KR20090065156A - Thermosetting adhesive composition and adhesive film using thereof - Google Patents

Abstract

A thermosetting adhesive composition, and an adhesive film using the composition are provided to improve adhesive strength, heat resistance and chemical resistance and to obtain a stable adhesive strength even in case of the exposure to a solvent, an acid or a base. A thermosetting adhesive composition comprises 10-30 parts by weight of a siloxane imide which is prepared by reacting an acid anhydride and siloxane diamine; 100 parts by weight of a modified epoxy resin which is prepared by reacting 70-90 parts by weight of an epoxy resin; a curing agent; and 0.5-40 parts by weight of an additive. The adhesive composition has a glass transition temperature of 130 °C or more and an adhesive strength of 0.3N/mm or more.

Description

Thermosetting adhesive composition and adhesive film using the same

The present invention relates to a thermosetting adhesive composition and an adhesive film using the same, and more particularly, to a thermosetting adhesive composition having excellent adhesion and heat resistance and an adhesive film using the same.

BACKGROUND ART With the miniaturization and high density of electronic devices, high integration of semiconductor chips is in progress. At the same time, the shape of the semiconductor continues to change. As an insulating substrate of a package, an organic substrate made of an epoxy resin, a polyimide resin, or an inorganic substrate made of a metal plate is used. Therefore, bonding different types of materials such as substrates and chips has become an important factor in determining the reliability of the entire package. That is, in addition to the function of bonding the dissimilar materials, the materials to be bonded should have characteristics such as antistatic effect, heat dissipation, and insulation so as to properly exhibit their inherent functions.

Among many packages, a chip scale package (CSP) refers to a package that is equal to or slightly larger than the chip size. The trend toward small size, light weight, and thinness is a chip-size package technology that overcomes its shortcomings due to the large and thick ball grid array (BGA) package. Using this technology, the area of the motherboard can be used efficiently and the size and weight can be reduced together, ultimately achieving the goal of cost reduction. In addition, memory available in the market can be used in conjunction with other devices, reducing overall system cost. The CSP consists of a wafer, a substrate, and a dicing die-bond adhesive that bonds the two together.

Silver paste is mainly used for joining the conventional semiconductor element and the support member for semiconductor element mounting. However, with the recent miniaturization and high performance of semiconductor devices, the use of conventional silver pastes has revealed limitations. That is, the silver paste is difficult to control the thickness of the adhesive sheet and there is a possibility of defects during the wire bonding began to use the adhesive on the film as a way to replace this. Dicing die-bonded adhesive in the form of a film showed high workability by reducing the die bonding film lamination process and the dicing film lamination process in one process in the semiconductor manufacturing process.

Dicing die-bonding adhesive is a four-layer structure consisting of an adhesive, an adhesive, and two films to protect it. The adhesive plays a role of connecting the chip and the organic substrate or the chip and the chip. The adhesive should have heat resistance and chemical resistance required by semiconductor products and have excellent storage stability against adhesion. In addition, since the wafer is thinned and adhered at a high temperature, warpage of the wafer occurs, more excellent low-temperature adhesiveness is required for the film adhesive. In particular, in recent years, the number of chip stacks in a package increases, and the temperature and time for wire bonding to the chips become higher and prolonged, resulting in a poor filling of the surface of the substrate. Therefore, in order to secure reliability, the film adhesive is required to have excellent embedding properties under more stringent wire bond conditions. In addition, due to the reflow process, the adhesion loss at high temperature (260 ° C) should be small, and it is necessary to have only a small amount of volatile components causing the contamination of the circuit.

Since polyimide resins are excellent in heat resistance and electrical insulation, they are widely used as varnishes and flexible printed circuit board materials for electronic parts. However, since the polyimide resin is rigid, the flexibility is insufficient, the glass transition temperature is too high, the handling is difficult, and there is a problem that the solubility in organic solvents is insufficient.

Therefore, siloxane was introduced during polyimide synthesis to improve the adhesion to the base material while at the same time to secure the heat resistance. In addition, a blend adhesive composed of a mixture of a thermoplastic resin and a thermosetting resin has been proposed. Although it is reported that heat resistance is ensured through a blend of a thermoplastic polyimide resin and a thermosetting epoxy resin, there is a problem that an unreacted component may remain.

In order to solve the above problems, the present invention synthesizes a modified epoxy resin by reacting the ends of the synthesized siloxane imide with an epoxy group, and includes a curing agent and additives to improve heat resistance and adhesion, and improve mechanical properties The purpose is to provide.

In addition, an object of the present invention is to provide an adhesive film produced using the thermosetting adhesive composition.

In order to achieve the above object, the present invention

Thermosetting adhesive composition comprising a siloxane imide (A) synthesized by reacting an acid anhydride and a siloxane diamine, and a modified epoxy resin (C), a curing agent (D), and an additive (E) synthesized by reacting an epoxy resin (B). as,

The siloxane imide (A) is 10 to 30 parts by weight, the epoxy resin (B) is 70 to 90 parts by weight based on 100 parts by weight of the modified epoxy resin (C),

The additive (E) is 0.5 to 40 parts by weight based on 100 parts by weight of the modified epoxy resin (C),

It provides a thermosetting adhesive composition having a glass transition temperature of 130 ° C. or more and an adhesive force of 0.3 N / mm or more.

In order to achieve the above another object, the present invention

It provides an adhesive film prepared using the thermosetting adhesive composition.

Hereinafter, the present invention will be described in detail with reference to the drawings.

1 shows a dicing die bond adhesive for semiconductors, an adhesive layer 2 attached to a back side of a polyolefin 1 serving as a semiconductor wafer, an adhesive layer 3 adhered to another surface of the adhesive layer 2, and It has a laminated structure comprising the polyimide film 4 adhered to the pressure-sensitive adhesive layer (3).

The adhesive composition used for the adhesive layer 2 should have properties such as relaxation of thermal stress, heat resistance or chemical resistance, excellent adhesion. In addition, when the adhesive leaks to the electrode portion provided in the semiconductor chip, poor connection of the electrode occurs, and if there is a gap between the circuit and the adhesive, problems with heat resistance, adhesive strength, etc. occur, and therefore, it is necessary to adjust heat resistance, durability, and adhesive strength. Accordingly, the present invention includes a siloxane imide (A) synthesized by reacting an acid anhydride with a siloxane diamine, a modified epoxy resin (C), a curing agent (D), and an additive (E) synthesized by reacting an epoxy resin (B). As the thermosetting adhesive composition, the siloxane imide (A) is 10 to 30 parts by weight, the epoxy resin (B) is 70 to 90 parts by weight based on 100 parts by weight of the modified epoxy resin (C), the additive ( E) is 0.5 to 40 parts by weight based on 100 parts by weight of the modified epoxy resin (C), the adhesive layer is characterized by having a glass transition temperature of 130 ℃ or more and more than 0.3N / mm (when the adhesive thickness 20μm) or more. .

According to the present invention, siloxane-imide resins obtained from acid anhydrides and siloxane diamines are prepared. The glass transition temperature of the siloxane-imide is preferably 50 ° C to 200 ° C. In addition, the present invention is characterized by producing a modified epoxy resin with improved adhesion and thermal properties by introducing a commercial epoxy to the synthesized siloxane-imide.

The siloxane imide of the present invention is obtained from acid anhydrides and siloxane diamines. Acid anhydrides are pyromellitic acid dianhydrides, hydroxy phthalic anhydrides, cyclopentane-1,2,3,4-tetracarboxylic dianhydrides (cyclopentane-1,2,3) , 4-tetraacrboxylic acid dianhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride) , And 4,4'-oxydiphthalic acid dianhydride (4,4-oxydiphthalic acid dianhydride) may be used, but is not limited thereto. The use amount of acid anhydride is preferably 2: 1 of diamine and molar ratio. If the content of the acid anhydride is higher than the content of the diamine, unreacted residues may occur, so that the synthesis is difficult to perform properly.

The siloxane diamines according to the invention are ω, ω'-bis (2-aminoethyl) polydimethylsiloxane (ω, ω'-bis (2-aminoethyl) polydimethylsiloxane), ω, ω'-bis (2-aminopropyl) poly Dimethylsiloxane (ω, ω'-bis (2-aminopropyl) polydimethylsiloxane), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (ω, ω'-bis (2-aminopropyl) tetramethyldisiloxane), ω, ω ' -Bis (2-aminopropyl) polydimethylphenylsiloxane (ω, ω'-bis (2-aminopropyl) polydimethylphenylsiloxane) and the like can be used, but is not limited thereto. The content of siloxane diamine is 1: 2 by molar ratio with acid anhydride. When the content of siloxane diamine is less than the acid anhydride, it is not preferable because a synergistic effect of the adhesive strength is not expected, and when the content of the siloxane diamine is more than the acid anhydride, unreacted residues may also occur, making it difficult to obtain a desired compound.

In order to produce an imide resin, it reacts at the temperature between 0 degreeC-200 degreeC under nitrogen atmosphere, and synthesize | combins a polyamic acid. The imide resin can be synthesize | combined by dehydrating the acid amide part normally at 100 degreeC-200 degreeC of obtained polyamic-acid resin. The solvent used for the reaction includes NMP (N-methyl pyrrolidine), DMAc, cyclopentanone, 1,4-dioxane, dimethylformamide, and the like. A solvent can be used individually by 1 type or in combination of 2 or more type.

In the present invention, a modified epoxy resin is synthesized using an indirect method. In this case, the terminal of the imide to be synthesized must have a COOH or OH functional group to react with a commercial epoxy resin to synthesize a modified epoxy resin. In the basic synthesis method in which a COOH or OH functional group is provided at the terminal, an acid anhydride such as trimellitic anhydride or pyromellitic anhydride and an aminophenol or aminobenzoic acid are used to prepare a compound having a benzoic acid group or a phenol group at the terminal. Synthesis examples are shown in Formula 1:

The thermosetting adhesive composition of the present invention may include a modified epoxy resin, a curing agent, and additives. The additives include curing accelerators, rubbers, coupling agents, fillers, and the like.

The modified epoxy resin may be prepared by reacting the siloxane imide synthesized above with various commercial epoxy resins. The kind of commercial epoxy resin is as follows.

Examples of the epoxy resins include polyfunctional resins such as phenol novolac epoxy resins and cresol novolac epoxy resins, epoxy resins such as diglycidyl bisphenol A, and bisphenol F (bisphenol F). F) An epoxy resin, a urethane modified epoxy resin, an acrylic modified epoxy resin, etc. can be used, These can be used individually or in mixture, respectively, It is not limited to this. Although the use content of an epoxy resin can add 1-100 weight part, when it exceeds this range, hardening defect may arise by the influence of an uncured powder.

Amine and carboxylic anhydride are the most widely used curing agents for epoxy resins, but diaminodiphenyl sulfone, phenol novolac resin, bisphenol novolac resin, and cresol noblock ( cresol novolac) resin and the like can be used, it is preferable to use 0.6 to 1.2 equivalents per epoxy resin in consideration of the correlation with the epoxy equivalents. Too much or too little hardener may result in insufficient reactions and adversely affect physical properties.

As an additive, a curing accelerator can be used. Hardening accelerators are most commonly used imidazole. 2-methyl imidazole, 2-ethyl imidazole, 1-cyano ethyl 2-phenyl imidazole, 1- (2 -Cyanoethyl) -2-phenyl imidazole (1- (2-cyano ethyl) -2-phenyl imidazole), triphenylphosphine, etc. can be used, but it is not limited to this. It is preferable to mix | blend 0.1-1 weight part with respect to 100 weight part of modified epoxy resins. If it is less than 0.1 part by weight, the curing speed is very slow, which may cause process problems.

As the additive, a high molecular weight resin having compatibility with an epoxy resin and having a weight average molecular weight of 10,000 or more, a rubber containing a highly polar functional group, a reactive rubber containing a large polar functional group, or the like is used. Examples of such rubbers include NBR resins containing acrylonitrile, SBR resins containing styrene, and the like. These rubbers may be used alone or in combination. 1 to 100 parts by weight may be added based on 100 parts by weight of the modified epoxy resin, but when it exceeds 100 parts by weight, handling may be difficult, and when it is 1 or less, sufficient adhesive strength may not appear.

In addition, a coupling agent may be blended for interfacial bonding between different materials. Examples of such a coupling agent include a silane coupling agent, a titanate coupling agent, and the like. Of these, a silane coupling agent (for example, (γ-mercaptopropyl) trimethoxysilane) is most preferred. It is preferable that the compounding quantity of a coupling agent mix | blends 0.1-5 weight part with respect to 100 weight part of modified epoxy resins. If it is less than 0.1 part by weight, it is difficult to achieve the purpose of improving the adhesive force, and if it exceeds 5 parts by weight, a decrease in physical properties may occur.

In addition, a filler may be used to adjust the viscosity of the adhesive. As such a filler, silica, graphite, aluminum, aluminum hydroxide and the like can be used, but the present invention is not limited thereto. It is preferable that a filler mix | blends 1-30 weight part with respect to 100 weight part of modified epoxy resins. If it is less than 1 part by weight, it is difficult to improve viscosity and improve mechanical properties of the adhesive. If it is more than 30 parts by weight, it is difficult to handle the adhesive composition as well as causing problems such as deterioration of electrical properties due to void remaining.

According to the adhesive composition of this invention, while showing the outstanding adhesive force, it shows heat resistance and chemical-resistance, and shows the stable adhesive force even when exposed to solvent, acid, and a base.

Example

matter

Siloxane diamine monomer: 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1,3-bis (3-aminopropyl) tetramethyldisiloxane (TCI))

Acid Anhydride Monomer: Hydroxyphthalic anhydride

Epoxy Resin: DGEBA (YD-128, Kukdo Chemical)

Curing agent: diaminodiphenyl sulfone (DDS, Aldrich)

Curing accelerator: 1- (2-cyanoethyl) -2-phenyl imidazole (1- (2-cyanoethyl) -2-phenyl imidazole (TCI))

Rubber: Carboxylated Nitrile-Butadiene Rubber (XNBR)

Coupling Agent: (γ-mercaptopropyl) trimethoxysilane ((γ-mercaptopropyl) trimethoxysilane (TCI))

Filler: AEROSIL R972 (DEGUSSA)

Siloxane Imide ( siloxan - imide ) synthesis

500 ml four-necked flask with stirrer, nitrogen inlet, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, hydroxy phthalic anhydride, NMP (N-methyl-2-pyrrolidinone (1-methyl-2) -pyrrolidinone)) was added and stirred for 30 minutes until completely dissolved in a nitrogen atmosphere. After confirming that dissolved was reacted for 6 hours at room temperature to obtain amic acid. In the imidization, Dean-Stark trap was installed in the reactor, m-xylene was injected into the reaction, and refluxed for 24 hours to remove water generated in the reaction. The resulting material was cooled and then precipitated in distilled water to obtain a powder. The synthesized siloxane imide chemical structure was confirmed by FT-IR, glass transition temperature (Tg) was evaluated using DSC, and thermal stability of siloxane imide synthesized using TGA was evaluated.

Preparation of Modified Epoxy Resin

A new type of modified epoxy resin was synthesized by reacting the terminal of the synthesized siloxane imide with the terminal of a commercial epoxy resin. 1) 10% by weight siloxane imide, 90% by weight epoxy resin, 2) 20% by weight siloxane imide, 80% by weight epoxy resin, 3) siloxane imide 30 in a 500 ml four-necked flask equipped with a stirrer, thermometer and nitrogen inlet. 160% by weight, 70% by weight of epoxy resin The reaction was carried out at 占 폚. Stirring was started and a small amount of the epoxy resin being synthesized was removed every 10 minutes to determine the equivalent weight. First, the weight of the collected amount was measured and dissolved in methylene cellulsolve (MC) and reacted with 30 ml of HCI for 30 minutes. After 30 minutes, 2-3 drops of methyl orange were dropped and titrated with NaOH. At this time, the amount of NaOH was calculated by calculating the experimental value to determine the equivalent, and the reaction time was obtained by comparing this with the theoretical value. The reaction was terminated when the theoretical equivalent was reached even during the measurement. After the modified epoxy resin was prepared, an amine curing agent was introduced into the epoxy resin as a curing agent. Application solvents were methyl ethyl ketone (MEK) or cyclohexanone.

In addition, XNBR was introduced to secure the flexibility of the adhesive, and other curing accelerators, coupling agents, and fillers were applied. The modified epoxy composition was compared with the existing epoxy composition to evaluate thermal and mechanical properties.

Example 1

The sum of the synthesized siloxane imide and the epoxy resin was 100 phr (part per hundred resin), and 10 phr of the siloxane imide was reacted with 90 phr of the bifunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 5 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 2

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 10 phr of the siloxane imide was reacted with 90 phr of the bifunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 10 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 3

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 10 phr of the siloxane imide was reacted with 90 phr of the bifunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 20 wt% of rubber, 1 wt% of coupling agent, and 5 wt% of filler to the modified epoxy resin.

Example 4

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 10 phr of the siloxane imide was reacted with 90 phr of the bifunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 30 wt% of rubber, 1 wt% of coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 5

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 20 phr of the siloxane imide was reacted with 80 phr of the difunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 5 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 6

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 20 phr of the siloxane imide was reacted with 80 phr of the difunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 10 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 7

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 20 phr of the siloxane imide was reacted with 80 phr of the difunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 20 wt% of rubber, 1 wt% of coupling agent, and 5 wt% of filler to the modified epoxy resin.

Example 8

A total amount of the synthesized siloxane imide and the epoxy resin was 100 phr, and 20 phr of the siloxane imide was reacted with 80 phr of the difunctional epoxy resin to prepare a modified epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 30 wt% of rubber, 1 wt% of coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 9

The sum of the synthesized siloxane imide and the epoxy resin was 100 phr, and a modified epoxy resin was prepared by reacting 30 phr of the siloxane imide and 70 phr of the bifunctional epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 5 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 10

The sum of the synthesized siloxane imide and the epoxy resin was 100 phr, and a modified epoxy resin was prepared by reacting 30 phr of the siloxane imide and 70 phr of the bifunctional epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 10 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Example 11

The sum of the synthesized siloxane imide and the epoxy resin was 100 phr, and a modified epoxy resin was prepared by reacting 30 phr of the siloxane imide and 70 phr of the bifunctional epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 20 wt% of rubber, 1 wt% of coupling agent, and 5 wt% of filler to the modified epoxy resin.

Example 12

The sum of the synthesized siloxane imide and the epoxy resin was 100 phr, and a modified epoxy resin was prepared by reacting 30 phr of the siloxane imide and 70 phr of the bifunctional epoxy resin. An adhesive composition was prepared by adding 1 wt% of a curing accelerator, 30 wt% of rubber, 1 wt% of coupling agent, and 5 wt% of a filler as an amine curing agent and an additive to the modified epoxy resin.

Comparative Example 1

The bifunctional epoxy resin was 100 phr, and an adhesive composition was prepared by adding 1 wt% of a curing accelerator, 5 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive.

Comparative Example 2

The bifunctional epoxy resin was 100 phr, and an adhesive composition was prepared by adding 1 wt% of a curing accelerator, 10 wt% of a rubber, 1 wt% of a coupling agent, and 5 wt% of a filler as an amine curing agent and an additive.

Comparative Example 3

The bifunctional epoxy resin was 100 phr, and an adhesive composition was prepared by adding 1 wt% of a curing accelerator, rubber 20 wt%, coupling agent 1 wt%, filler 5 wt%, and the like with an amine curing agent and an additive.

Comparative Example 4

The bifunctional epoxy resin was 100 phr, and an adhesive composition was prepared by adding 1 wt% of a curing accelerator, 30 wt% of a rubber, 1 wt% of a coupling agent, 5 wt% of a filler, and the like with an amine curing agent and an additive.

Evaluation and Results

Specimen Fabrication

The adhesive compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were applied to a polyimide film and then placed in an oven at 80 ° C. for 5 minutes to completely remove the solvent. After removing the solvent, the adhesive was bonded to the polyimide film and cured at 150 ° C. for 3 hours to complete the specimen.

Adhesion test

Peel strength of the specimens was subjected to 180˚ peel test at room temperature using a universal testing machine (INSTRON 4485) based on JIS Z0237.

Content  exam

The specimen was immersed in 10N Nitric acid, 10N NaOH, MEK for 2 minutes at room temperature, and then subjected to 180˚ peel test using a universal testing machine (INSTRON 4485) based on JIS Z0237.

Heat resistance test

After 2 seconds at 250 ℃, 2 seconds at 25 ℃ 5 cycles in the oven 180 ° Peel test was carried out in a room temperature atmosphere.

Glass transition temperature measurement

The glass transition temperature was measured using a differential scanning calorimeter (Mettler Toledo DSC 822e) at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere.

Viscoelastic  Behavior analysis

The storage modulus of the adhesive was measured using DMA (Dynamic Mechanical Analysis) from −50 ° C. to 250 ° C. at a rate of 10 ° C./min at 150 ° C. for 3 hours.

The evaluation results of Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Tables 1 and 2 below. In Table 1 and Table 2, the total amount of the siloxane imide and the epoxy resin is 100 parts by weight, and the other components represent wt%.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Siloxane imide 10 10 10 10 20 20 Epoxy resin 90 90 90 90 80 80 XNBR 5 - - - 5 - - 10 - - - 10 - - 20 - - - - - - 30 - - Curing accelerator One One One One One One Coupling agent One One One One One One Silica 5 5 5 5 5 5 Adhesive force (N / mm) normal 0.35 0.38 0.40 0.42 0.41 0.42 nitric acid 0.33 0.35 0.35 0.39 0.37 0.38 NaOH 0.30 0.34 0.34 0.36 0.35 0.37 MEK 0.31 0.34 0.36 0.38 0.34 0.37 250 ℃ 0.30 0.37 0.38 0.39 0.40 0.40 Glass transition temperature (℃) 135 130 - - 146 140 Storage modulus (MPa) ＠ 250 ℃ 7 - - - 10 -

Item Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Siloxane imide 20 20 30 30 30 30 Epoxy resin 80 80 70 70 70 70 XNBR - - 5 - - - - - - 10 - - 20 - - - 20 - - 30 - - - 30 Curing accelerator One One One One One One Coupling agent One One One One One One Silica 5 5 5 5 5 5 Adhesive force (N / mm) normal 0.45 0.47 0.42 0.44 0.46 0.50 nitric acid 0.42 0.44 0.38 0.43 0.44 0.45 NaOH 0.40 0.42 0.36 0.39 0.41 0.42 MEK 0.39 0.45 0.35 0.38 0.40 0.41 250 ℃ 0.44 0.47 0.41 0.44 0.45 0.48 Glass transition temperature (℃) - - 155 148 - - Storage modulus (MPa) ＠ 250 ℃ - - 3 - - -

Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Siloxane imide - - - - Epoxy resin 100 100 100 100 XNBR 5 - - - - 10 - - - - 20 - - - - 30 Curing accelerator One One One One Coupling agent One One One One Silica 5 5 5 5 Adhesive force (N / mm) normal 0.25 0.32 0.35 0.39 nitric acid 0.24 0.30 0.31 0.35 NaOH 0.19 0.29 0.29 0.33 MEK 0.20 0.26 0.30 0.36 250 ℃ 0.22 0.31 0.28 0.35 Glass transition temperature (℃) 130 127 120 114 Storage modulus (MPa) ＠ 250 ℃ 3 - - -

 (Unit: wt%)

Looking at the case where 5% by weight of XNBR is added in Table 1 and Table 2, in the case of a commercial epoxy (Comparative Example 1) showed an adhesive force of 0.25N / mm, 10% by weight of siloxane imide (Example 1) When 0.35N / mm Yen and 20% by weight of siloxane imide were added (Example 5) When 0.41N / mm Yen and 30% by weight of siloxane imide were added (Example 9), 0.42N / mm was added. Indicated. The adhesion of the modified epoxy system in Examples 1 to 12 showed all values of 0.3 N / mm or more. It can be seen that the modified epoxy resin system exhibits better adhesion strength than commercial epoxy resin systems.

When 10% by weight of XNBR content is added (Examples 2, 6, 10, Comparative Example 2), when 20% by weight of XNBR content is added (Examples 3, 7, 11, and Comparative Example 3), the XNBR content is 30 The same result can be confirmed also when the weight% is injected (Examples 4, 8, 12, and Comparative Example 4). It is judged that the adhesive strength of the modified epoxy resin is higher due to the influence of siloxane groups. When the specimens were measured for adhesive strength under acid, base, solvent, and thermal environment, most specimens showed retention of more than 70%. This is because the chemical resistance and heat resistance are improved due to the influence of the imide ring and the benzene ring, so that the decrease in adhesive strength is not so great.

Modified epoxy systems exhibit improved glass transition temperature values than commercial epoxy systems. Example 1, Example 2, Example 5, Example 6, Example 9 and Example 10 showed a glass transition temperature of 130 ℃ to 155 ℃. On the other hand, the glass transition temperature of Comparative Examples 1 to 4 was 114 ℃ to 130 ℃. It is judged that the modified epoxy system has improved heat resistance under the influence of the imide ring. In the case of 30% modification, the glass transition temperature of 150 ° C. or higher was increased due to the increase in the content of the imide ring, and thus, the degree of modification of the epoxy resin was most increased.

In addition, when the storage modulus at high temperature is in the range of 20 to 2000 MPa at 25 ° C and 3 to 50 MPa at 250 ° C, thermal stress generated by the difference in thermal expansion coefficient between the semiconductor wafer and the substrate can be alleviated. In Examples 1, 5, 9 and Comparative Example 1, the storage modulus was 3 to 10 MPa. Therefore, it is determined that the adhesive composition according to the present invention can alleviate the stress caused by the difference in thermal expansion coefficient between the semiconductor wafer and the substrate.

Chemical resistance

The adhesive was immersed in 10% HCl, 10% NaOH solution to immerse at room temperature for 24 hours and then checked for weight loss. The change in moisture content was measured by comparing the weight of the adhesive dried in an oven for 48 hours with the adhesive exposed for 72 hours at a temperature of 121 ° C. and a humidity of 100%.

Evaluation results such as chemical resistance of Examples 1, 5, 9 and Comparative Example 1 are shown in Table 3 below:

Referring to Table 3, both the commercial epoxy (Comparative Example 1) and the modified epoxy (Examples 1, 5, and 9) were reduced in their acid and base conditions under the original weight, and were treated with 100% humidity. The weight was increased. Specifically, in the case of the modified epoxy, as the siloxane imide content is increased, the wt% loss is decreased under acidic and basic conditions, and the wt% loss is increased under 100% humidity. As the content of siloxane imide increases, the chemical resistance is excellent due to the imide ring and the benzene ring, but the weight is increased due to the possibility of hydrogen bonding with water due to the increase of the imide ring.

Figure 1 shows an embodiment of an adhesive film prepared by applying the thermosetting adhesive composition according to the present invention.

<Explanation of symbols for the main parts of the drawings>

1 ... polyolefin film 2 ... adhesive layer

3.Adhesive layer 4 ... Polyimide film

Claims (8)

Thermosetting adhesive composition comprising a siloxane imide (A) synthesized by reacting an acid anhydride and a siloxane diamine, and a modified epoxy resin (C), a curing agent (D), and an additive (E) synthesized by reacting an epoxy resin (B). as, The siloxane imide (A) is 10 to 30 parts by weight, the epoxy resin (B) is 70 to 90 parts by weight based on 100 parts by weight of the modified epoxy resin (C), The additive (E) is 0.5 to 40 parts by weight based on 100 parts by weight of the modified epoxy resin (C), A thermosetting adhesive composition having a glass transition temperature of 130 ° C. or more and an adhesive force of 0.3 N / mm or more. According to claim 1, wherein the curing agent (D) is one or more selected from amine resin, carboxylic acid anhydride, phenol noblock resin, bisphenol noblock resin, and cresol noblock resin, 1 equivalent of modified epoxy resin (C) A thermosetting adhesive composition, characterized in that the use of 0.6 to 1.2 equivalents. The thermosetting adhesive composition of claim 1, wherein the additive comprises at least one selected from a curing accelerator, a rubber, a coupling agent, and a filler. The method of claim 3, wherein the curing accelerator is 2-methyl imidazole, 2-ethyl imidazole, 1-cyano ethyl-2-phenyl imidazole (1-cyano ethyl 2-phenyl imidazole), and triphenylphosphine (triphenylphosphine) is at least one selected from the group consisting of a thermosetting adhesive composition. 4. The thermosetting adhesive composition according to claim 3, wherein the rubber is NBR resin or SBR resin. The thermosetting adhesive composition of claim 3, wherein the coupling agent is a silane coupling agent or a titanate coupling agent. 4. The thermosetting adhesive composition according to claim 3, wherein the filler is silica, graphite, aluminum, or aluminum hydroxide. Adhesive film produced using the thermosetting adhesive composition according to claim 1.

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