KR102055334B1 - Adhesive resin, self-assembled conductive bonding paste comprising the same and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an adhesive resin, a self-sealing conductive connection paste including the same, and a method for manufacturing the same, and more particularly, excellent adhesive strength, low connection resistance, and excellent printability, insulation, and self-adhesion property. The present invention relates to an adhesive resin, a self-sealing conductive connection paste including the same, and a manufacturing method thereof.

Description

Adhesive resin, self-bonding conductive connection paste comprising the same and a method for manufacturing the same {Adhesive resin, self-assembled conductive bonding paste comprising the same and manufacturing method

The present invention relates to an adhesive resin, a self-sealing conductive connection paste including the same, and a method for manufacturing the same, and more particularly, not only has excellent adhesive strength, but also has low connection resistance and excellent printability, insulation, and self-adhesion property. The present invention relates to an adhesive resin, a self-sealing conductive connection paste including the same, and a method of manufacturing the same.

In general, the conductive adhesive may be classified into an anisotropic conductive adhesive and an isotropic conductive adhesive. In particular, an anisotropic conductive film made of an anisotropic conductive adhesive component may be used for electronic components such as semiconductors, for example, flat panel display devices such as LCD, PDP, and EL. Used for mounting. The anisotropic conductive film contains an adhesive component that is cured by conductive powder and heat, and is mainly used for electrical connection of LCD panels, TCP, or PCBs and TCP.

Such anisotropic conductive adhesive films (ACFs) are useful as one of wiring devices and serve as connection members. Specifically, referring to FIG. 1, an anisotropic conductive film (ACF) will be described as an anisotropic conductive film composed of a metal, graphite or similar conductive particles dispersed in a sufficient amount in an adhesive resin and this resin. The anisotropic conductive film is placed between a plurality of circuit members (FPC, IC, ITO Glass, CPT, LCD panel, etc.) to be connected, and a process of applying heat and pressure is performed. And some of the conductive particles included in the anisotropic conductive film by pressure are formed in the electrode portions of the plurality of circuit members to generate an electrical connection between the circuit members. Cured to bond a plurality of circuit members. In the vertical direction of the direction in which pressure is applied, conductive particles are distracted from each other to maintain electrical insulation.

As such, anisotropic conductive films have disadvantages such as unstable and high connection resistance, low bonding strength, and ion migration due to relatively low conductivity because only specific contacts are in physical contact. In addition, the conductive particles used in the technology has a disadvantage that the quality control is difficult and expensive because a separate noble metal plating treatment and insulation treatment is required for a polymer elastic ball of uniform size below the required pitch.

In addition, a contact method using an anisotropic conductive film requires a separate expensive facility for contact, and the pressure is applied in addition to the temperature and time, there is a risk of damaging the circuit board or electronic components to be deposited. have.

Accordingly, there is a need for a conductive adhesive that can not only make electrical connection between circuit members, but also improve adhesion between adherends, reduce connection resistance, and eliminate pressure damage between components without additional expensive equipment.

Korean Laid-Open Patent No. 2012-0122943 (Published Date: 2012.11.07)

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and is intended to provide electrical connection between circuit members (circuit boards, semiconductor chips, ITO Class, terminal parts of plastic element boards, etc.) through contact conduction by molten metal without applying pressure. In addition to providing a good adhesive strength between the adherends, low connection resistance, excellent printability, insulation and self-adhesive adhesive resin, self-sealing conductive connection paste comprising the same and a method for manufacturing the same There is this.

In order to solve the above problems, the adhesive resin of the present invention may include a rubber modified epoxy resin and a bisphenol A type epoxy resin, and the rubber modified epoxy resin and the bisphenol A type epoxy resin may be included in a weight ratio of 1: 1.86 to 2.8. have.

At this time, the adhesive resin can be used for self-sealing conductive connection paste.

In one preferred embodiment of the present invention, the adhesive resin may be an epoxy equivalent of 230 ~ 250 g / eq.

As a preferred embodiment of the present invention, the adhesive resin may have a viscosity of 80 ~ 3,300 mPas at 60 ~ 120 ℃.

As a preferred embodiment of the present invention, the adhesive resin may have a number average molecular weight (Mn) of 361 ~ 543, a weight average molecular weight (Mw) of 2733 ~ 4100.

In one preferred embodiment of the present invention, the rubber modified epoxy resin may have a number average molecular weight (Mn) of 702 ~ 1054, a weight average molecular weight (Mw) of 12002 ~ 18004.

As a preferred embodiment of the present invention, the bisphenol A epoxy resin may have a number average molecular weight (Mn) of 278 to 418, a weight average molecular weight (Mw) of 348 to 524.

In a preferred embodiment of the present invention, the rubber of the modified epoxy resin may include at least one of carboxylic terminated butadiene acrylonitrile (CTBN), nitrile butadiene rubber (NBR), acrylic rubber and silicone (silicone) have.

As a preferred embodiment of the present invention, the epoxy resin of the rubber-modified epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, naphthalene epoxy resin, and dicyclo It may contain one or more of pentadiene (DCPD) type epoxy resin.

On the other hand, the self-sealing conductive connection paste of the present invention contains the above-mentioned adhesive resin, conductive particles, a reducing agent and a solvent.

As a preferred embodiment of the present invention, with respect to 100 parts by weight of the adhesive resin, may include 567 ~ 851 parts by weight of the conductive particles, 80 to 120 parts by weight of the reducing agent and 23 to 36 parts by weight of the solvent.

In one preferred embodiment of the present invention, the conductive particles are bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel ( Ni) and one or more selected from these alloys.

In one preferred embodiment of the present invention, the conductive particles are an alloy of bismuth (Bi) and tin (Sn), and may include bismuth and tin in a weight ratio of 1: 0.57 to 0.87.

In one preferred embodiment of the present invention, the particle diameter of the conductive particles may be 2 ~ 75㎛.

As a preferred embodiment of the present invention, the reducing agent may include one or more selected from rosin-based reducing agents, organic acid reducing agents, metallic reducing agents and amine salt reducing agents.

The solvent is diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether. diethyl ether) and diethylene glycol methyl ethyl ether.

As a preferred embodiment of the present invention, the self-sealing conductive connection paste of the present invention may have an adhesive force of 2 to 5 kgf / cm, adhesion resistance of 0.001 ~ 1 Ω / cm at a temperature of 150 ~ 180 ℃.

As a preferred embodiment of the present invention, the self-sealing conductive connection paste of the present invention may have a viscosity of 30 to 3,000 mPa · s at a temperature of 100 to 180 ° C.

As a preferred embodiment of the present invention, the self-sealing conductive connection paste of the present invention may bond one or more selected from a circuit board, a semiconductor chip, an ITO glass, or a plastic material substrate.

On the other hand, the method for producing the self-sealing conductive connection paste of the present invention is a first step of preparing a mixture by mixing 80 to 120 parts by weight of the reducing agent and 23 to 36 parts by weight of the solvent with respect to 100 parts by weight of the adhesive resin and the adhesive to the mixture A second step of preparing a self-adhesive conductive connection paste may be included by mixing 567 to 851 parts by weight of the conductive particles with respect to 100 parts by weight of the resin.

The adhesive resin of the present invention, a self-sealing conductive connection paste including the same, and a method of manufacturing the same are used in a circuit member (circuit board, semiconductor chip, ITO class, terminal part of a plastic element substrate) through contact conduction by molten metal without applying pressure. Etc.) not only realize electrical connection, but also excellent adhesion between adherends, low connection resistance, and excellent printability, insulation and self-adhesion.

In addition, according to the present invention, the conductive particles included in the self-sealing conductive connection paste are selectively formed only on the electrode portion of the circuit member, and other than the electrode portion, the conductive particles may be formed of an adhesive resin (including a reducing agent) to protect the electrode portion. It can prevent the circuit damage by external shock.

1 is a view schematically showing a conductive method of the conventional anisotropic conductive film (ACF).
FIG. 2 is a view schematically showing a conduction method of a self-assembled conductive bonding paste of the present invention.
3 is a view showing a preferred specific embodiment of the present invention, in which the self-fusion conductive connection paste of the present invention is heat-treated, whereby conductive particles are agglomerated to the electrode portion of the circuit member, thereby causing electrical conduction between the circuit members.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. The drawings and description are to be regarded as illustrative in nature and not restrictive. Like reference numerals designate like elements throughout the specification.

In the conventional anisotropic conductive film, the conductive particles constituting the film are connected to the upper and lower electrodes to pursue the inter-circuit conduction by physical contact, but since they are physically contacted only through specific contacts, they are unstable and have high connection resistance due to relatively low conductivity. Although it has disadvantages such as low bonding strength and ion migration, the self-sealing conductive connection paste of the present invention includes a specific component in a specific content range, and has excellent self fusion using adhesive properties between metals. The connection resistance, printability and insulation are also excellent.

Specifically, referring to FIG. 2, in the self-assembled conductive bonding paste of the present invention, the conductive particles are melted only by heat treatment without applying pressure, and the molten conductive particles are melted. Has the effect of selectively self-sealing only on the electrode portion of the circuit member (circuit board, semiconductor chip, ITO Class, terminal part of the plastic element substrate, etc.). At this time, there is no conductive particles remaining in the resin composition (Resin), so that the adhesive force is excellent, the connection resistance is low, and the insulation is excellent.

The adhesive resin of the present invention includes a rubber modified epoxy resin and a bisphenol A epoxy resin.

At this time, the rubber-modified epoxy resin and the bisphenol A epoxy resin may be included in a weight ratio of 1: 1.86 to 2.8, preferably 1: 2.1 to 2.57 parts by weight, more preferably 1: 2.21 to 2.45. If the adhesive resin of the present invention includes a rubber-modified epoxy resin and a bisphenol-A epoxy resin in less than 1: 1.86 weight ratio, a problem may occur in that printability is low due to low viscosity, and if it includes more than 1: 2.8 weight ratio, The problem that the time-lapse of the paste containing the adhesive resin of the present invention may deteriorate.

The adhesive resin of the present invention is a substance which is cured by heat treatment to bond a plurality of circuit members, and can be used for self-sealing conductive connection paste.

In addition, the adhesive resin of the present invention may be an epoxy equivalent of 230 ~ 250 g / eq.

In addition, the adhesive resin of the present invention has a viscosity of 80 to 3,300 mPa · s, preferably 80 to 3,000 mPa · s, more preferably 80 to 2,700 mPa · s at 60 to 120 ° C. It may be a resin.

Meanwhile, the adhesive resin of the present invention may have a number average molecular weight (Mn) of 361 to 543, preferably a number average molecular weight (Mn) of 406 to 500, and more preferably a number average molecular weight (Mn) of 429 to 475. have. In addition, the adhesive resin of the present invention may have a weight average molecular weight (Mw) of 2733 to 4100, preferably a weight average molecular weight (Mw) of 3075 to 3760, more preferably a weight average molecular weight (Mw) of 3246 to 3588. have.

The bisphenol A epoxy resin of the present invention is a liquid, which has a number average molecular weight (Mn) of 278 to 418, preferably a number average molecular weight (Mn) of 313 to 383, and more preferably a number average molecular weight (Mn) of 330 to 366. ) In addition, the bisphenol A epoxy resin of the present invention has a weight average molecular weight (Mw) of 348 to 524, preferably a weight average molecular weight (Mw) of 392 to 480, more preferably a weight average molecular weight (Mw) of 414 to 458 It can have If the number average molecular weight of the bisphenol A epoxy resin of the present invention is less than 278, or if the weight average molecular weight is less than 348, the viscosity may be low, causing problems with time of the paste, and the number average molecular weight is greater than 418, or the weight average If the molecular weight exceeds 524, a problem of printability may occur.

The rubber modified epoxy resin of this invention is resin which modified | denatured by rubber reaction to an epoxy resin.

At this time, the epoxy resin of the rubber-modified epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, naphthalene epoxy resin, and dicyclopentadiene (DCPD) type epoxy One or more kinds of resin may be included, Preferably it may contain one or more types of bisphenol A type epoxy resin and bisphenol F type epoxy resin.

In addition, the rubber of the rubber-modified epoxy resin may include at least one of CTBN (Carboxylic terminated butadiene acrylonitrile), NBR (nitrile butadiene rubber), acrylic (acrylic rubber) and silicone (silicone), preferably CTBN (Carboxylic terminated butadiene acrylonitrile).

In addition, when the rubber-modified epoxy resin contains CTBN (Carboxylic terminated butadiene acrylonitrile), the CTBN has a glass transition temperature (Tg) of -50 to -10 ° C, preferably -40 to -20 ° C, more preferably. Is -45 ~ -25 ℃, the number average molecular weight (Mn) may be 2520 to 3780, preferably 2835 to 3465, more preferably 2992 to 3308.

On the other hand, the rubber-modified epoxy resin of the present invention has a number average molecular weight (Mn) of 702 ~ 1054, preferably a number average molecular weight (Mn) of 790 ~ 966, more preferably a number average molecular weight (Mn) of 834 ~ 922 Can have In addition, the rubber-modified epoxy resin of the present invention has a weight average molecular weight (Mw) of 12002 to 18004, preferably a weight average molecular weight (Mw) of 13502 to 16504, more preferably a weight average molecular weight (Mw) of 14252 to 15754. Can have If the number average molecular weight of the rubber-modified epoxy resin of the present invention is less than 702, or if the weight average molecular weight is less than 12002, the viscosity of the paste may be low and there may be a problem that contamination occurs due to the flow of the resin during the process. If the average molecular weight exceeds 1054, or if the weight average molecular weight exceeds 18004, there may be a problem that interferes with the fusion of the conductive particles during the process due to excessive viscosity rise.

On the other hand, the self-sealing conductive connection paste of the present invention contains the above-mentioned adhesive resin, conductive particles, a reducing agent and a solvent.

Conductive particles of the present invention is a material for electrically conducting a plurality of circuit boards, with respect to 100 parts by weight of the adhesive resin, 567 to 851 parts by weight, preferably 638 to 781 parts by weight, more preferably May include 673 to 745 parts by weight.

If the conductive particles contain less than 567 parts by weight with respect to 100 parts by weight of the adhesive resin, there may be a problem that a nonuniform self-fusion is formed or a problem that the electrical properties are lowered, and if it exceeds 851 parts by weight of the electrical The problem of insufficient insulation may occur.

The conductive particles are selected from bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel (Ni), and alloys thereof. It may include at least one species, preferably may include at least one selected from the alloy of bismuth (Bi), tin (Sn) and silver (Ag) and the alloy of bismuth (Bi) and tin (Sn) More preferably, an alloy of bismuth (Bi) and tin (Sn).

As conductive particles, when containing an alloy of bismuth (Bi), tin (Sn) and silver (Ag), 58.2 to 87.4 parts by weight of tin, preferably 65.5 to 80.1 parts by weight, more preferably, based on 100 parts by weight of bismuth. Preferably 69.1 to 76.5 parts by weight. Further, when the conductive particles include an alloy of bismuth (Bi), tin (Sn), and silver (Ag), 0.41 to 0.63 parts by weight of silver, preferably 0.46 to 0.58 parts by weight, based on 100 parts by weight of bismuth, More preferably, it may comprise 0.49 to 0.55 parts by weight.

On the other hand, when the bismuth (Bi) and tin (Sn) alloys are included as the conductive particles, bismuth and tin are 1: 0.57 to 0.87 weight ratio, preferably 1: 0.65 to 0.8 weight ratio, more preferably 1: 0.68. It may be included in a weight ratio of 0.77.

Furthermore, the particle diameter of the electroconductive particle of this invention may be 2-75 micrometers, Preferably it is 5-45 micrometers, More preferably, it may be 10-38 micrometers. If the particle diameter of the conductive particles is less than 2 μm, the reduction of the surface of the oxidized particles may not occur properly due to the increase of the specific surface area, as well as the viscosity of the paste may be very high, thereby making it difficult to apply the coating process. If the thickness is larger than 25 μm, precipitation of the conductive particles may occur during storage and use of the paste, and a problem of uniform self fusion may be difficult.

Next, the reducing agent of the present invention may include 80 to 120 parts by weight, preferably 90 to 110 parts by weight, more preferably 95 to 105 parts by weight based on 100 parts by weight of the adhesive resin.

If the reducing agent contains less than 80 parts by weight with respect to 100 parts by weight of the adhesive resin, there may be a problem in that self-fusion is unstable due to deterioration of the melting of the conductive particles or electrical properties may be deteriorated due to the reduction of the conductive particles. Exceeding the weight part may cause a problem in paste formation or high reactivity, which may result in deterioration of time.

The reducing agent of the present invention may include one or more selected from rosin-based reducing agents, organic acid-based reducing agents, metallic reducing agents and amine salt reducing agents, preferably may include organic acid-based reducing agents, more preferably organic acid-based reducing agents It may include one or more of phosphoric adipic acid (cipic acid) and citric acid (citric acid).

Next, the solvent of the present invention is a material capable of improving the solubility of the adhesive resin, and when the circuit member is applied using the conductive connection paste of the present invention, volatilization is performed at a general process temperature of 160 to 180 ° C. The branch may be a substance.

The solvent of the present invention may include 23 to 36 parts by weight, preferably 26 to 33 parts by weight, and more preferably 28 to 32 parts by weight based on 100 parts by weight of the adhesive resin.

If the solvent contains less than 23 parts by weight based on 100 parts by weight of the adhesive resin, the problem of deterioration of time may occur, and if the solvent is contained more than 36 parts by weight, the problem of deterioration of printability may occur.

The solvent of the present invention is diethylene glycol dimethyl ether (ethylene glycol dimethyl ether), ethylene glycol dimethyl ether (Ethylene glycol dimethyl ether), triethylene glycol dimethyl ether (triethylene glycol dimethyl ether), diethylene glycol diethyl ester ( Diethylene glycol diethyl ether, Diethylene glycol methyl ethyl ether, Diethylene glycol methyl butyl ether, Triethylene glycol methyl butyl ether, Propylene glycol It may include one or more of propylene glycol dimethyl ether, dipropylene glycol dimethyl ether and methyl ethyl ketone, preferably diethylene glycol dimethyl ester (diethylene glycol dimethyl ether), ethylene glycol the In ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether It may include one or more, more preferably may include diethylene glycol dimethyl ether (diethylene glycol dimethyl ether).

Furthermore, the self-sealing conductive connection paste of the present invention has a viscosity of 100,000 to 168,000 mPa · s at room temperature, preferably 15 to 35 ° C, more preferably 20 to 30 ° C, preferably 110,000 to It can have a viscosity of 165,000 mPa · s.

At this time, the self-sealing conductive connection paste of the present invention has a viscosity of 30 to 3,000 mPa · s, preferably 30 to 2,000 mPa · s at a temperature of 100 to 180 ° C., more preferably 30 to 1,500 It may have a viscosity of mPa · s, and if the viscosity is less than 30 mPa · s at a temperature of 100 to 180 ° C., a problem may occur that contamination of an unnecessary portion due to excessive flowability of the adhesive resin occurs at curing temperature, 3,000 When it exceeds mPa * s, self-adhesion property may fall.

The self-sealing conductive connection paste of the present invention has a viscosity of 30 to 3,000 mPa · s, preferably 30 to 2,000 mPa · s, more preferably 30 to 1,500 mPa · s at a temperature of 100 to 180 ° C. If the viscosity is less than 30mPa · s at a temperature of 100 ~ 180 ℃, there may be a problem that the contamination of unnecessary parts due to excessive flow of the adhesive resin at the curing temperature may occur, exceeding 3,000mPa · s If it is, self-adhesion may be lowered.

Specifically, the self-sealing conductive connection paste of the present invention includes a specific component in a specific content range, so that the conductive particles are selectively selected only at the electrode portion of the circuit member (circuit board, semiconductor chip, ITO Class, terminal part of the plastic element substrate, etc.). It may have a viscosity range in which self-fusion may occur so as to be connected and conductive.

This can be confirmed in FIG. 3. Referring to FIG. 3, the self-fusion conductive connection paste 3a of the present invention before curing has the entire distribution of conductive particles, but the self-fusion conductive of the present invention cured through heat treatment. In the connection paste 3b, it can be confirmed that the conductive particles are agglomerated at the electrode portion, and electrical conduction between the circuit members through the electrode is achieved. In addition, as can be seen in Figure 3, the self-sealing conductive connection paste 3b of the present invention cured through heat treatment is composed of an adhesive resin (including a reducing agent) in addition to the electrode portion to protect the electrode portion from external impacts, etc. It is possible to prevent damage to the circuit member due to the impact.

In addition, the self-sealing conductive connection paste of the present invention may have an adhesive force of 2 to 5 kgf / cm, preferably 2.2 to 4 kgf / cm at a temperature of 150 to 180 ° C.

In addition, the self-fusion conductive connection paste of the present invention may have an adhesion resistance of 0.001 ~ 1 Ω / cm at a temperature of 150 ~ 180 ℃.

Meanwhile, the self-fusion conductive connection paste of the present invention may bond one or more selected from a circuit board, a semiconductor chip, an ITO glass, or a plastic material, but is not limited thereto.

Furthermore, the manufacturing method of the self-fusion conductive connection paste of this invention is as follows.

First, a mixture may be prepared by mixing the adhesive resin, the reducing agent and the solvent in the first step. At this time, the mixture may be mixed with 80 to 120 parts by weight of the reducing agent and 23 to 36 parts by weight of the solvent with respect to 100 parts by weight of the adhesive resin.

Next, the self-fusion conductive connection paste may be prepared by mixing the conductive particles and the solvent in the mixture prepared in the first step in the second step. At this time, the electroconductive particle can mix 567-851 weight part with respect to 100 weight part of adhesive resins.

On the other hand, the self-sealing conductive connection paste of the present invention is used to electrically connect a substrate (= circuit member) on which a plurality of circuits are printed. The method for manufacturing a circuit member including such a self-melting conductive connection paste is As follows.

First, a first circuit member having a plurality of first electrodes may be stacked on one surface of the self-fusion conductive connection paste, and a second circuit member having a plurality of second electrodes may be stacked on the other surface thereof to face the first electrode. .

Thereafter, using a heating tool, heating may be performed at 140 to 260 ° C. for 10 seconds to 60 minutes, preferably 30 seconds to 50 minutes, and more preferably 1 minute to 30 minutes. Through such heating, the conductive particles included in the self-fusion conductive connection paste are melted, and the molten particles may be self-fused so that the first electrode and the second electrode are electrically conductive. If the temperature is less than 140 ° C., there may be a problem that the conductive particles are not fused, and when the temperature of the heating tool exceeds 260 ° C., there may be a problem that damage to the component due to heat occurs. The range is good.

The heating tool is not particularly limited as long as it is a means capable of melting conductive particles by applying heat to the connection film of the present invention, and may include, for example, a heating oven or a reflow drying stage.

The present invention has been described above with reference to the embodiments, which are merely exemplary and are not intended to limit the embodiments of the present invention. Those of ordinary skill in the art to which the embodiments of the present invention belong will have the essential characteristics of the present invention. It will be appreciated that various modifications and applications not illustrated above are possible without departing from the scope of the invention. For example, each component specifically shown in the embodiment of the present invention may be modified. And differences relating to such modifications and applications will have to be construed as being included in the scope of the invention defined in the appended claims.

Preparation Example 1 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a bisphenol A epoxy resin (YD128, Kukdo Chemical).

At this time, the rubber modified epoxy resin and the bisphenol-A epoxy resin were mixed in a 1: 2.33 weight ratio.

Preparation Example 2 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a bisphenol A epoxy resin (YD128, Kukdo Chemical).

At this time, the rubber-modified epoxy resin and the bisphenol A epoxy resin were mixed in a 1: 2.1 weight ratio.

Preparation Example 3 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a bisphenol A epoxy resin (YD128, Kukdo Chemical).

At this time, the rubber modified epoxy resin and the bisphenol-A epoxy resin were mixed in a 1: 2.57 weight ratio.

Comparative Preparation Example 1 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a bisphenol A epoxy resin (YD128, Kukdo Chemical).

At this time, the rubber modified epoxy resin and the bisphenol-A epoxy resin were mixed in a weight ratio of 1: 1.63.

Comparative Preparation Example 2 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a bisphenol A epoxy resin (YD128, Kukdo Chemical).

At this time, the rubber modified epoxy resin and the bisphenol-A epoxy resin were mixed at a weight ratio of 1: 3.03.

Comparative Preparation Example 3 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a cresol novolac epoxy resin (YDCN-500-7P, Kukdo Chemical).

At this time, the rubber-modified epoxy resin and the cresol novolac epoxy resin were mixed in a 1: 2.33 weight ratio.

Comparative Preparation Example 4 Preparation of Adhesive Resin

An adhesive resin was prepared by mixing a rubber modified epoxy resin (TSR-601, EPICLON) and a DCPD type epoxy resin (KR-102, Kukdo Chemical).

At this time, the rubber modified epoxy resin and the DCPD type epoxy resin were mixed in a 1: 2.33 weight ratio.

Example 1 Preparation of Self-Fusing Conductive Paste

To 100 parts by weight of the adhesive resin prepared in Preparation Example 1, 100 parts by weight of citric acid was mixed to prepare a mixture.

709.1 parts by weight of conductive particles (alloy containing 20 to 38 μm, Sn and Bi in a weight ratio of 28:42) and diethylene glycol dimethyl ester based on 100 parts by weight of the rubber-modified epoxy resin in the prepared mixture. dimethyl ether) was mixed with 29.87 parts by weight, and subjected to insulation treatment to prepare a self-sealing conductive connection paste.

Examples 2 to 13

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, by varying the weight parts of the conductive particles, diethylene glycol dimethyl ester, and citric acid mixed in the adhesive resin as shown in Table 1 below to prepare a self-fusion conductive connection paste.

Example 14

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, instead of diethylene glycol dimethyl ester, methyl ethyl ketone was used to prepare a self-sealing conductive connection paste.

Example 15

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, a self-fusion conductive connection paste was produced without using a solvent.

Example 16

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using the adhesive resin prepared in Preparation Example 2 instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Example 17

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using the adhesive resin prepared in Preparation Example 3 instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Comparative Example 1

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using the adhesive resin prepared in Comparative Preparation Example 1 instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Comparative Example 2

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using the adhesive resin prepared in Comparative Preparation Example 2 instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Comparative Example 3

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using the adhesive resin prepared in Comparative Preparation Example 3 instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Comparative Example 4

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using the adhesive resin prepared in Comparative Preparation Example 4 instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Comparative Example 5

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using only the rubber modified epoxy resin (TSR-601, EPICLON) instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Comparative Example 6

A self-sealing conductive connection paste was prepared in the same manner as in Example 1. However, using only bisphenol A epoxy resin (YD128, Kukdo Chemical) instead of the adhesive resin prepared in Preparation Example 1, a self-sealing conductive connection paste was prepared.

Experimental Example 1

The self-fusion conductive connection pastes prepared in Examples and Comparative Examples were evaluated based on the following physical property evaluation methods, and the results are shown in Table 2 below.

(1) Connection resistance measurement (Ω / cm)

The conductive connection pastes prepared in Examples and Comparative Examples were each formed on a first circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) using a stencil (metal mask) and a squeegee to a thickness of 80 μm. After coating, the second circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) was pressed and overlapped with terminals, and then cured and self-fused for 10 minutes in a drying oven at 120 to 170 ° C., Using an instrument (Keithley's 2000 Multimeter), a test current of 1 mA was applied in a 4-probe manner, and the initial connection resistance was measured to calculate the average value.

(2) Adhesive force measurement (kgf / cm)

The conductive connection pastes prepared in Examples and Comparative Examples were applied to the first circuit member (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) with a thickness of 80 μm using a stencil and squeegee, and then After press-fitting the second circuit board (terminal 100 µm, distance between terminals 50 µm, terminal height 35 µm), the plurality of specimens were prepared after curing and self-fusion for 10 minutes in a drying oven at 180 ° C. The 10 N Load Cell was mounted using a UTM measuring machine (Universal Testing Machine, Hounsfield, H5KT model), the grip was installed, the preparation was completed, the sample was bitten into the grip, and the tensile test was performed. test speed) Adhesion was measured at 20 mm / min speed conditions.

(3) insulation measurement

The conductive connection pastes prepared in Examples and Comparative Examples were each formed on a first circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) using a stencil (metal mask) and squeegee to a thickness of 80 μm. After coating, the second circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) was pressed and overlapped with terminals, and then cured and self-fused for 10 minutes in a drying oven at 120 to 170 ° C., Using a multi tester (HIOKI, 3244-60 CARD HITESTER), the insulation was measured by checking the electrical conduction between adjacent circuits of the circuit board.

(4) Self-adhesiveness measurement

The conductive connection pastes prepared in Examples and Comparative Examples were each formed on a first circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) using a stencil (metal mask) and a squeegee to a thickness of 80 μm. After coating, the second circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) was pressed and overlapped with terminals, and then cured and self-fused for 10 minutes in a drying oven at 120 to 170 ° C., Using a multi-tester (HIOKI, 3244-60 CARD HITESTER), the presence of electrical conduction of the circuit terminals of the first and second circuit boards connected by the paste was checked, and the appearance was checked by a high-magnification microscope to measure self-adhesiveness. .

(5) printability measurement

The conductive connection pastes prepared in Examples and Comparative Examples were each formed on a first circuit board (terminal 100 μm, distance between terminals 50 μm, terminal height 35 μm) using a stencil (metal mask) and squeegee to a thickness of 80 μm. After coating, the appearance was visually checked (or microscope) to determine printability.

(6) viscosity measurement

Using the PCU-205 manufactured by Malcom, the viscosity of the self-sealing conductive connection pastes prepared in Examples and Comparative Examples was measured in a temperature range of 25 ° C. based on the JIS measurement method.

Referring to Table 2, the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 are significantly better in adhesive strength, lower in connection resistance, and better in self-adhesion than the conductive connections prepared in Example 8. Could confirm.

In addition, it was confirmed that the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 were significantly better in insulation than the conductive connections prepared in Example 9, and better in self-adhesion and printability.

In addition, the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 had lower connection resistance than the conductive connection prepared in Example 10, significantly improved adhesion and insulation, and excellent self-adhesion and printability. Could.

In addition, it was confirmed that the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 were significantly superior in printability than the conductive connections prepared in Examples 11 and 12.

In addition, it was confirmed that the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 had lower connection resistance, remarkably superior adhesion and printability, and better self-adhesion than the conductive connections prepared in Example 13. .

In addition, it was confirmed that the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 were significantly superior in printability than the conductive connections prepared in Examples 14 and 12.

In addition, the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 were remarkably excellent in printability prepared in Example 15, and were excellent in self-adhesion and insulation properties.

In addition, it was confirmed that the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 were significantly superior in printability than the conductive connections prepared in Comparative Examples 1, 2, 5, and 6.

In addition, the conductive connection pastes prepared in Examples 1 to 7, 16, and 17 had lower connection resistance than the conductive connections prepared in Comparative Examples 3 and 4, significantly improved adhesion and insulation, and excellent self-adhesion and printability. Could confirm.

Simple modifications or variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be regarded as being included in the scope of the present invention.

Claims (17)

Rubber modified epoxy resins having a number average molecular weight (Mn) of 702 to 1054 and a weight average molecular weight (Mw) of 12002 to 18004; And
Bisphenol A type epoxy resins having a number average molecular weight (Mn) of 278 to 418 and a weight average molecular weight (Mw) of 348 to 524; Including,
Adhesive resin, characterized in that the rubber-modified epoxy resin and bisphenol A epoxy resin 1: 1.86 to 2.8 by weight ratio.
The method of claim 1,
Adhesive resin, characterized in that the epoxy equivalent of 230 ~ 250 g / eq.
The method of claim 1,
Adhesive resin, characterized in that the adhesive resin has a viscosity of 80 ~ 3,300 mPas at 60 ~ 120 ℃.
The method of claim 1,
The adhesive resin adhesive resin, characterized in that the number average molecular weight (Mn) of 361 ~ 543, the weight average molecular weight (Mw) of 2733 ~ 4100.
delete The method of claim 1,
The rubber of the rubber-modified epoxy resin includes at least one of CTBN (Carboxylic terminated butadiene acrylonitrile), NBR (nitrile butadiene rubber), acrylic (silry rubber) and silicone (silicone)
The epoxy resin of the rubber-modified epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, naphthalene epoxy resin, and dicyclopentadiene (DCPD) type epoxy resin Adhesive resin, characterized in that it comprises one or more.
The adhesive resin of any one of claims 1 to 4, 6;
Electroconductive particle;
reducing agent; And
menstruum;
Self-sealing conductive connection paste comprising a.
The method of claim 7, wherein
Self-sealing conductive connection paste, comprising 567 to 851 parts by weight of conductive particles, 80 to 120 parts by weight of reducing agent, and 23 to 36 parts by weight of solvent based on 100 parts by weight of the adhesive resin.
The method of claim 7, wherein
The conductive particles are selected from bismuth (Bi), tin (Sn), indium (In), silver (Ag), copper (Cu), zinc (Zn), antimony (Sb), nickel (Ni), and alloys thereof. A self-sealing conductive connection paste comprising at least one kind.
The method of claim 9,
The conductive particles are an alloy of bismuth (Bi) and tin (Sn),
A self-sealing conductive connection paste comprising bismuth and tin in a weight ratio of 1: 0.57 to 0.87.
The method of claim 9,
The particle diameter of the said electroconductive particle is 2-75 micrometers, The self-fusion conductive connection paste characterized by the above-mentioned.
The method of claim 7, wherein
And the reducing agent comprises at least one selected from rosin-based reducing agents, organic acid reducing agents, metallic reducing agents and amine salt reducing agents.
The method of claim 7, wherein
The solvent is diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ester A self-sealing conductive connection paste comprising at least one of diethyl ether and diethylene glycol methyl ethyl ether.
The method of claim 7, wherein
The conductive connection paste has an adhesive strength of 2 to 5 kgf / cm, adhesive resistance of 0.001 ~ 1 Ω / cm at a temperature of 150 ~ 180 ℃, self-fusion conductive paste.
The method of claim 7, wherein
The conductive connection paste has a viscosity of 30 ~ 3,000mPa · s at a temperature of 100 ~ 180 ℃ self-fusion conductive paste.
The method of claim 7, wherein
The conductive connection paste is a self-bonding conductive connection paste, characterized in that for bonding at least one selected from a circuit board, a semiconductor chip, ITO Glass or a plastic substrate.
A first step of preparing a mixture by mixing 80 to 120 parts by weight of a reducing agent and 23 to 36 parts by weight of a solvent based on 100 parts by weight of the adhesive resin; And
A second step of preparing self-adhesive conductive connection paste by mixing 567 to 851 parts by weight of the conductive particles with respect to 100 parts by weight of the adhesive resin in the mixture; Including,
The adhesive resin is a rubber-modified epoxy resin having a number average molecular weight (Mn) of 702 ~ 1054, a weight average molecular weight (Mw) of 12002 ~ 18004 and a number average molecular weight (Mn) of 278 ~ 418, a weight average molecular weight of 348 ~ 524 A method for producing a self-sealing conductive connection paste, comprising a bisphenol A epoxy resin having a (Mw) in a weight ratio of 1: 1.86 to 2.8.

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