powder is first melted at a low temperature (138 ° C. to 187 ° C.) to change into a liquid phase. Primary soldering occurs while being distributed between the pores of the face and the copper powder. Thereafter, shrinkage is achieved by secondary curing of the thermosetting resin at 150 ° C to 200 ° C. As a result, adhesiveness may be increased and may exhibit stronger adhesive force than conventional conductive adhesives. Meanwhile, as the low melting point alloy powder is melted for a short time, the conductive filler may not have sufficient fluidity and thus the conductivity of the conductive filler may be deteriorated. Thus, the nanopowder is further dispersed between the copper particles. As a result, the nano-powder fills the pores between the copper powder and the low-temperature alloy powder, acting as a bridge, thereby minimizing resistance and increasing electrical conductivity.

In addition, solvents, hardeners, activators, rust inhibitors, reducing agents, thixotropic agents and thickeners may be used as additives.

As the solvent, at least one of glycidyl ethers (GLYCIDYL ETHERS), glycol ethers (GLYCOL ETHERS), and alpha-terpineol may be used.

As the curing agent, an aliphatic amine curing agent (epoxy curing agent), an acid anhydride curing agent, an amide curing agent, an idasol curing agent, a latent curing agent or the like can be used. In particular, latent curing agents such as dicyandiamide, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea), 2 -Phenyl-4-methyl-5-hydroxymethylimidazole, amine adduct-based compound, dihydride compound, onium salt (sulfonium salt, phosphonium salt, etc.), biphenyl ether blockcarboxylic acid, polycarboxylic acid Active esters can be used. The latent curing agent is a curing accelerator which accelerates the curing of the curing agent, and can be adjusted when added to lower the curing temperature.

Active agents include succinic acid, ADIPIC ACID, palmitic acid, PALMITIC ACID, 3-boron fluoride ethyl amide complex, butyl amine hydrobromide, butyl amine hydrochloride, ethyl amine hydrobromide, pyridine Hydrobromide, cyclohexyl amine hydrobromide, ethyl amine hydrochloride, 1,3-diphenyl guanidine hydrobromide, 2,2-bis hydroxymethyl propionate, 2,3-dibromo-1- At least one material of the propanol may be used. Activators play a role in activating and functioning rosin's abies acid. The main component of rosin, abiate, helps low-melting alloy powder to melt and easily change into a liquid phase.Allows the oxide film formed on the copper plate on the substrate surface of the electronic device to be removed (cleaned) with almost no tolerance. Ensure good bonding to the substrate side of the substrate. However, when the content of additives such as the first binder and the copper powder is increased in addition to the low melting point alloy powder in the conductive adhesive, such an function is inhibited, the activator assists and activates the function of the above-mentioned abienic acid.

As a rust inhibitor, at least one or more of an amine rust inhibitor and an ammonium rust inhibitor may be used. The anti-rusting agent is evaporated slowly at 100 ℃ or higher to remove humidity and oxygen when moisture and oxygen present in the solvent are evaporated during the heat curing and moisture and oxygen existing between air humidity and metal powder pores are released. Complex compounds are formed outside the metal powder to prevent corrosion of the metal powder.

As the reducing agent, hydrazine-based and aldehyde-based reducing agents may be used. The reducing agent serves to reduce electrical conductivity by reducing it when the conductive metal is oxidized. Hydrazine-based reducing agents include hydrazine, hydrazine hydrate, hydrazine sulfate, hydrazine carbonate and hydrazine hydrochloride.

And aldehyde-based reducing agents include formaldehyde, acetaldehyde, propion aldehyde.

Thixotropic agents are intended to improve printability, which can increase wettability, wettability and thixotropy so that the adhesive can be applied smoothly and quickly hardened. Thixotropic agents include hydrogenated cast wax, polyamide wax, polyolefin wax, dimer acid, monomeric acid, polyester modified polydimethylsiloxane, polyamineamide carboxylate, carnauba wax (CARNAUBA WAX), colloidal silica, bentonite clay Can be used. Thickeners may be used to increase the viscosity. Examples of the thickeners include ETHYL CELLULOSE and HYDROPROPYL CELLULOSE. On the other hand, the resistance value required for the low voltage adhesive and the high voltage adhesive are different. For example, low-voltage conductive adhesives are used for bonding semiconductor chips and require sheet resistance of 100mΩ ~ 1000m 주로 and are primarily important for adhesion. High-voltage conductive adhesives require sheet resistance of less than 50mΩ and are more important for electrical properties than adhesion. In order to control this, the content of copper powder, low melting point alloy powder, and nano powder can be appropriately adjusted. In addition, nano powder may be added or omitted as necessary.

In the conductive adhesive according to an embodiment of the present invention, the metal powder is preferably 30 to 85% by weight, 5 to 50% by weight of the low melting point alloy powder, and 3 to 13% by weight of the nanopowder. It is preferable that the organic compound including the second binder and the additive is included in an amount of 7 to 15% by weight. However, this is only one embodiment and does not limit the scope of the invention.

As another example, 61.6 wt% of the copper powder, 26.4 wt% of the low melting point powder, 0 wt% of the nanopowder, 1.25 wt% of the first binder, and 0.63 wt% of the second binder may be included in the entire conductive adhesive. Silver additives may be included. On the other hand, when the amount of copper powder is increased, the amount of the first binder is also increased, and when the amount of copper powder is decreased, the amount of the first binder is also reduced and the amount of the second binder is preferably increased.

The conductive adhesive according to another embodiment of the present invention includes a metal powder, a low melting alloy powder, a nano powder as the conductive filler, and may include only copper powder as the metal powder. In addition, the first binder, the second binder, and other additives may be included in the same or similar to the above-described embodiment, and the nano powder may be added or omitted as necessary.

The conductive adhesive according to another embodiment of the present invention may include copper powder as a metal powder, and may include silver nanopowder together. At this time, the particle size of the copper powder is 0.05μm ~ 10μm, the particle size of the silver nanopowder is preferably 20nm ~ 100nm. In addition, it is preferable to include 50 to 90% by weight of the copper powder and 5 to 20% by weight of the silver nanopowder in the entire conductive adhesive. Meanwhile, the first binder, the second binder, and other additives may be used similarly or the same as in the above-described embodiment, and the nano powder may be added or omitted as necessary.

In addition, in the case of the conductive adhesive according to another embodiment of the present invention, only the silver powder may be used as the metal powder. At this time, the particle size of the silver powder is 0.05μm ~ 10μm, the particle size of the low melting point alloy powder is preferably 0.05μm ~ 10μm. In addition, it is preferable to contain 30 to 80 weight% of silver powder and 15 to 50 weight% of low melting-point alloy powder among all the conductive adhesives. At this time, the conductive adhesive made of silver powder and low melting point alloy powder has better electrical conductivity and adhesion than the silver powder conductive adhesive, and the low melting point alloy powder is 100 times cheaper than silver (Ag), thereby reducing cost. Excellent performance and the first binder, the second binder, and other additives can be used similarly or identically to the above-described embodiment, and the nano powder can be added or omitted as necessary.

Preparation of Conductive Adhesive and Evaluation of Physical Properties

Next, although the conductive adhesive of this invention is demonstrated in detail with reference to the following Example and a comparative example, this does not limit or limit this invention in any form.

Example 1 Preparation of Conductive Adhesive for IC Chip Bonding

Phenolic novolacs having a molecular weight of 150 or more and a boiling point of 69.58% or more by weight of glycidyl ether or glycol ether are used as solvents, and have an EEW (epoxy equivalent weight) of 170 to 190 (g / eq) as the first binder. 10.40% by weight of epoxy (Phenol Novolac Epoxy Rosen) and 5.30% by weight of hydrogenated rosin (hydrogenated rosin) with a second binder were dissolved with stirring at less than 100 ° C, followed by 3 or 4-methyl-1, 5% by weight of 2,3,6-tetrahydrophthalic anhydride (3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride) and 1.15% by weight of latent curing agent DICYANDIAMIDE at 80 ° C or higher Stir and dissolve. Thereafter, 0.10% by weight of ethylamine hydrobromide, 0.17% by weight of butylamine hydrochloride and 3.80% by weight of adipic acid were heated and stirred at 100 ° C to dissolve as a activator to prepare a flux. 1.5 wt% triethanolamine (TEA) as a stabilizer, 0.5 wt% azole-based vaporizable rust preventive agent and 0.5 wt% reducing agent hydrazine were added to the prepared flux, stirred and dissolved with warming at 80 ° C., followed by thixotropic agent and As a thickener, 1.5 wt% of hydrogenated cast wax and 0.5 wt% of polyester-modified polydimethylsiloxane were added to adjust the viscosity to prepare a composite.

100 g of the finished compound was mixed with 513.33 g of copper powder (1 to 3 μm) and 220 g (1 to 5 μm) of SnBi powder, stirred and degassed, and dispersed in a 3-roll mill (roll gap 5 μm) to prepare a conductive adhesive.

Example 2 Preparation of Conductive Adhesive for Through Hole Filling

Diglycidyl ether of bisphenol A having EEW of 184 to 190 (g / eq) as the first binder using 47.68% by weight of a substance having a molecular weight of 150 or higher and a boiling point of 200 ° C or higher as a solvent in glycidyl ether or glycol ethers (diglycidyl ether of bisphenol-A) 13.38% by weight and 10.39% by weight of hydrogenated rosin (hydrogenated rosin) with a second binder with agitation and dissolution at below 100 ° C, and then a phenol-melamine polycondensation resin as a third binder and curing agent 10.00% by weight of acid anhydride-based curing agent and 5% by weight of 3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride (3 or 4-methyl-1,2,3,6-tetrahydrophthalic anhydride)

As a curing accelerator, 1.15 wt% of 2,4,6-tri (dimethylaminomethyl) phenol (2,4,6-tris (dimethylaminomethyl) phenol), which is a tertiary amine curing agent, is dissolved while stirring at less than 100 ° C. Thereafter, 0.15% by weight of ethylamine hydrobromide, 0.25% by weight of butylamine hydrochloride, and 4.50% by weight of adipic acid are heated and stirred at 100 ° C. as a activator to prepare a solvent. 2.5 wt% of triethanolamine (TEA) as a stabilizer, 0.5 wt% of an azole vaporizable rust preventive agent as a rust preventive agent, and 0.5 wt% of hydrazine as a reducing agent were added to the solvent, and stirred and dissolved while warming at 150 ° C. As a thickener, 2.5 wt% of hydrogenated cast wax and 1.5 wt% of polyester-modified polydimethylsiloxane were added to adjust the viscosity to prepare a composite. 373.33 g of copper powder (1 to 3 μm), 350 g (1 to 5 μm) of SnBi powder, and 70 g of silver nanopowder (0.1 μm) were mixed with 100 g of the finished compound, and then stirred and degassed by 3-Roll Mill ( A conductive adhesive was prepared by dispersing in a roll gap of 5 m).

Example 3 Preparation of Conductive Adhesive for EMI

After modifying 33.38% by weight of a high performance epoxy resin having a EEW of 190 to 220 (g / eq) as a binder to 5% by weight of hydrogenated cast wax, a substance having a molecular weight of 150 or more and a boiling point of 200 ° C or more in glycidyl ether or glycol ethers Was dissolved at less than 80 DEG C using 48.47% by weight of a solvent, and then 3% by weight of DICYANDIAMIDE was added as a curing agent, and 3- (3,4-dichlorophenyl) -1,1- was used as a curing accelerator. 1.15% by weight of dimethylurea (3- (3,4-dichlrophenyl) -1,1-dimethylurea) is added, and 1.00% by weight of polyoxyethylene sorbitan monooleate is added as a dispersant, followed by less than 80 ° C. Dissolve while stirring at. Thereafter, 2.5% by weight of triethanolamine (TEA) as a stabilizer, 1.50% by weight of an azole-based vaporizable rust preventive agent as a rust preventive agent, and 1.00% by weight of hydrazine as a reducing agent were added thereto, and stirred to dissolve while warming at 100 ° C. Next, 1.5% by weight of polyester-modified polydimethylsiloxane and 1.5% by weight of polyester-modified polydimethylsiloxane were added as a thixotropic agent and a thickener to prepare a composite.

100 g of the finished compound was mixed with 723.33 g of copper powder (1 to 3 μm) and 70 g of silver nano powder (0.1 μm) as a filler, followed by stirring and defoaming, and then dispersed in a 3-roll mill (roll gap 5 μm) to form a conductive adhesive. Was prepared.

Comparative Example 1 Conventional Conductive Adhesive

A commercially available silver conductive adhesive (manufactured by Ablestik, product name: ABLEBOND 8390) was prepared.

Comparative Example 2 Conventional Conductive Adhesive

A commercially available silver conductive adhesive (manufactured by Mitsui Corporation, product name: MSP-812B) was prepared.

Experimental Example 1 Evaluation of Conductive Adhesive (IC Chip Bonding)

The adhesive of Comparative Example 1 and the adhesive of Example 1 were applied onto an IC chip using a dispenser-type mounting machine, and then cured at 175 ° C. for 15 minutes using an oven. After that, the viscosity, bond strength, sheet resistance, and hardness were measured, and whether there was a change in resistance in the low temperature high temperature shock test (TC) and the constant temperature and humidity deflection test (THB) was measured. Table 1 shows the test items and the test results. Referring to Table 1, the adhesive of Example 1 exhibits characteristics that meet the requirements or are close to the requirements in viscosity, bond strength, sheet resistance, hardness, low temperature high temperature shock test (TC), and constant temperature and humidity deflection test (THB) results. It can be seen that. In particular, the adhesive of Example 1 exhibits better properties than the adhesive of Comparative Example 1 in viscosity and bonding strength.

Item Comparative Example 1 Example 1 Requirements standard How to measure equipment Viscosity / T.I 55kcps /0.55 65kcps /0.60 60 ± 10kcps /0.5~0.6  25 ℃, 5rpm (JIS Z 3284) Brookfield HBDV2 + pro Bonding strength  25 N / ㎡ 38 N / ㎡ 20 N / ㎡ KS M 3721 1605 HTP Aikoh High temperature low temperature impact test (TC) No resistance change No resistance change No resistance change -65 ℃ 30 minutes ↔ 10 minutes ↔150 ℃ 30 minutes / 1,000 times (JIS C 0027) T / C Equipment Temperature-Humidity bias test (THB) No resistance change No resistance change No resistance change 85 ℃ / 85% 3.6V 1,000hr (JIS C0022) Constant temperature and humidity Sheet resistance 450mΩ 320mΩ 400mΩ 4-pole sheet resistance measurement Low resistance meter Hardness 28 HVI 36 HVI 25 ~ 35 HVI Advanced frictionless loading shaft mechanism Vickers Hardness Tester HVS-50 5-2900HVI

Experimental Example 2 Conductive Adhesive Evaluation Items (for Through Hole Filling)

The adhesive of Comparative Example 2 and the adhesive of Example 2 were applied on a printed circuit board (PCB) using a metal mask in a screen manner and then cured in an oven. After that, viscosity, bond strength, sheet resistance, and hardness were measured, and whether the resistance change was measured in the thermal shock test, the cold heat circulation (TC) test, the constant temperature and humidity deflection test (THB), and the like. Table 2 shows the test items and the test results. Referring to Table 2, it can be seen that the adhesive of Example 2 exhibits characteristics satisfying or close to the requirements in viscosity, bonding strength, sheet resistance, hardness, TC test, and constant temperature and humidity deflection test (THB) results. . In particular, the adhesive of Example 2 exhibits better properties than the adhesive of Comparative Example 2 in viscosity, bonding strength and hardness.

Item Comparative Example 2 Example 2 Requirements standard How to measure equipment Viscosity / Thyso (T.I)  273kcps /0.60  320kcps /0.65 350 ± 50kcps /0.6~0.7 25 ℃, 10rpm (JIS Z 3284) Brookfield HBDV2 + pro Bonding strength 15 N / ㎡ 20N / ㎡ 15N / ㎡ KS M 3721 1605 HTP Aikoh Thermal Shock Test Cold Heat Circulation No resistance change No resistance change No resistance change -65 ℃ 30 minutes ↔ 10 minutes ↔150 ℃ 30 minutes / 1,000 times (JIS C 0027) T / C Equipment Temperature-Humidity bias test (THB) No resistance change No resistance change No resistance change 85 ℃ / 85% 3.6V 1,000hr (JIS C0022) Constant temperature and humidity Sheet resistance  7mΩ  12mΩ 10 mΩ ± 3 4-pole sheet resistance measurement (HIOKI 3541) Low resistance meter Hardness 55HVI 36 HVI 45HVI Advanced frictionless loading shaft mechanism Vickers Hardness Tester HVS-50 5-2900HVI Curing condition 185 ° C / 40 minutes 185 ° C / 40 minutes  170 ° C / 20 minutes Hot air 2-stage curing (1st 80 ℃, 2nd 185 ℃) Oven

Experimental Example 3 Conductive Adhesive Evaluation Items (for EMI)

Evaluation of the physical properties of the conductive adhesive prepared in Example 3 showed a viscosity of 400Kcps (Brookfield 25 degrees, 10 PPM), thixotropy 6.8cp, sheet resistance 850mΩ, which can be used for EMI.

Manufacturing method of conductive adhesive

Hereinafter, a method of manufacturing a conductive adhesive according to an embodiment of the present invention will be described with reference to FIG. 1. 1 is a schematic block diagram showing a method of manufacturing a conductive adhesive according to an embodiment of the present invention. 1, the method of manufacturing a conductive adhesive according to an embodiment of the present invention is a step of mixing a solvent, a binder and an additive (S11), mixing-stirring a filler and then defoaming (S12), the mixture Dispersing and defoaming in the 3-Roll Mill (S13) and the step of inspecting and packaging the prepared conductive adhesive (S14).

In step S11, the thermosetting resin and the rosin are dissolved in a solvent, a modifier, a thixotropic agent, an activator, a rust inhibitor, and the like are added to form an organic compound, and then the temperature is lowered to room temperature and aged. In particular, the thermosetting resin and the rosin compound have weak toughness, so that the joint surface may be broken due to a strong impact, and the parts may be shorted. It is desirable to modify. In the S12 process, a metal powder, a low melting alloy powder, and a nano powder, which are fillers, are mixed in a stirrer and degassed. Thereafter, in the S13 process, the material mixed in the stirrer is dispersed in the 3-roll mill. Finally, in the S14 process, the manufactured conductive adhesive is packaged after the performance test and the factory inspection.

Copper, silver or a mixture of copper and silver may be used as the metal powder in the method for producing a conductive adhesive according to an embodiment of the present invention, and the particle size of the metal powder is preferably 0.05 μm to 10 μm. The particle size of the low melting point alloy powder is preferably 0.05 μm to 10 μm, and as the low melting point alloy powder, one or more of Sn / Bi, Sn / In, and Sn / Pb is used. Sn42 / Bi58 alloy powder may be used in the manufacturing method of the conductive adhesive according to an embodiment of the present invention. As the nanopowder, at least one material selected from the group consisting of Ag, Cu, Al, Ni, expanded graphite, carbon nanotubes (CNT), carbon, and graphene may be used, and the particle size of the nanopowder is 10 nm to 100 nm. Is preferably.

Epoxy resin, phenolics, melamine resin, urea resin, unsaturated polyester resin as a thermosetting resin in the conductive adhesive manufacturing method according to an embodiment of the present invention One or more materials of unsaturated polyester, silicone, polyurethane, allyl resin and thermosetting acrylic resin, phenol-melamine polycondensation resin, urea melamine polycondensation resin may be used. Also, rosin compounds include gum rosin, rosin esters, polymerized rosin esters, hydrogenated rosin esters, disproportionated rosin esters, and dibasic acid denatured. One or more of the materials may be used as the dibasic acid modified rosin esters, the phenol-modified rosin esters, the phthalene phenol copolymer resin, the maleic acid modified resin and the acrylic modified hydrogenated resin.

In addition, the manufacturing method of the conductive adhesive according to an embodiment of the present invention includes the steps of adding together or separately a polyhydric alcohol solvent, a curing agent, an activator, a rust inhibitor, a reducing agent, a thixotropic agent, a thickener, etc. as necessary. It may further include.

Electronic device

The conductive adhesive prepared as described above includes semiconductor through hole bonding, formation of plasma display panel electrodes, formation of semiconductor elements on electrodes, formation of driving chips on liquid crystal displays, formation of solar cell electrodes, and indium tin oxide. (ITO) can be used in a variety of electronic devices, such as electrode replacement, bonding for printed circuit boards. 2 is a cross-sectional view illustrating a semiconductor device including a conductive adhesive according to one embodiment of the present invention. 2, a semiconductor device 100 according to an embodiment of the present invention includes a substrate 110, an electrode 120 formed on the substrate 110, a conductive adhesive 130, and a semiconductor device 140. . In the semiconductor device 100 according to an embodiment of the present invention, the conductive adhesive 130 bonds the electrode 120 and the semiconductor element 140, and electrically connects the semiconductor device 100 to perform a function. . The conductive adhesive 130 may be coated on the electrode 120, which is a bonding surface, and then cured to bond the electrode 120 to the semiconductor device 140. As the coating method, methods such as screen printing, spraying, dipping, and dispenser may be mainly used. Although the semiconductor device has been described as an example, the scope of the present invention is not limited to the semiconductor device but corresponds to an electronic device including the conductive adhesive according to the present invention.

So far I looked at the center of the preferred embodiment for the present invention. Those skilled in the art will appreciate that the present invention can be implemented in a modified form without departing from the essential features of the present invention. Therefore, the disclosed embodiments should be considered in descriptive sense only and not for purposes of limitation. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.

1 is a schematic block diagram showing a method of manufacturing a conductive adhesive according to an embodiment of the present invention,

2 is a cross-sectional view illustrating a semiconductor device including a conductive adhesive according to one embodiment of the present invention.

Claims (20)

Metal powder; Low melting point alloy powder comprising at least one material selected from the group consisting of Sn / Bi, Sn / In and Sn / Pb; Nano powder comprising at least one material selected from the group consisting of Ag, Cu, Al, Ni, expanded graphite, carbon nanotubes (CNT), carbon, and graphene; A first binder comprising a thermosetting resin; And A conductive adhesive comprising a second binder comprising a rosin compound. The conductive adhesive of claim 1, wherein the metal powder comprises at least one material selected from the group consisting of Cu, Ag, Au, Ni, and Al. The method of claim 1, wherein the first binder is an epoxy resin, a phenolics, a melamine resin, a urea resin, an unsaturated polyester resin, or a silicone. (silicon), polyurethane (allyurethane), allyl resin (allyl resin), thermosetting acrylic resin, phenol-meramine condensation polymerization resin, urea-melamine polycondensation resin comprising at least one material selected from the group consisting of glue. The method of claim 1, wherein the second binder is gum rosin, rosin esters, polymerized rosin esters, hydrogenated rosin esters, disproportionated rosin esters At least one selected from the group consisting of Rosin Esters, Dibasic Acid Modified Rosin Esters, Phenolic Modified Rosin Esters, Talphene Phenolic Copolymers, Maleic Acid Modified Resins, and Acrylic Modified Hydrogenated Resins A conductive adhesive comprising a material. The conductive adhesive of claim 1, wherein the conductive adhesive further comprises a rust preventive agent, and the rust preventive agent comprises an amine compound or an ammonium compound. delete  The particle size of the metal powder, the low melting alloy powder and the nano-injection is a particle of the metal powder ≥ particles of the low melting alloy powder ≥ particles of the nano powder, or particles of the low melting alloy powder ≥ metal Conductive adhesive consisting of particles of powder ≥ nano powder particles. The conductive adhesive of claim 1, wherein the metal powder is 30 to 85 wt%, the low melting point alloy powder is 5 to 50 wt%, and the nano powder is 3 to 13 wt%. The conductive adhesive of claim 1, wherein the metal powder is made of only copper powder. delete delete delete delete delete delete delete delete Modifying the thermosetting resin and the rosin compound by adding one or more substances selected from the group consisting of hydrogenated cast oil, siloxaneimide, liquid polybutadiene rubber, silica, and acrylate; The thermosetting resin and the rosin compound include a metal powder, a low melting point alloy powder including at least one material selected from the group consisting of Sn / Bi, Sn / In, and Sn / Pb, particle size of 10 nm to 100 nm, and Ag Mixing nano powders including at least one material selected from the group consisting of Cu, Al, Ni, expanded graphite, carbon nanotubes (CNT), carbon, and graphene to form a mixture; And Dispersing said mixture. delete Metal powder; Low melting point alloy powder comprising at least one material selected from the group consisting of Sn / Bi, Sn / In and Sn / Pb; Nano powder comprising at least one material selected from the group consisting of Ag, Cu, Al, Ni, expanded graphite, carbon nanotubes (CNT), carbon, and graphene; A first binder comprising a thermosetting resin; And An electronic device comprising a conductive adhesive comprising a second binder comprising a rosin compound.

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