KR101731677B1 - A composition for use of anisotropic conductive film, anisotropic conductive film, and semiconductor device - Google Patents

Abstract

[화학식 2]

상기 화학식 1 및 화학식 2에서, R₁ 이 아세틸기, 알콕시카르보닐기, 벤조일기 또는 벤질옥시카르보닐기이고, R₈ 이 수소 원자 또는 C_1-6 알킬기이고, R₂ 내지 R₅, 및 R₉ 내지 R₁₂는 각각 독립적으로, 수소 원자, C_1-4 알킬기, 하이드록시기, 및 할로겐으로 이루어진 군으로부터 선택되고, R₆, R₇, R₁₃, 및 R₁₄ 는 각각 독립적으로 C_1-6 알킬기, 벤질기, o-메틸 벤질기, m-메틸 벤질기, p-메틸 벤질기 및 나프틸메틸기로 이루어진 군으로부터 선택된다.The present invention relates to a composition for an anisotropic conductive film comprising a cationic polymerizable resin, a compound of the formula (1) and a compound of the formula (2), an anisotropic conductive film and a semiconductor device connected therewith. There is provided an anisotropic conductive film which is rapidly cured at a low temperature upon thermal pressure application, has sufficient stability, and exhibits excellent connection properties after bonding, and a semiconductor device using the same.
[Chemical Formula 1]

(2)

Wherein R ₁ is an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₈ is a hydrogen atom or a C _1-6 alkyl group, R ₂ to R ₅ , and R ₉ to R ₁₂ Are independently selected from the group consisting of a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group, and a halogen, R ₆ , R ₇ , R ₁₃ , and R ₁₄ are each independently a C _1-6 alkyl group, benzyl An o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group, and a naphthylmethyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for anisotropic conductive films, an anisotropic conductive film, and a semiconductor device,

TECHNICAL FIELD The present invention relates to an anisotropic conductive film which is rapidly cured at a low temperature under thermal pressure application, has sufficient stability, and exhibits excellent connection properties after bonding, and a semiconductor device using the same.

An epoxy resin adhesive is used as an adhesive used for bonding an FPC (flexible printed circuit) or a TAB (tape automated bonding) 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 resin composition is used as such an anisotropic conductive adhesive composition. As the cationic polymerizable resin composition, a cationic curing catalyst which generates protons by heat and light to initiate cationic polymerization is used. Typically, sulfonium antimonate complexes are known. However, since the sulfonium antimonate complex has SbF6, which is bonded to antimony, which is a fluorine atom metal, as a counter anion, it generates a large amount of fluorine ions during cationic polymerization and causes migration between the dissimilar metals, There is a problem that the connection pad is corroded. Accordingly, there is a need for various cationic curing catalysts having no corrosion problem and having reactivity capable of curing at low temperature.

In this connection, Japanese Patent Application Laid-Open No. 2008-308596 discloses an epoxy resin and a sulfonium-based cationic polymerization initiator. However, the polymerization initiator has a short storage stability in an epoxy solution of 1 hour or less and needs to be improved in stability.

Therefore, development of an anisotropic conductive film which is rapidly cured at low temperature, has sufficient storage stability, and exhibits excellent connection properties after bonding is required.

Japanese Patent Laid-Open No. 2008-308596 (published on December 25, 2008)

Accordingly, an object of the present invention is to provide an anisotropic conductive film which is rapidly cured at a low temperature upon thermal compression bonding, has sufficient stability, and exhibits excellent connection characteristics after bonding, and a semiconductor device using the same.

In one aspect of the present invention, there is provided a composition or film for an anisotropic conductive film comprising a cationic polymerizable resin, a compound of formula (1), and a compound of formula (2).

[Chemical Formula 1]

(2)

Wherein R ₁ is an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₈ is a hydrogen atom or a C _1-6 alkyl group, R ₂ to R ₅ , and R ₉ to R ₁₂ Are independently selected from the group consisting of a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group, and a halogen, R ₆ , R ₇ , R ₁₃ , and R ₁₄ are each independently a C _1-6 alkyl group, benzyl An o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group, and a naphthylmethyl group.

Further, in one embodiment of the present invention, a composition comprising a cationic polymerizable resin, a compound of Formula 1, and a compound of Formula 2,

There is provided a composition or film for an anisotropic conductive film, wherein the weight ratio of the compound of formula (1) to the compound of formula (2) is 0.5: 1 to 4: 1, based on the total weight of solids in the composition for anisotropic conductive films.

The present invention also provides a semiconductor device connected by a film formed from an anisotropic conductive film according to one aspect of the present invention or a composition for an anisotropic conductive film according to one aspect of the present invention.

The anisotropic conductive film of the present invention and the semiconductor device using the same are rapidly cured at a low temperature, have sufficient stability, and exhibit excellent connection properties after bonding.

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 adhesive layer 10 of an anisotropic conductive film according to the present invention, which is located between contacted members and connects the first electrode and the second electrode .

According to one aspect of the present invention, there is provided a composition for an anisotropic conductive film comprising a cationic polymerizable resin, a compound of formula (1), and a compound of formula (2).

[Chemical Formula 1]

(2)

Wherein R ₁ is an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₈ is a hydrogen atom or a C _1-6 alkyl group, R ₂ to R ₅ , and R ₉ to R ₁₂ Are independently selected from the group consisting of a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group, and a halogen, R ₆ , R ₇ , R ₁₃ , and R ₁₄ are each independently a C _1-6 alkyl group, benzyl An o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group, and a naphthylmethyl group.

The R ₈ of R ₁ with a compound of formula 2 in the compound of formula (1) comprises a different substituent. In this case, the rate at which the compound of formula (1) reacts with the cationic polymerizable resin is faster than the rate at which the compound of formula (2) reacts with the cationic polymerizable resin. The compound of formula 2 can act as a stabilizer by delaying the cationic polymerization reaction by displacing a portion of the cationic polymerization catalyst of the compound of formula 1 due to the relatively slow reaction rate and trapping the Lewis acid in the cationic polymerization. By controlling the curing speed, it is possible to cure rapidly at a low temperature and secure storage stability at room temperature.

Specifically, R ₁ is an acetyl group or an alkoxycarbonyl group, R ₂ to R ₅ are hydrogen atoms, R ₆ is C _1-4 alkyl, R ₇ is benzyl group, o-methylbenzyl group, methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group, R ₈ in the general formula (2) is a hydrogen atom, R ₉ to R ₁₂ are a hydrogen atom, R ₁₃ is C _1-6 alkyl, R ₁₄ may be a benzyl group, an o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group or a naphthylmethyl group.

The compound of formula (1) may be a compound of formula (3).

(3)

Examples of the compound of formula (2) include compounds of formula (4) and compounds of formula (5).

[Chemical Formula 4]

[Chemical Formula 5]

The weight ratio of the compound of Formula 1 to the compound of Formula 2 may be from 0.5: 1 to 4: 1, more specifically from 1: 1 to 3: 1, based on the total solid weight of the composition for the anisotropic conductive film. If the weight ratio is in the above range, it can be rapidly cured at a low temperature and have sufficient storage stability. The compound of formula (1) may be used in an amount of 0.4 to 20% by weight, and specifically 1 to 15% by weight, based on the total solid content of the composition for anisotropic conductive films. The compound of the general formula (2) may be used in an amount of 0.1 to 5% by weight, specifically 0.2 to 1% by weight, based on the total solid weight of the composition for anisotropic conductive films.

The cationic polymerizable resin that can be used in the present invention is not particularly limited, and a cationic polymerizable resin conventionally used for bonding electronic materials can be used. Examples of the cationic polymerizable resin which can be preferably used in the present invention include cationic polymerizable vinyl compounds, cyclic lactones, cyclic ethers and the like. Examples of the cationic polymerizable vinyl compound include styrene and vinyl ether. Examples of cyclic ethers include epoxy compounds, oxetane compounds, spiroorthoesters, and the like. An epoxy resin can also be preferably used.

Specifically, an epoxy resin, specifically, a thermosetting epoxy resin can be used. For example, an epoxy resin having an epoxy equivalent of about 90 to 5000 g / eq and having two or more epoxy groups in the molecule can be used.

Specifically, it may include at least one of an epoxy monomer, an epoxy oligomer and an epoxy polymer selected from the group consisting of bisphenol type, novolak type, glycidyl type, aliphatic and alicyclic type.

As the epoxy resin, there can be used any of known epoxy compounds including at least one bonding structure which can be selected from among molecular structures such as bisphenol type, novolak type, glycidyl type, aliphatic and alicyclic type have.

In one example, an epoxy resin which is solid at room temperature and a liquid epoxy resin at room temperature can be used in combination, and a flexible epoxy resin can be additionally used in combination. Examples of the epoxy resin which is solid at normal temperature include phenol novolac type epoxy resin, cresol novolac type epoxy resin, epoxy resin having dicyclo pentadiene as a main skeleton, bisphenol A Type or F-type polymer, or a modified epoxy resin, but is not limited thereto.

Examples of the liquid epoxy resin at room temperature include bisphenol A type, F type or mixed epoxy resin, but are not limited thereto.

Non-limiting examples of the flexible epoxy resin include a dimer acid-modified epoxy resin, an epoxy resin having propylene glycol as a main skeleton, and a urethane-modified epoxy resin.

As the aromatic epoxy resin, at least one selected from the group consisting of naphthalene-based, anthracene-based, and pyrene-based resins may be used, but the present invention is not limited thereto.

The cationic polymerizable resin may be used in an amount of 20 to 60% by weight, specifically 30 to 50% by weight, based on the total solid content of the composition for the anisotropic conductive film.

According to another embodiment of the present invention, the composition for anisotropic conductive films may further comprise a binder resin.

The binder resin is not particularly limited and binder resins commonly used in the art can be used.

Examples of the binder resin that can be used in the present invention include a polyimide resin, a polyamide resin, a phenoxy resin, an epoxy resin, a polymethacrylate resin, a polyacrylate resin, a polyurethane resin, an acrylate modified urethane resin, , Styrene-butadiene-styrene (SBS) resins and epoxy modified products, styrene-ethylene-butylene-styrene (SEBS) resins and modified products thereof, or acrylic Rhenitrile butadiene rubber (NBR) and hydrogenated products thereof. These may be used alone or in combination of two or more. The larger the weight-average molecular weight of the binder resin, the more easily the film is formed, but the binder resin is not particularly limited. For example, the weight average molecular weight of the binder resin may be specifically from 5,000 to 150,000 g / mol, and more specifically from 10,000 to 80,000 g / mol. When the weight average molecular weight of the binder resin is less than 5,000 g / mol, film formation may be inhibited, and when it is more than 150,000 g / mol, miscibility with other components may deteriorate. The binder resin may be contained in an amount of 15 to 50% by weight, specifically 18 to 45% by weight, based on the total weight of the solid composition of the anisotropic conductive film. For example, the binder resin may be contained in an amount of 20 to 40% . Good film forming ability and adhesion can be obtained within the above range.

According to another embodiment of the present invention, the composition for anisotropic conductive films may further include a filler.

The filler used in this embodiment is not particularly limited and fillers conventionally used in the art can be used.

Non-limiting examples of the filler that can be used in this embodiment include inorganic or organic fillers. Examples of the inorganic filler include gold powder, silver powder, copper powder, and nickel, which are metal elements. Alumina, Magnesium, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, magnesium oxide, aluminum oxide, aluminum nitride, silica, boron nitride, titanium dioxide, glass, iron oxide and ceramics. Rubber-based fillers, and polymer-based fillers. The shape and size of the filler are not particularly limited, but may preferably be spherical, and the size is preferably in the range of 500 nm to 10 mu m.

The filler may be contained in an amount of 0.05 to 20% by weight, preferably 0.1 to 15% by weight based on the total weight of the composition for anisotropic conductive films. Within the above range, the reinforcing effect by the addition of the filler becomes sufficient, and the anisotropic conductive film can be formed and the adhesion to the adherend can be enhanced. According to another embodiment of the present invention, the composition for anisotropic conductive film May further comprise conductive particles.

The conductive particles used in this embodiment are not particularly limited, and conductive particles commonly used in the art can be used.

Non-limiting examples of conductive particles usable in this embodiment include metal particles including Au, Ag, Ni, Cu, solder 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; Insulating particles coated with insulating particles, and the like. These may be used alone or in combination of two or more.

The average particle size of the conductive particles may vary depending on the pitch of the applied circuit, and may be selected in accordance with the application in the range of 1 to 20 μm. Specifically, the conductive particles having a mean particle size of 1 to 10 μm Particles can be used.

The conductive particles may include 1 to 30% by weight, specifically 1 to 25% by weight, based on the total weight of the composition for anisotropic conductive films.

Stable connection reliability can be ensured within the above range, and a low connection resistance can be exhibited.

According to another embodiment of the present invention, the composition for anisotropic conductive films may further comprise a stabilizer.

Examples of the stabilizer include sulfoniums, amines, phenols, crown esters, phosphines, triazines and the like. The amount of the stabilizer added may vary depending on the characteristics of the compound, so that it is not particularly limited, but it is preferably 0.01 to 5% by weight, more preferably 0.02 to 3% by weight based on the total solid weight of the composition for anisotropic conductive film good.

In another embodiment of the present invention, the composition for an anisotropic conductive film may further comprise a silane coupling agent in addition to the above components.

Examples of the silane coupling agent include polymerizable fluorinated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane and (meth) acryloxypropyltrimethoxysilane; Silicon compounds having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. ; And 3-chloropropyltrimethoxysilane, and the like, but are not limited thereto.

The silane coupling agent may be contained in an amount of 1 to 10% by weight based on the total solid weight of the composition for anisotropic conductive films.

In another embodiment of the present invention, the anisotropic conductive film may further include additives such as a polymerization inhibitor, an antioxidant, a heat stabilizer and the like in order to provide additional physical properties without impairing the basic physical properties. The additive is not particularly limited, but may be contained in an amount of 0.01 to 10% by weight based on the solid content of the anisotropic conductive film composition.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine, or a mixture thereof. As the antioxidant, a phenolic or hydroxycinnamate-based material can be used. For example, tetrakis- (methylene- (3,5-di-t-butyl-4-hydoxinnamate) methane, 3,5-bis (1,1-dimethylethyl) -4- -2,1-ethanediyl ester and the like can be used.

According to still another aspect of the present invention, there is provided an anisotropic conductive film formed from the composition for an anisotropic conductive film according to any one of the above-mentioned embodiments.

Herein, the anisotropic conductive film may include an anisotropic conductive adhesive layer and a release film formed from the composition for anisotropic conductive film. The release film can be removed when the anisotropic conductive film is pressed against the first to-be-connected members or the second to-be-connected members. Therefore, an anisotropic conductive film can be used in this application in a compatible manner with an anisotropic conductive adhesive layer.

In the present invention, the anisotropic conductive film may have a single-layer structure including one anisotropic conductive adhesive layer, a two-layer structure in which a non-conductive adhesive layer containing no conductive particles and a conductive adhesive layer containing conductive particles are sequentially laminated, Layer structure in which a non-conductive adhesive layer is laminated on both sides. The composition for anisotropic conductive films disclosed herein can be used for a non-conductive adhesive layer, a conductive adhesive layer, or both.

According to another embodiment of the present invention, after the anisotropic conductive film is left at 20 ° C for 170 hours, the film left between the adhering materials is placed, and the film is heated at 150 ° C and 70 MPa for 5 seconds, It can be 5 Ω or less. Specifically, it may be 3 Ω or less, more specifically 0.2 Ω or less, for example, 0.18 Ω or less.

The method of measuring the connection resistance is as follows. At 20 ℃ area bump with the anisotropic conductive film was allowed to stand for 170 hours 1200㎛ ^2, by using the glass substrate, and a bump area 1200㎛ ^2, IC having a thickness of 1.5mm with an indium tin oxide (ITO) circuit having a thickness of 2000Å, the , The lower interface is squeezed, and the specimen is prepared by pressurization and heating under the conditions of 150 ° C, 70 Mpa, and 5 seconds. Using the Keithley 2000 Multimeter, measure the connection resistance by applying a test current of 1 mA using the 4-point probe measurement method.

When the connection resistance is within the above range, the connection stability of the anisotropic conductive film is improved and the connection reliability can be excellent.

According to still another embodiment of the present invention, the anisotropic conductive film has an initial temperature of 65 to 75 ° C and a peak temperature of 105 to 113 ° C, ° C and a peak temperature of 107 to 112 ° C, and an initial temperature of the thermal differential scanning calorimeter measured after leaving the anisotropic conductive film at 20 ° C for 170 hours is 70 to 77 ° C and a peak temperature is 108 to 116 ° C, Specifically, there is provided an anisotropic conductive film having a starting temperature of 70 to 75 占 폚 and a peak temperature of 109 to 115 占 폚.

The starting temperature and the peak temperature are measured as follows. The adhesive layer of the anisotropically conductive film left for 170 hours at the initial stage and at 20 占 폚 was subjected to heat treatment at a rate of 10 占 폚 / min in a nitrogen gas atmosphere using a DSC (differential scanning calorimeter, TA Instruments Q20) The temperature at the time when the inclination of the DSC graph is firstly increased by heat generation is measured. Also, the temperature at the point where the heat generation amount is maximum in the DSC graph is measured as the peak temperature.

When the initiation temperature and the peak temperature are within the above ranges, the anisotropic conductive film can be rapidly cured at a low temperature, for example, 150 DEG C or less, and the storage stability can be excellent.

According to still another aspect of the present invention, there is provided an anisotropic conductive film having a rate of change in calorific value of 30% or less as measured by DSC after storage at 20 ° C for 170 hours.

[Formula 1]

Heating rate change rate (%) = [(H ₀ -H ₁ ) / H ₀ ] × 100

In the above formula (1), H ₀ represents the calorific value on DSC measured at 20 ° 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 20 ° C. for 170 hours.

The method of measuring the rate of change of the calorific value is not particularly limited and can be measured according to a method commonly used in the art. 1 mg of the anisotropic conductive film of the present embodiment is measured and measured at 20 ° C using a differential scanning calorimeter, for example, a TA 20 Q 20 model at 10 ° C / 1 min, The initial calorific value is measured (H ₀ ) in the temperature range of -50 to 250 ° C., and then the film is allowed to stand at 20 ° C. for 170 hours, and the calorific value is measured by the same method (H ₁ ) do.

When the rate of change in the calorific value is within the above range, the storage stability of the anisotropic conductive film is good, and the adhesion or the connection resistance can be prevented from increasing.

The anisotropic conductive film of the above embodiment may include any one of the above-mentioned compositions for anisotropic conductive films.

According to still another aspect of the present invention, there is provided a semiconductor device connected with any one of the anisotropic conductive films. Specifically, the semiconductor device includes: a first connected member containing a first electrode; A second connected member containing a second electrode; And an anisotropic conductive film according to an embodiment of 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, or an anisotropic conductive film according to one aspect of the present invention And a semiconductor device including an anisotropic conductive film formed from a composition for a conductive film. The wiring board and the semiconductor chip are not particularly limited, and those known in the art can be used. 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, the semiconductor device 30 includes a first connected member 50 including a first electrode 70 and a second connected member 60 including a second electrode 80, Through the anisotropic conductive adhesive layer (10) including the conductive particles (3) described herein, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode They can be bonded to each other. Further, the method of manufacturing the semiconductor device of this embodiment is not particularly limited, and can be performed by a method known in the art.

Hereinafter, the present invention will be described in more detail by describing Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are merely examples of the present invention, and the present invention should not be construed as being limited thereto.

Examples and Comparative Examples

Preparation of anisotropic conductive film

The anisotropic conductive films of Examples 1 to 3 and Comparative Examples 1 to 3 were produced in the compositions and contents shown in Table 1 below.

Raw material product name Example Comparative Example One 2 3 One 2 3 Phenoxy resin YP50 30 30 30 30 30 30 Epoxy resin YD128 40 40 40 40 40 40 The compound of formula (1) SI-B2A 1.4 1.2 1.0 2 0 1.2 The compound of formula 2 SI-B3 0.6 0.8 1.0 0 2 0 Compound of Formula 1: Compound of Formula 2 2.3: 1 1.5: 1 1: 1 - - - Compounds of formula 6 - - - - - 0.8 Filler EMIX300 8 8 8 8 8 8 Conductive particle AUL704F 20 20 20 20 20 20 Total 100 100 100 100 100 100

Example 1

40 wt% of an epoxy resin (YD128, Kukdo Chemical Co., Ltd.) as a curing portion accompanied by a curing reaction, 30 wt% of a phenoxy resin (YP50, National Kagaku KK) as a binder resin serving as a matrix for film formation, (EMIX300, TATSUMORI) as a filler for increasing the adhesiveness of an anisotropic conductive film, 1.4 wt% of a compound (Si-B3, SANSHIN CHEMICAL, Japan) , 20 wt% of conductive particles (AUL704, average particle diameter 4 mu m, SEKISUI Co., Ltd., Japan) for imparting conductive performance to the anisotropic conductive film were insulated and mixed to prepare an anisotropic conductive film composition.

Each of the compositions for anisotropic conductive films prepared as described above was coated on a white release film, followed by evaporating the solvent in a drier at 60 ° C for 5 minutes to obtain a dried anisotropic conductive film having a thickness of 16 μm.

Example 2

Except that 1.2% by weight of the compound of the formula (1) (Si-B2A, Sanshin Chemical Co., Japan) and 0.8% by weight of the compound of the formula (Si-B3, 1, an anisotropic conductive film was prepared.

Example 3

Except that 1.0% by weight of the compound of the formula (1) (Si-B2A, Sanshin Chemical, Japan) and 1.0% by weight of the compound of the formula (2) (Si-B3, 1, an anisotropic conductive film was prepared.

Comparative Example 1

An anisotropic conductive film was produced in the same manner as in Example 1, except that 2.0 weight% of the compound of the formula (1) (Si-B2A, Sanshin Chemical, Japan) was used and the compound of the formula .

Comparative Example 2

Except that the compound of the formula (1) (Si-B2A, Sanshin Chemical, Japan) was not used and 2.0% by weight of the compound of the formula (2) (Si-B3, An anisotropic conductive film was prepared in the same manner as in Example 1.

Comparative Example 3

(Si-B3, Sanshin Chemical, Japan) was used instead of the compound of the formula (2) (Si-B2A, , Sanxin Chemical Co., Ltd., Japan) was used in an amount of 0.8% by weight, to prepare an anisotropic conductive film.

[Chemical Formula 6]

Experimental Example

The DSC phase initiation temperature, peak temperature, rate of change in calorific value and connection resistance of the anisotropic conductive film

The initiation temperature, peak temperature, rate of change in heating rate, and connection resistance of the anisotropic conductive film produced in the above Examples and Comparative Examples were measured according to the following methods, and the results are shown in Table 2 below.

(1) initial and 20 hours after 170 hours, DSC onset temperature and peak temperature

The adhesive layer of the anisotropically conductive film left for 170 hours at the initial stage and at 20 占 폚 was subjected to heat treatment at a rate of 10 占 폚 / min in a nitrogen gas atmosphere using DSC (differential scanning calorimeter, TA Instruments Q20) The temperature at which the inclination of the DSC graph was first increased due to heat generation during the measurement was measured. Also, the peak temperature was measured at the peak temperature in the DSC graph.

(2) Rate of change in calorific value after 170 hours at 20 ° C

And 170 hours, respectively, of the anisotropic conductive adhesive film was allowed to stand during the initial and 20 ℃ to 1mg aliquots using a TA社Q20 model, 10 ℃ / 1min, calorific value (H ₀ of the initial film in the temperature range -50 ~ 250 ℃ ) And the heating value (H ₁ ) of the film left for 170 hours were measured. The rate of change of the calorific value of the film left for 170 hours in comparison with the calorific value of the initial film is then calculated as a percentage.

(3) Connection resistance after 170 hours at 20 캜

20 ℃ in order to identify the electrical characteristics of the anisotropic conductive film over the anisotropic conductive film 170 hours leaving a bump area 1200㎛ ^2, a glass substrate, and a bump area with indium tin oxide (ITO) circuit having a thickness of 2000Å 1200㎛ ^2, Using a 1.5 mm-thick IC, the upper and lower interfacial surfaces were squeezed, and then pressed and heated under the conditions of 150 DEG C, 70 Mpa, and 5 seconds to prepare specimens. Using the Keithley 2000 Multimeter, the test resistance was measured by applying a test current of 1 mA to the 4 point probe method (ASTM F43-64T).

Condition Example Comparative Example One 2 3 One 2 3 Initial Onset (℃) 70 72 72 66 76 75 Peak (° C) 108 110 111 107 115 116 20 ℃
/ 170 hours Onset (℃) 71 73 74 72 78 77 Peak (° C) 110 111 114 115 116 117 Rate of change in calorific value (%) 15 14 12 46 8 6 Connection resistance (Ω) 150 ℃
/ 70 MPa Initial 0.12 0.16 0.14 0.12 3.26 5.68 20 ° C / 170 hours 0.16 0.18 0.16 250 5.28 6.89

In Table 2, the anisotropic conductive films of Examples 1 to 3 have a DSC phase initiation temperature within the range of 65 to 75 ° C and a peak temperature within the range of 105 to 113 ° C, so that the low temperature fast curing is possible. %, And the storage stability is excellent. The connection resistance is as small as 0.2 Ω or less. On the other hand, in the case of Comparative Example 1 in which the compound of Formula 2 was not added, the storage stability was inhibited by a change in the calorific value of 30% or more, and the connection resistance was as large as 250? Under the condition of 150 占 폚 and 70 MPa. In the case of Comparative Example 2 in which the compound of Formula 1 was not added, the starting temperature and the peak temperature were high, and the connection resistance was as high as 5.28? Under the condition of 150 占 폚 and 70 MPa. In Comparative Example 3 in which a conventionally known stabilizer was added in place of the compound of Formula 2, the connection temperature and peak temperature were high, and the connection resistance was as high as 6.89? Under the condition of 150 占 폚 and 70 MPa.

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 (12)

An anisotropic conductive film comprising a cationic polymerizable resin, a compound of Formula 1, and a compound of Formula 2.
[Chemical Formula 1]

(2)

Wherein R ₁ is an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₈ is a hydrogen atom or a C _1-6 alkyl group, R ₂ to R ₅ , and R ₉ to R ₁₂ Are independently selected from the group consisting of a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group, and a halogen, R ₆ , R ₇ , R ₁₃ , and R ₁₄ are each independently a C _1-6 alkyl group, benzyl An o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group, and a naphthylmethyl group. The anisotropic conductive film according to claim 1, wherein the film has a rate of change in calorific value of 30% or less as measured by a differential scanning calorimeter (DSC) after being left at 20 占 폚 for 170 hours.
[Formula 1]
Heating rate change rate (%) = [(H ₀ -H ₁ ) / H ₀ ] × 100
In the above formula (1), H ₀ represents the calorific value on DSC measured at 20 ° 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 20 ° C. for 170 hours. The anisotropic conductive film of claim 1, wherein the weight ratio of the compound of formula (1) to the compound of formula (2) is 0.5: 1 to 4: 1, based on the total solid weight of the composition for preparing an anisotropic conductive film. The anisotropic conductive film according to claim 2, wherein the anisotropic conductive film has an onset temperature in a thermal differential scanning calorimeter range of 65 to 75 ° C and an exothermic peak temperature of 105 to 113 ° C. The method for manufacturing the anisotropic conductive film according to any one of claims 1 to 4, wherein the anisotropic conductive film is left at 20 DEG C for 170 hours, then the film left between the members to be connected is placed, The anisotropic conductive film having a connection resistance measured after heating and pressing is 5 or less. A composition for an anisotropic conductive film comprising a cationic polymerizable resin, a compound of formula (1), and a compound of formula (2).
[Chemical Formula 1]

(2)

Wherein R ₁ is an acetyl group, an alkoxycarbonyl group, a benzoyl group or a benzyloxycarbonyl group, R ₈ is a hydrogen atom or a C _1-6 alkyl group, R ₂ to R ₅ , and R ₉ to R ₁₂ Are independently selected from the group consisting of a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group, and a halogen, R ₆ , R ₇ , R ₁₃ , and R ₁₄ are each independently a C _1-6 alkyl group, benzyl An o-methylbenzyl group, an m-methylbenzyl group, a p-methylbenzyl group, and a naphthylmethyl group. The composition for an anisotropic conductive film according to claim 6, wherein the weight ratio of the compound of formula (1) to the compound of formula (2) is 0.5: 1 to 4: 1 relative to the total weight of the total solid content of the composition for anisotropic conductive films. The composition for anisotropic conductive films according to claim 6, wherein the composition for anisotropic conductive films further comprises a binder resin and conductive particles. The composition for an anisotropic conductive film according to claim 8, wherein the cationic polymer resin is 30 to 50 wt%, the compound of the formula 1 is 0.4 to 20 wt%, the compound of the formula 2 is 0.1 to 5 wt% By weight of the binder resin, 15 to 50% by weight of the binder resin, and 1 to 30% by weight of the conductive particles. 10. The composition for anisotropic conductive films according to any one of claims 6 to 9, wherein the composition for anisotropic conductive films further comprises a stabilizer. The composition for an anisotropic conductive film according to claim 10, wherein the stabilizer is a sulfonium, an amine, a phenol, a crown ester, a phosphine, or a triazine. A first connected member containing a first electrode;
A second connected member containing a second electrode; And
The anisotropic conductive film according to any one of claims 1 to 4, which is located between the first connected member and the second connected member and connects the first electrode and the second electrode, A semiconductor device comprising a film formed by the composition for an anisotropic conductive film according to any one of claims 9 to 12.

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