KR101712703B1 - Adhesive composition, anisotropic conductive film and the semiconductor device using thereof - Google Patents

Abstract

상기 화학식 1에서, R₁ 내지 R₅는 각각, 독립적으로 수소 원자, 알킬기, 아세틸기, 알콕시카르보닐기, 벤조일기 또는 벤질옥시카르보닐기이고, R₆ 및 R₇은 각각, 독립적으로 알킬기, 벤질기, o-메틸벤질기, m-메틸벤질기, p-메틸벤질기 또는 나프틸메틸기이며,
[화학식 2]

상기 화학식 2에서, R₈ 내지 R₁₂는 각각, 독립적으로 수소 원자, 알킬기, 아세틸기, 알콕시카르보닐기, 벤조일기 또는 벤질옥시카르보닐기이고, R₁₃ 및 R₁₄는 각각, 독립적으로 알킬기, 벤질기, o-메틸벤질기, m-메틸벤질기, p-메틸벤질기 또는 나프틸메틸기이며, X₁은 할로겐 원자 또는 알킬황산을 나타낸다.The present invention relates to a bonding composition comprising an alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 ° C of a thermal differential scanning calorimeter, a cationic polymerization catalyst of formula (1) and a compound of formula (2), an anisotropic conductive film using the same, To a semiconductor device connected thereto.
[Chemical Formula 1]

Wherein R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₆ and R ₇ each independently represent an alkyl group, a benzyl group, A methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group,
(2)

Wherein R ₈ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₁₃ and R ₁₄ each independently represent an alkyl group, a benzyl group, an o A methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, and X ₁ represents a halogen atom or an alkylsulfuric acid.

Description

TECHNICAL FIELD [0001] The present invention relates to an adhesive composition, an anisotropic conductive film, and a semiconductor device using the same. BACKGROUND ART [0002]

The present invention relates to an adhesive composition, an anisotropic conductive film and a semiconductor device using the same.

Anisotropic conductive film (ACF) generally refers to a film-like adhesive in which conductive particles are dispersed in a resin such as an epoxy resin. An anisotropic conductive film (ACF) is a film-like adhesive in which conductive particles are dispersed in a resin such as epoxy, Means a polymer membrane having anisotropy and adhesion.

An epoxy resin adhesive is used as an adhesive used for bonding an FPC (flexible printed circuit) or a TAB (tape automation joint) and a circuit substrate such as a PCB (printed circuit board) or a glass circuit board, Is used as an anisotropic conductive adhesive. The main characteristic required for such an adhesive is that it can be cured within a short time at a relatively low temperature so as not to cause thermal damage to the circuit substrate and provide electrical connection between the substrates.

A cationic polymerizable epoxy resin composition is used as such an anisotropic conductive film composition. The cationic polymerizable epoxy resin composition uses a cationic polymerization catalyst which generates protons by heat and light to initiate cationic polymerization. Typically, sulfonium antimonate complexes are known. However, since the sulfonium antimonate complex has SbF6, which is bound to antimony which is a fluorine atom metal, as a counteranion, a large amount of fluorine ions are generated at the time of cationic polymerization and migration is caused between the dissimilar metals, Or the connection pad is corroded. Accordingly, there is no need for such a cationic polymerization catalyst having the above-mentioned problems of reactivity capable of curing at low temperature without the problem of corrosion.

In addition, the cationic polymerizable epoxy resin composition has the advantage of being capable of curing at a low temperature, but it also has a problem of lowering stability. To solve this problem, a part of the cation polymerization catalyst is substituted and a Lewis acid or other cationic active species A polymer compound for delaying or stabilizing the cationic polymerization reaction has been studied (Korean Patent Application Publication No. 2011-0122928).

Korean Patent Application Publication No. 2011-0122928 (Published on May 31, 2013)

It is an object of the present invention to provide an adhesive composition or an anisotropic conductive film having improved storage stability, moisture resistance and heat resistance while achieving low temperature fast curing by utilizing heat curing.

Another object of the present invention is to provide a bonding composition or an anisotropic conductive film which can be connected at a connection temperature of 150 DEG C or less, while exhibiting excellent adhesion and reliability.

In one example of the present invention, there is provided an adhesive composition comprising an alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 占 폚 of a thermal differential scanning calorimeter, a cationic polymerization catalyst of formula (1) and a compound of formula (2).

[Chemical Formula 1]

Wherein R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₆ and R ₇ each independently represent an alkyl group, a benzyl group, A methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group,

(2)

Wherein R ₈ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₁₃ and R ₁₄ each independently represent an alkyl group, a benzyl group, an o A methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, and X ₁ represents a halogen atom or an alkylsulfuric acid.

In another example of the present invention, a binder resin; An alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 DEG C of a thermal differential scanning calorimeter; The cationic polymerization catalyst of Formula 1; The compound of formula 2; And an anisotropic conductive film containing conductive particles.

In another example of the present invention, a first connected member containing a first electrode; A second connected member containing a second electrode; And a semiconductor device connected by the anisotropic conductive film described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode.

In the anisotropic conductive film according to one example of the present invention, the use of an alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 DEG C of a thermal differential scanning calorimeter allows the inclusion of chlorine in comparison with other epoxy resins, Connection at a connection temperature is possible, and electrical characteristics such as adhesion and reliability are excellent. It also has the advantage of being rapidly cured at low temperatures and improving storage stability.

1 shows a first embodiment of the present invention in which a first connected member 50 including a first electrode 70, a second connected member 60 including a second electrode 80, 2 is a cross-sectional view of a semiconductor device 30 according to an embodiment of the present invention, including an anisotropic conductive film as described herein, which is located between connected members and connects the first electrode and the second electrode.

An example of the present invention relates to a bonding composition comprising an alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 캜 of a thermal differential scanning calorimeter (DSC), a cationic polymerization catalyst of the formula (1) and a compound of the formula (2).

[Chemical Formula 1]

Wherein R ₁ to R ₅ are each independently a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₆ and R ₇ each independently represent an alkyl group, a benzyl group, - methylbenzyl group, m-methylbenzyl group, p-methylbenzyl group or naphthylmethyl group.

Specifically, R ₁ may be a hydrogen atom or an acetyl group, and more specifically, it may be an acetyl group. R ₂ to R ₅ may each be a hydrogen atom, and R ₆ may specifically be a benzyl group, an o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, Specifically, it may be an o-methylbenzyl group. R ₇ may specifically be an alkyl group, and more specifically may be a methyl group.

(2)

Wherein R ₈ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₁₃ and R ₁₄ each independently represent an alkyl group, a benzyl group, an o A methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, and X ₁ represents a halogen atom or an alkylsulfuric acid.

Specifically, R ₈ to R ₁₂ may each be a hydrogen atom. Each of R ₁₃ and R ₁₄ may independently be an alkyl group, a benzyl group, an o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group and specifically includes an alkyl group, . X ₁ may be specifically alkylsulfuric acid, more specifically methylsulfuric acid.

The exothermic peak temperature of the DSC is determined by adding a cycloaliphatic epoxy resin and a cationic polymerization catalyst to the solvent and then measuring the temperature at 10 ° C / 1 min using a Q20 model manufactured by TA Corporation. As the cationic polymerization catalyst, the compound of the above formula (1) can be used. Specifically, benzyl (4-acetoxyphenyl) methylsulfonium tetrakis (pentafluorophenyl) borate can be used. In the present invention, the exothermic peak temperature of the alicyclic epoxy resin is 60 to 105 캜, specifically 80 to 105 캜. If the exothermic peak temperature is within the above range, it is quickly cured at a connection temperature of 150 DEG C or less, for example, a connection temperature of 140 DEG C or less, for example, a connection temperature of 130 DEG C or less, . The alicyclic epoxy resin can exclude the chlorine content from other epoxy resins and has an advantage of excellent electrical characteristics. The epoxy equivalent of the alicyclic epoxy resin is usually in the range of about 100 to 470 g / eq, specifically about 120 to about 400 g / eq, more specifically about 130 to about 350 g / eq. Within the above range, the viscosity and flow characteristics can be good without lowering the adhesive strength.

Since the alicyclic epoxy resin has an epoxy structure close to an alicyclic ring, the ring-opening reaction is rapid and the curing reaction is better than other epoxy resins. The alicyclic epoxy resin in the present invention can be used without limitation as long as it has a structure in which a direct bond is bonded to an alicyclic ring or an epoxy structure exists through another linking group. Specifically, alicyclic epoxy resins of the following formulas (3) to (6) can be used.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

N, s, t, u, v, m and f are each independently an integer of 1 to 50, and R is an alkyl group, an acetyl group, an alkoxy group or a carbonyl group. Specifically, n, s, t, u, v, m and f are each independently an integer of 1 to 25, and R is an alkyl group, an acetyl group or an alkoxy group.

In another example of the present invention, the adhesive composition or film may further include an epoxy resin other than the alicyclic epoxy resin. As the epoxy resin that can be used, at least one selected from the group consisting of bisphenol type, novolak type, glycidyl type, aliphatic and aromatic epoxy resins can be used, but not limited thereto. In the above example, the alicyclic epoxy resin may be contained in an amount of 3 to 50 parts by weight, specifically 10 to 40 parts by weight, based on 100 parts by weight of the total epoxy resin. If the above range is set, the DSC-induced heat generation starting temperature of the film may be 75 캜 or less, thereby improving the electrical characteristics.

The cationic polymerization catalyst of formula (1) may be contained in an amount of 0.1 to 20 parts by weight, and more specifically 0.1 to 10 parts by weight, based on 100 parts by weight of the alicyclic epoxy resin. When the amount of the cationic polymerization catalyst is more than 20 parts by weight, the storage stability is deteriorated. When the amount is less than 0.1 parts by weight, curing becomes insufficient.

The compound of formula (2) may be contained in an amount of 0.1 to 30 parts by weight, more specifically 3 to 10 parts by weight, per 100 parts by weight of the cationic polymerization catalyst. If the amount of the compound of formula (2) exceeds 30 parts by weight, the curing of the composition may be inhibited. If the amount of the compound is less than 0.1 parts by weight, the characteristics of stabilizing the function of the cation polymerization catalyst may not be exhibited.

Another example of the present invention relates to a composition for an anisotropic conductive film or an anisotropic conductive film further comprising a binder resin and conductive particles in addition to the above composition.

The binder resin used in the present invention is not particularly limited, and resins commonly used in the art can be used. Non-limiting examples of the binder resin include polyimide resin, polyamide resin, phenoxy resin, polymethacrylate resin, polyacrylate resin, polyurethane resin, polyester resin, polyester urethane resin, polyvinyl butyral resin , Styrene-butylene-styrene (SBS) resin and epoxy-modified resin, styrene-ethylene-butylene-styrene (SEBS) resin and modified resin thereof, acrylonitrile butadiene rubber (NBR) And the like. These resins may be used alone or in admixture of two or more. Concretely, a resin compatible with an epoxy resin can be used, and a phenoxy resin can be preferably used.

The binder resin may be contained in an amount of 20 to 60% by weight based on the solid weight of the entire film, specifically 25 to 55% by weight, more specifically 30 to 50% by weight.

In the present invention, the conductive particles may be metal particles, or organic or inorganic particles coated with a metal such as gold or silver. Further, in order to secure electrical insulation at the time of excessive use, the conductive particles may be subjected to an insulating treatment. For example, the conductive particles may include metal particles including Au, Ag, Ni, Cu, Pb, and the like; carbon; Particles comprising a resin including polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol or the like and particles of the modified resin coated with a metal such as Au, Ag, Ni or the like; And insulating particles coated with insulating particles thereon may be used.

The conductive particles may be contained in an amount of 1 to 30% by weight, preferably 1 to 25% by weight based on the solid weight of the entire film.

The alicyclic epoxy resin may be contained in an amount of 20 to 50% by weight, specifically 25 to 45% by weight, more specifically 25 to 40% by weight, based on the solid weight of the entire film. have.

The cationic polymerization catalyst may be 1 to 20% by weight, specifically 5 to 10% by weight, based on the solid weight of the entire film.

The compound of Formula 2 may be present in an amount of 0.01 to 10% by weight, and more preferably 0.05 to 5% by weight, based on the solid weight of the entire film.

Another example of the present invention also provides an anisotropic conductive film having a heat generation rate change rate of 25% or less after initiation temperature on a DSC (differential scanning calorimetry) of 50 to 75 캜 and after being left at 25 캜 for 150 hours. Onset temperature on DSC refers to the temperature at which the slope of the DSC graph first increases due to heat generated during DSC measurement. Specifically, the DSC phase start temperature may be 53 to 70 占 폚 and the rate of change in calorific value may be 20% or less. In this range, curing can be started at a low temperature, and storage stability is also excellent.

As a non-limiting example of measuring the initiation temperature on the DSC, the bonding composition is heated at a rate of 0 deg. C / min at a rate of 10 deg. C / min under a nitrogen gas atmosphere using DSC (thermal differential scanning calorimeter, TA instruments, Q20) There is a method of measuring the initiation temperature of DSC in the range of 300 캜.

A non-limiting example of measuring the rate of change of the calorific value after being left at 25 DEG C for 150 hours is as follows.

1 mg of the anisotropic conductive film of this embodiment is measured and the initial calorific value (H ₀ ) is measured at 25 ° C in a temperature range of -50 ° C to 250 ° C at 10 ° C / 1min using a differential scanning calorimetry calorimeter, for example, and, then, this was allowed to stand at 25 ℃ 150 hours after and calculates the rate of change according to the following formula 1, the amount of heat generated in the same manner therefrom is measured (H _1).

[Formula 1]

(%) = [(H ₀ -H ₁ ) / H ₀ ] Χ 100

In the formula (1), H ₀ represents the calorific value on DSC measured at 25 ° C. at 0 ° C. for the anisotropic conductive film, and H ₁ represents the calorific value on DSC after the anisotropic conductive film is left at 25 ° C. for 150 hours.

The rate of change in calorific value is 25% or less relates to improvement in storage stability or storage stability of the anisotropic conductive film, and the starting temperature of the DSC phase is in the range of 50 캜 to 75 캜, which is related to the low temperature fast curing property.

Another example of the present invention also provides an anisotropic conductive film having a connection resistance of 2? Or less after reliability evaluation. Specifically, the connection resistance after the reliability evaluation may be 1.6 Ω or less. In this range, it is possible to maintain a low connection resistance while being able to be cured at a low temperature, thereby improving the connection reliability, and also there is an advantage that the storage stability can be maintained for a long period of time.

The method of measuring the connection resistance after the above reliability evaluation is not particularly limited, and a non-limiting example is as follows.

 The specimens were connected at 70 ° C and 1.0 MPa for 1 second under the pressure condition of 130 ° C and 70 MPa for 5 seconds, respectively. Five specimens were prepared and maintained at 85 ° C and 85% relative humidity for reliability evaluation. After storing the circuit connections in a high temperature and high humidity chamber for 500 hours, measure the resistance using the 4 point probe method. The resistance measuring device applies 1mA and the resistance is calculated by the measured voltage.

The anisotropic conductive films according to the above examples include the above-mentioned alicyclic epoxy resin; A cationic polymerization catalyst of formula (1); And a compound of formula (2), and may further include a binder resin and / or conductive particles. Therefore, the description of the alicyclic epoxy resin, the cationic polymerization catalyst of formula (1), or the compound of formula (2), for example, the content and the kind, and the like can be applied to the above examples.

Another example of the present invention is that,

A first connected member containing a first electrode;

A second connected member containing a second electrode; And

An anisotropic conductive film as described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode, or a film formed from the composition for an anisotropic conductive film described herein To a semiconductor device.

The first member to be connected may be, for example, a chip on film (COF) or a flexible printed circuit board (fPCB), and the second member to be connected may be a glass panel or a printed circuit board .

1, a first connecting member 50 including a first electrode 70 and a second connected member 60 including a second electrode 80 are formed on the surface of the semiconductor substrate 30, , An anisotropic conductive adhesive layer (10) comprising conductive particles (3) described in the present invention, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode, Can be adhered.

The present invention provides an anisotropic conductive film formed from an anisotropic conductive film composition. No special equipment or equipment is required to form the anisotropic conductive film. For example, the anisotropic conductive film composition of the present invention is dissolved in an organic solvent such as toluene to be liquefied, and then the conductive particles are agitated for a predetermined time in a range in which the conductive particles are not pulverized. And then dried for a predetermined time to volatilize toluene or the like to obtain an anisotropic conductive film containing an anisotropic conductive adhesive layer and a release film.

Examples of the release film include polyolefin films such as polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, ethylene / vinyl acetate copolymer, mixture of polyethylene / styrene butadiene rubber, and polyvinyl chloride Can be used. Further, polymers such as polyethylene terephthalate, polycarbonate and poly (methyl methacrylate), thermoplastic elastomers such as polyurethane and polyamide-polyol copolymer, and mixtures thereof can be used. The thickness of the release film can be selected from an appropriate range, for example, 10-50 占 퐉.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example  And Comparative Example

Preparation of adhesive composition

The adhesive composition was prepared by dissolving an epoxy resin, a thermosetting cationic polymerization catalyst, and a compound of Formula 2 as a stabilizer in a solvent, Propylene Glycol Monomethyl Ether Acetate (PGMEA), as shown in Table 1 below. Table 1 shows the contents based on 100 parts by weight of the epoxy resin.

Raw material product name Maker Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Epoxy resin SER-2001 SHINA T & C 100 100 CELLOXIDE 2081 DAICEL CHEMICAL 100 CELLOXIDE 2000 DAICEL CHEMICAL 100 SEV-3410 SHINA T & C 100 Cationic polymerization catalyst SI-B3A SANSHIN CHEMICAL 5 5 5 5 5 stabilizator SI-S SANSHIN CHEMICAL 0.25 0.25 0.25 0.25

Example  One

5 parts by weight of a thermosetting cationic polymerization catalyst (SI-B3A, SANSHIN CHEMICAL Co., Japan) based on 100 parts by weight of an alicyclic epoxy resin (SER-2001, SHINA T & C, EEW 135 g / Based on 100 parts by weight of the polymerization catalyst, 5 parts by weight of a compound of the formula (2) (SI-S, SANSHIN CHEMICAL, Japan) as a stabilizer were mixed to prepare a bonding composition.

Example  2

An adhesive composition was prepared in the same manner as in Example 1, except that the alicyclic epoxy resin was changed to CELLOXIDE 2081 (DAICEL CHEMICAL, Japan, EEW 200 g / eq).

Comparative Example  One

An adhesive composition was prepared in the same manner as in Example 1, except that the stabilizer (SI-S, SANSHIN CHEMICAL, Japan) was not used.

Comparative Example  2

Except that DCPD (Dicyclopentadiene) type epoxy resin (SEV-3410, SHINA T & C, Japan, EEW 300 g / eq) was used in place of the alicyclic epoxy resin in Example 1 A composition was prepared.

Comparative Example  3

An adhesive composition was prepared in the same manner as in Example 1, except that the alicyclic epoxy resin was changed to CELLOXIDE 2000 (DAICEL CHEMICAL, Japan, EEW: 126 g / eq).

Experimental Example  : Evaluation of physical properties of adhesive composition

Of epoxy resin DSC Peak temperature measurement

The peak temperatures on the DSC of the epoxy resins of Examples 1 and 2 and Comparative Examples 1 to 3 were measured in the following manner:

A composition was prepared by mixing 2 mg of an epoxy resin and 0.1 mg of a thermosetting cationic polymerization catalyst (SI-B3A, SANSHIN CHEMICAL, Japan) with PGMEA as a solvent. Using a DSC (thermal differential scanning calorimeter, TA instruments, Q20) The exothermic peak temperature on the DSC was measured at a rate of 10 캜 / min from 0 to 300 캜.

After 24 hours at < RTI ID = 0.0 > 25 C < GEL Measure anger

The adhesive composition was allowed to stand at 25 占 폚 for 24 hours, and then it was measured whether it was converted into GEL. Fifty percent of the 25 ml vial bottle was filled with resin and tilted to observe flowability, and it was judged to be GEL when no flow was observed.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 DSC peak (占 폚) 98 100 96 114 58 GEL (25 ℃, 24 hours) Good Good GEL Good GEL

Example  : Preparation of anisotropic conductive film

Example  3

On the basis of the solid weight of the whole film, 40 wt% of a binder resin serving as a matrix for film formation, 40 wt% of a phenoxy resin (PKHH, Inchemrez, USA) dissolved in a xylene / ethyl acetate azeotropic mixed solvent, 30 wt% of an alicyclic epoxy resin (SER-2001, SHINA T & C, Japan, EEW 135 g / eq) as a curing part accompanied by a curing reaction, 9 wt% of a thermosetting cationic polymerization catalyst (SI-B3A, SANSHIN CHEMICAL, (AUL-704, average particle diameter 4 μm, SEKISUI Co., Ltd., Japan) as a filler for imparting conductivity to an anisotropic conductive film as a stabilizer, 1 wt% of a compound represented by the formula (SI-S, SANSHIN CHEMICAL, 20% by weight was insulated and mixed to prepare a composition for anisotropic conductive film.

The above composition for anisotropic conductive films was coated on a white release film, and the solvent was evaporated for 5 minutes in a drier at 60 캜 to obtain a dried anisotropic conductive film having a thickness of 16 탆.

Example  4

An anisotropic conductive film was produced in the same manner as in Example 3, except that the alicyclic epoxy resin was changed to CELLOXIDE 2081 (DAICEL CHEMICAL, Japan, EEW 200 g / eq).

Comparative Example  4

An anisotropic conductive film was produced in the same manner as in Example 3, except that the stabilizer (SI-S, SANSHIN CHEMICAL Co., Ltd.) was not used.

Comparative Example  5

Except for using DCPD (Dicyclopentadiene) type epoxy resin (SEV-3410, SHINA T & C, Japan, EEW 300 g / eq) instead of alicyclic epoxy resin in Example 3, To prepare a conductive film.

Comparative Example  6

An anisotropic conductive film was produced in the same manner as in Example 3, except that the alicyclic epoxy resin was changed to CELLOXIDE 2000 (DAICEL CHEMICAL, Japan, EEW: 126 g / eq).

Experimental Example  : Evaluation of Physical Properties of Anisotropically Conductive Film

DSC Phase start temperature ( Onset 온도 ) Measure

The initiation temperature of the anisotropic conductive film was measured by DSC (thermal differential scanning calorimeter, TA instruments, Q20) in a nitrogen gas atmosphere at a rate of 10 占 폚 / min in the range of 0 to 300 占 폚. Onset temperature on DSC refers to the temperature at which the slope of the DSC graph first increases due to heat generated during DSC measurement.

Change in calorific value after 150 hours at 25 ° C

1 mg of each of the anisotropically conductive films prepared above was dispensed and the initial calorific value at 25 占 폚 in the range of 25 占 폚, 10 占 폚 / 1 minute, and -50 to 250 占 폚 using DSC (thermal differential scanning calorimeter, TA instruments, Q20) (H ₀ ) and the heating value (H ₁ ) after being left at 25 ° C for 150 hours, and the amount of change in calorific value was calculated as a percentage.

Measurement of connection resistance after evaluation of connection resistance and reliability

In order to understand the electrical characteristics of the anisotropic conductive film, a glass substrate having a bump area of 1200 mu m < 2 > and an indium tin oxide (ITO) circuit having a thickness of 2000 ANGSTROM and an IC having a bump area of 1200 mu m & And each of the anisotropic conductive films prepared according to the comparative examples was pressed under the following conditions under the conditions of 130 DEG C and 70 MPa for 5 seconds to produce five specimens per each sample Respectively. The connection resistance is measured by the following method, and this is referred to as an initial connection resistance (T ₀ ).

For reliability evaluation, the circuit connection was stored in a high temperature and high humidity chamber maintained at 85 ° C and 85% relative humidity for 500 hours. Then, the connection resistance was measured in the same manner and the connection resistance T ₁ do.

The connection resistance measurement is a 4 point probe method, which can use a resistance measuring device. Measure the resistance between 4 points using the four probes connected to the device. The resistance measuring device applies 1mA and the resistance is calculated by the measured voltage.

Example 3 Example 4 Comparative Example 4 Comparative Example 5 Comparative Example 6 DSC phase start temperature (캜) 62 63 59 119 60 Rate of change in calorific value (%) 21 14 32 8 45 Connection resistance
(Ω) (T ₀ ) 0.12 0.23 0.11 1.23 0.09 responsibility
Connection resistance (Ω) (T ₁ ) 1.25 1.54 1.15 3.87 1.87

In Table 3, the anisotropic conductive films of Examples 3 and 4 of the present invention showed a change in calorific value after 25 hours at 25 DEG C of 25% or less, indicating that the curing reaction did not proceed and storage stability was excellent. The initial connection resistance (T ₀ ) of less than ₁ Ω and the reliability connection resistance (T ₁ ) of 3.0 Ω or less were measured at low temperature fast curing conditions.

On the other hand, in Comparative Example 4 which did not contain a stabilizer, the storage stability was deteriorated by measuring the change in calorific value at 32% after 150 hours at 25 DEG C, and in Comparative Example using an epoxy resin whose DSC peak temperature was out of the range of 60 to 105 DEG C 5 and 6, the reliability connection resistance (T ₁ ) was 1.87 to 3.87 OMEGA, and the rate of increase of the connection resistance in the pressurization and final compression under the condition of low temperature fast curing was large.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that such detail is solved by the person skilled in the art without departing from the scope of the invention. will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (14)

An alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 DEG C of a thermal differential scanning calorimeter, a cationic polymerization catalyst of formula (1) and a compound of formula (2).
[Chemical Formula 1]

Wherein R 1 to R ₅ are each independently a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₆ And R ₇ are each independently an alkyl group, a benzyl group, an o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group,
(2)

Wherein R ₈ to R ₁₂ each independently represent a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₁₃ and R ₁₄ each independently represent an alkyl group, a benzyl group, an o A methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, and X ₁ represents a halogen atom or an alkylsulfuric acid. The adhesive composition according to claim 1, wherein the alicyclic epoxy resin has a structure represented by any one of formulas (3) to (6).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

N, s, t, u, v, m and f are each independently an integer of 1 to 50, and R is an alkyl group, an acetyl group, an alkoxy group or a carbonyl group. The method of claim 1 or 2, wherein R ₁ is a hydrogen atom or an acetyl group, R ₂ to R ₅ are each a hydrogen atom, R ₆ is a benzyl group, an o-methylbenzyl group, A benzyl group, a p-methylbenzyl group or a naphthylmethyl group, and R ₇ is an alkyl group. The method according to claim 1 or 2, wherein R ₈ to R ₁₂ are each a hydrogen atom, R ₁₃ and R ₁₄ each independently represent an alkyl group, a benzyl group, an o-methylbenzyl group, A methylbenzyl group or a naphthylmethyl group, and X < ₁ > is an alkyl sulfuric acid. The process according to claim 1 or 2, further comprising 0.1 to 20 parts by weight of a cationic polymerization catalyst per 100 parts by weight of the alicyclic epoxy resin, and 0.1 to 30 parts by weight of the compound of formula ≪ / RTI > Binder resin;
An alicyclic epoxy resin having an exothermic peak temperature of 60 to 105 DEG C of a thermal differential scanning calorimeter;
A cationic polymerization catalyst of formula (1);
A compound of formula 2; And
An anisotropic conductive film comprising conductive particles.
[Chemical Formula 1]

Wherein R ₁ to R ₅ each represent a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₆ and R ₇ each represent an alkyl group, a benzyl group, an o- , m-methylbenzyl group, p-methylbenzyl group or naphthylmethyl group,
(2)

Wherein R ₈ to R ₁₂ each represent a hydrogen atom, an alkyl group, an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₁₃ and R ₁₄ each represent an alkyl group, a benzyl group, an o- , an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, and X ₁ represents a halogen atom or an alkylsulfuric acid. The anisotropic conductive film according to claim 6, wherein the alicyclic epoxy resin has a structure represented by the following formulas (3) to (6).
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

N, s, t, u, v, m and f are each independently an integer of 1 to 50, and R is an alkyl group, an acetyl group, an alkoxy group or a carbonyl group. The method of claim 6 or 7, wherein R ₁ is a hydrogen atom or an acetyl group, R ₂ to R ₅ are each a hydrogen atom, R ₆ is a benzyl group, an o-methylbenzyl group, A benzyl group, a p-methylbenzyl group or a naphthylmethyl group, and R ₇ is an alkyl group. The anisotropic conductive film according to claim 6 or 7, wherein R ₈ to R ₁₂ in the general formula (2) are hydrogen, R ₁₃ and R ₁₄ are alkyl groups, and X ₁ is alkylsulfuric acid. The process according to claim 6 or 7, wherein 0.1 to 20 parts by weight of the cationic polymerization catalyst is added to 100 parts by weight of the alicyclic epoxy resin, and 0.1 to 30 parts by weight of the compound of formula ≪ / RTI > [7] The method of claim 6, wherein the binder resin is 20 to 60 wt%, the alicyclic epoxy resin is 20 to 50 wt%, the cationic polymerization catalyst is 1 to 20 wt% Wherein the compound of Formula 2 is contained in an amount of 0.01 to 10% by weight and the conductive particles are contained in an amount of 1 to 30% by weight. The anisotropic conductive film according to claim 6, wherein the film of the following formula (1) has a change in the calorific value after storage at 25 DEG C and a starting temperature of 50 to 75 DEG C on a differential scanning calorimeter (DSC) of 25% or less.
[Formula 1]
Change in calorific value (%) = [(H ₀ -H ₁ ) / H ₀ ] Х100
In the formula (1), H ₀ represents the calorific value on DSC measured at 25 ° C. at 0 ° C. for the anisotropic conductive film, and H ₁ represents the calorific value on DSC after the anisotropic conductive film is left at 25 ° C. for 150 hours. 7. The method for producing an anisotropic conductive film according to claim 6, wherein said anisotropic conductive film is pressure bonded at 70 DEG C, 1.0 MPa for 1 second, and then pressure bonded at 130 DEG C and 70 MPa for 5 seconds under the conditions of 85 DEG C and 85% And the post-reliability connection resistance measured by being left for a time is 2? Or less. A first connected member containing a first electrode;
A second connected member containing a second electrode; And
And the anisotropic conductive film of the sixth or seventh aspect, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode.

Images