KR100914821B1 - A epoxy resin composition for semiconductor's packages - Google Patents

Abstract

The present invention relates to an epoxy resin composition used for mounting a semiconductor device, and more particularly, a one-component material used for bonding a semiconductor chip and a printed circuit board during curing, and has a large difference in coefficient of thermal expansion due to the nature of the adhesive material. The present invention relates to an epoxy resin composition used for mounting a semiconductor device, which has to absorb internal stress generated therein and is excellent in securing storage stability and reliability in the B-Stage step.

Description

Epoxy resin composition used for mounting of semiconductor device {A EPOXY RESIN COMPOSITION FOR SEMICONDUCTOR'S PACKAGES}

The present invention relates to an epoxy resin composition used for mounting a semiconductor device, and more particularly, a one-component material used for bonding a semiconductor chip and a printed circuit board during curing, and has a large difference in coefficient of thermal expansion due to the nature of the adhesive material. The present invention relates to an epoxy resin composition used for mounting a semiconductor device, which has to absorb internal stress generated therein and is excellent in securing storage stability and reliability in the B-Stage step.

Recently, with the rapid development of electronic devices, new types of mounting methods such as semiconductor packages or bare chip mounting of semiconductors, which have a higher mounting density of electronic materials and a size equivalent to semiconductor chip sizes, have been applied.

Electronic devices have been enlarged with higher functions and larger capacities, but the size of semiconductor packages that implement them has become smaller. A new mounting method capable of high density and high density mounting of semiconductor chips suitable for such a change has been proposed. Among them, development and application of epoxy adhesives suitable for board on chip (BOC) package structures that bond substrates on chips proposed in memory devices to speed up signals and reduce package size due to wire bonding wire shortening are proposed. It is becoming.

The hot melt adhesive proposed in Japanese Patent Application Laid-Open No. 5-105850 has a problem in that the temperature required for adhesion is considerably high due to the high Tg of the adhesive resin, and in this process, the semiconductor chip or the printed circuit board is likely to cause thermal damage. In addition, lowering Tg in order to impart low temperature adhesion results in poor thermal resistance and high intrinsic elastic modulus of the adhesive resin, thereby reducing thermal stress between the chip and the printed circuit board caused by thermal history due to solder reflow of the printed circuit board. There is a problem that a package crack occurs because it cannot be mitigated.

U.S. Patent Application 09-549,639 proposed chip adhesion using maleimide compound or vinyl compound, but it is difficult to attach chip and printed circuit board because it is hardening method by UV irradiation and there is a problem in terms of reliability. have.

In Japanese Patent JP2001-01065, an adhesive using an epoxy resin, a curing agent, and an incompatible polymer compound has been proposed. However, the storage stability is poor and the curing conditions are sensitive. Thus, there is a problem in adhesion during process delay that may occur during the packaging process. In addition, attempts to solve the crack problem due to internal stress by inducing the island-in-sea structure of the cured product by using an incompatible system, but did not obtain a satisfactory adhesive strength due to the separation of the layer and the matrix of the island, there is a problem of peeling when evaluating the reliability.

Japanese Patent Application Laid-Open No. 61-138680 proposes an adhesive containing an inorganic filler and a compound having a urethane bond in both an acrylic resin and an epoxy resin molecule and having a primary amine at both ends. However, the film-type adhesive is mainly composed of acrylonitrile butadiene rubber, which has a drawback in that the adhesive strength is greatly reduced or the corrosion resistance is poor after long-term treatment at high temperature, and in particular, it is used due to the large deterioration of moisture resistance test results. In addition, the use of butadiene acrylonitrile copolymer and epoxy, which have been conventionally applied to solve the rigidity of epoxy resin, has a problem in controlling the reactivity, and acrylic and silicone are fundamentally inferior in adhesive strength, thereby evaluating reliability. It was not a satisfactory level.

An object of the present invention is to provide a one-component epoxy resin composition which is excellent in adhesive strength with various elements of a semiconductor mounting material and excellent storage stability according to the steps of the packaging process in order to solve the problems of the prior art as described above.

The epoxy resin composition of this invention is 10-50 weight part of aliphatic modified epoxy resins, 100-600 weight part of butadiene copolymers, 0.1-20 weight part of silane compounds, and 10-50 latent curing catalysts with respect to 100 weight part of epoxy resins. It is characterized by including 50 parts by weight and 200 parts by weight of the pigment.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

(1) epoxy resin

The epoxy resin used in the present invention is a main component of the composition used for the purpose of maintaining excellent adhesion and improving the durability of the material, etc., and has at least two or more epoxy groups in one molecule and an epoxy equivalent of 100 to 500 g / eq. It is more preferable that it is 150-300 g / eq.

Examples of the epoxy resins include bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, bisphenol-type epoxy resins such as bisphenol H, glycidyl ether epoxy resins, glycidyl amine epoxy resins, and phenol novolac types. An epoxy resin, a cresol novolak-type epoxy resin, a dimer acid modified epoxy resin, etc. are mentioned, These can be used individually or in mixture of 2 or more types. There is no restriction | limiting in particular in the mixing ratio at the time of mixing use, For example, when mixing bisphenol A and cresol novolak epoxy resin, it is preferable that the mixing ratio is 0.1-50: 99.9-50 in weight ratio, and cresol furnace with respect to bisphenol A is used. If the content ratio of the volac epoxy resin is less than 50, the adhesive strength and mechanical properties of the composition are poor, and if the content ratio is more than 99.9, the storage stability of the one-component composition and the storage stability of each process step are deteriorated.

(2) aliphatic modified epoxy resin

The aliphatic modified epoxy resin used in the present invention is a component for imparting excellent crack resistance, heat resistance, and reliable mechanical properties, which is a low molecular weight bisphenol-type epoxy resin or a polyhydric phenol compound in a mixed resin of this and a novolak epoxy resin. Or a mixture of this and an aliphatic epoxy resin in the presence of a catalyst.

The low molecular weight bisphenol-type epoxy resin used in the reaction for producing the aliphatic modified epoxy resin has a molecular weight of 200 to 3,000, an epoxy equivalent of 100 to 1000 g / eq, polyepoxide diglycidyl Ether mixtures, bisphenol-A epoxy resins, bisphenol F-type epoxy resins, and the like, and specific examples thereof include R-8815, R-8816, R-8827, R-8828, R-8829, N8010, N8020, and N8030 manufactured by KCC. Etc.

Examples of the polyhydric phenol compound used to prepare the aliphatic modified epoxy resin include 2,2-bis (p-hydroxyphenyl) propane, (2,4-dihydroxyphenyl) methane and bis (2-hydroxyphenyl). Methane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (2-isopropyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy Phenyl) ethane, 1,3-bis (3-methyl-4-hydroxyphenyl) propane, bis (4-hydroxy-2,6-dimethyl-3-methoxy) phenyl, 2,2-bis (4- Hydroxyphenyl) propane, 4,4-dihydroxyphenyl, bis (4-hydroxy-3-chloronaphthyl) ether, bis (4-hydroxy-3-bromophenyl) ether, 1,1-bis (4-hydroxyphenol) -2-phenylethane, 2,4-bis (p-hydroxyphenyl) -4-methylpentane, etc. are mentioned. It is preferable that the usage-amount of a polyhydric phenol compound is 0.1-2.0 mol with respect to 1 mol of the said low molecular weight bisphenol-type epoxy resins. If the amount of use is less than 0.1 mole, the modification rate for increasing the elongation rate is lowered, and if it exceeds 2.0 moles, the viscosity is high and workability becomes poor, which is not preferable.

The aliphatic epoxy resin that can be used in the reaction is preferably an epoxy equivalent of 200 ~ 1000g / eq, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol poly Glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentylglycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl It can select from ether, etc., and these derivatives, and it is specifically, EX-61 which is EX series by Nagase Chemical Co., Ltd. 1, EX-612, EX-512, EX-521, EX-411, EX-421, EX-301, EX-313, EX-314, EX-321, EX-211, EX-212, EX-252, EX-821, EX-830, EX-831, EX-841, EX-920, EX-921, EX-931, EPODIL-748 and EPODIL-750.

The aliphatic epoxy resin used in the reaction is preferably used in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the low molecular weight bisphenol-type epoxy resin, but when it is less than 10 parts by weight, the mechanical properties at low temperature are inferior, which is not preferable. When it exceeds 50 weight part, hardness becomes low and it is unpreferable.

As a catalyst used to prepare the aliphatic modified epoxy resin, basic amines such as sodium hydroxide, sodium hydrogen sulfate, lithium chloride, lithium oxide, tin chloride, zinc chloride, BF3-ether compound, BF3-composite compound, and quaternary ammonium salts (Lewis base); Ammonium halide salt compounds such as phenyltrimethylammonium chloride salt, tetramethylammonium salt, benzyltrimethylammonium chloride salt, dodecyltrimethylammonium chloride salt and tetraalkylammonium halogen; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2, Imidazoles such as 4-dimethylimidazole and 2-phenyl-4-methylimidazole; And ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, tri-allylphosphine, butyl allylphosphine, butyltriphenylphosphate formate, butyltriphenylphosphate oxalate, ethyltriphenylphosphate succinate, ethyltriphenyl Phosphonium salts, such as phosphonium salt compounds, its derivatives, etc. can be used.

Alternatively, the amount of the catalyst added is preferably 0.06 to 0.4 parts by weight based on 100 parts by weight of the polyhydric phenol compound. However, when the amount is less than 0.06 parts by weight, the reaction rate is lowered. Not desirable

The catalyst may be used by dissolving in solvents (ketone alcohols) for the diffusion effect.

In consideration of the effect on color during the reaction to prepare the aliphatic modified epoxy resin, an inert gas may be injected for the purpose of oxidation prevention, and a solvent may be added to adjust the reaction rate resulting from the bulk reaction. Ketone alcohol can be used as a main solvent. In addition, better results can be obtained by dividing the addition of the catalyst into primary and secondary reactions in order to control the reaction rate and excessive reaction.

When explaining the manufacturing process of the aliphatic modified epoxy resin used in the present invention in detail as follows.

When the low molecular weight bisphenol-type epoxy resin alone or this and a novolak epoxy resin are melted and a polyhydric phenol compound alone or a mixture of this and an aliphatic epoxy resin is added, the polymerization reaction is carried out at a reaction temperature of 150 to 200 ° C. It is not preferable because the physical properties of the product are deteriorated due to the remaining of the unreacted product, and if it exceeds 200 ° C, gelation due to rapid activation of the catalyst and polymerization of heterogeneous polymers appear.

It is preferable that the epoxy equivalent of the aliphatic modified epoxy resin obtained through the said reaction is 200-2000 g / eq.

The aliphatic modified epoxy resin is preferably used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the epoxy resin, but when it is less than 10 parts by weight, the mechanical strength tends to be lowered. It tends to be lowered and the elongation is high.

(3) butadiene polymer

Butadiene copolymer used in the present invention is used for the purpose of improving the adhesive strength and reliability.

The butadiene copolymer is a liquid butadiene acrylonitrile copolymer containing functional groups which react with epoxy resins such as carboxy, hydroxy or amino groups. For example, acrylonitrile-butadiene-methacrylic acid-copolymer, acrylonitrile-butadiene-methyl-methacrylate copolymer, methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-styrene-butadiene Copolymers, carboxylate butadiene acrylonitrile (CTBN), acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, chloroprene rubber and butadiene rubber, various synthetic rubbers, natural rubber, styrene-polybutadiene-styrene Styrene-based thermoplastics, such as synthetic rubbers, elastomers, polyethylene-EPDM synthetic rubbers, olefin-based thermoplastics, elastomers, caprolactone, adipate, or urethane-based thermoplastics, such as PTMG, elastomers, polybutylene terephthalate, methyl terpolymer Polyamide-based thermoplastics such as polyester-based thermoplastics, nylon-polyol-block copolymers or nylon-polyester block copolymers, such as copolymers, thermoplastics, 1,2-polybutadiene thermoplastics, and vinyl chloride-based thermoplastics. You can The elastomer components may be used alone, or may be used as a mixture of two or more of the components if the compatibility is good. Terminal-methanyl-modified polybutadienes can also be used. Among them, it is more preferable to mix and use methyl methacrylate-butadiene-styrene copolymer and acrylonitrile-butadiene rubber in terms of adhesive properties and solubility in acrylic monomers.

The butadiene copolymer is preferably used in an amount of 100 to 600 parts by weight based on 100 parts by weight of an epoxy resin. If it is less than 100 parts by weight, the adhesion is poor and adversely affects reliability. This defect causes a problem that the workability is remarkably deteriorated.

(5) silane compound

The silane compound used in the present invention is used to improve the adhesion with the epoxy resin, it may be used an alkoxy silane compound represented by the formula (2).

[Formula 2]

In said formula, R <_1> , R <_2> is a C1-C4 alkyl group, X is an alkyl group containing a functional group, and a and b represent the integer of 0-2, respectively.

Specific examples of the silane compound include β-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyl Silane coupling agents such as trimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropyltrimethoxysilane; And alkoxysilanes such as dimethylmethoxysilane, methyltrimethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, and phenyltrimethoxysilane. .

The amount of the silane compound used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin (1), but beyond this range, poor resin adhesion occurs, which is not preferable.

(6) latent curing catalyst

The latent curing catalyst used in the present invention is used for the curing rate of the epoxy resin composition, storage stability, and storage stability for each package process step, which can be prepared by reacting an amine compound with a low molecular weight epoxy resin.

The low molecular weight epoxy resin used in the reaction for preparing the latent curing catalyst to maintain the reactivity at the package temperature and storage stability in each process has a molecular weight of 200 ~ 3,000, epoxy equivalent 100 ~ 1000g / eq It is preferable that it is preferable, As said epoxy resin, Bisphenol-type epoxy resins, such as bisphenol A, bisphenol E, bisphenol F, bisphenol M, bisphenol S, bisphenol H, glycidyl ether type epoxy resin, glycidyl amine type epoxy resin And phenol novolac type epoxy resins, cresol novolac type epoxy resins, dimer acid-modified epoxy resins, and the like.

The amine compound that can be used in the reaction is preferably a molecular weight of 50 ~ 1000, for example, diethyltriamine (DETA), ethylenediamine (EDA), triethylenetetraamine (TETA), tetraethylenepentaamine (TEPA ), Aliphatic diamines such as diethylaminopropylamine (DEAPA), methanediamine (MDA), N-aminoethylpiperadine (N-AEP), m-xylenediamine (m-XDA), 1,3-bis Amino methyl cyclohexane (1,3-AC) isophoronediamine, diaminocyclohexane, 4,4-bisparaamino-cyclohexylmethane, diethylpropanediamine (N, N, -Diethyl-1,3-propanediamine) , Hydroxyethyl pentanediamine (N- (2-Hydroxyethyl) -1,3-pentanediamine), dibutylpropanediamine (N, N-di-n-butyl-1,3-propanediamine) and derivatives thereof Can be used.

The amine compound used in the reaction is preferably used in an amount of 10 to 50 parts by weight based on 100 parts by weight of an epoxy resin, but when it is less than 10 parts by weight, the active temperature of the prepared latent curing catalyst is lowered, which is not preferable because of poor storage stability. In addition, when the amount exceeds 50 parts by weight, the activity of the latent curing catalyst is lowered, which causes a problem in the function of the catalyst.

The latent curing catalyst used in the present invention is produced by melting, for example, a low molecular weight epoxy resin at 60 to 70 ° C, adding an amine compound to it, and performing a polymerization reaction at a reaction temperature of 100 to 120 ° C. If the temperature is lower than 100 ° C, the physical properties of the product are lowered due to the remaining of the unreacted material. At temperatures exceeding 120 ° C, the gelation and polymerization of the heterogeneous polymer are caused by the rapid reaction, which is not preferable.

It is preferable that the latent curing catalyst obtained through the said reaction has a molecular weight of 500-1000.

The latent curing catalyst is preferably 10 to 50 parts by weight based on (1) 100 parts by weight of the epoxy resin, but less than 10 parts by weight has a problem that the curing catalyst activity is low and the curing is delayed, 50 weight If the amount exceeds the storage stability is poor.

 (7) pigment

Pigments used in the present invention are used to control the flowability of the composition.

The amount of the pigment is preferably 50 to 200 parts by weight with respect to 100 parts by weight of the (1) epoxy resin, but less than 50 parts by weight is poor in flowability and a problem in workability, when the viscosity exceeds 200 parts by weight Becomes high, and the fall of spreadability comes.

Specific examples of the pigment include titanium dioxide (TiO ₂ ), barium sulfate (BaS0 ₄ ), calcium carbonate (CaC0 ₃ ), silica (SiO ₂ ), aluminum hydroxide (Al (OH) ₃ ), and the like.

In addition, within the scope of not impairing the object of the present invention, if necessary, conventional additives such as adhesion promoters, dispersants, thixotropic agents, antifoaming agents, wetting agents, and ion absorbers may be further included.

The epoxy resin composition of the present invention may be prepared through a vacuum degassing process after sufficiently dispersing each component by adding each component in a prescribed blending amount using a mixing stirrer. A freezer at -20 to -40 ° C within 8 hours after manufacture. It should be kept at the inside of the house and used within the pot life when used.

The present invention is explained in more detail by the following examples and comparative examples. The following examples are merely examples for illustrating the present invention and are not intended to limit the protection scope of the present invention.

Example  And Comparative example

<Potential curing catalyst Production Example >

Latent curing catalyst Production Example  One

50 g of triethylene tetraamine (available from Kukdo Chemical Co., Ltd., TETA) was placed in a flask and heated to 60 ° C. After raising the temperature, 400 g of a bisphenol A epoxy resin (equivalent 190 g / eq) was added dropwise using a dropping tank. The dropping time proceeded slowly over 4 hours so that no rapid fever occurred. The reaction was carried out at a reaction temperature of 100 to 120 ° C. for 3 hours to completely react the epoxy functional group to obtain a latent curing catalyst. Physical properties of the latent curing catalyst are as follows.

Melt viscosity: C (Butylcalbitol NV = 50%)

Latent curing catalyst Production Example  2

50 g of N-aminoethyl piperadine (N-AEP, sold by Kukdo Chemical Co., Ltd.) was placed in a flask and heated to 60 ° C. After raising the temperature, 400 g of a bisphenol A type epoxy resin (KCC Co., Equivalent: 190 g / eq) was added dropwise using a dropping tank. The dropping time proceeded slowly over 4 hours so that no rapid fever occurred. The reaction was carried out at a reaction temperature of 100 to 120 ° C. for 3 hours to completely react the epoxy functional group to obtain a latent curing catalyst. Physical properties of the latent curing catalyst are as follows.

Melt viscosity: E (Butylcalbitol NV = 50%)

Latent curing catalyst Production Example  3

50 g of diethylpropanediamine (N, N, -Diethyl-1,3-propanediamine, manufactured by OSHA) was placed in a flask and heated to 60 ° C. After raising the temperature, 300 g of a bisphenol A epoxy resin (KCC Co., Ltd., equivalent: 190 g / eq) was added dropwise using a dropping tank. The dropping time proceeded slowly over 4 hours so that no rapid fever occurred. The reaction was carried out at a reaction temperature of 100 to 120 ° C. for 3 hours to completely react the epoxy functional group to obtain a latent curing catalyst. Physical properties of the latent curing catalyst are as follows.

Melt viscosity: D (Butylcalbitol NV = 50%)

<Aliphatic Modified Epoxy Resin Production Example >

Production Example  One

600 g of polyepoxide diglycidyl ether mixture (equivalent 190 g / eq) was placed in a flask and heated to 120 to 130 ° C., and 239 g of bisphenol A and 1.2 g of ethyltriphenylphosphonium bromide (diluted 10% MeOH) were 100 ° C. And aliphatic epoxy resin (manufactured by Nagase Co., Ltd., EX931 (equivalent to 471 g / eq)) 114 g was added and reacted at 160 to 170 ° C. for about 5 hours until the phenolic OH group was completely consumed to obtain an aliphatic modified epoxy resin. . Physical properties of the resin are as follows.

Epoxy equivalent: 350g / eq, Melt viscosity: G (Butylcalbitol NV = 40%)

Production Example  2

600 g of polyepoxide diglycidyl ether mixture (equivalent 190 g / eq) was placed in a flask and heated to 120-130 ° C., and 242 g of bisphenol A and 1.2 g of triphenylphosphine (dilution of 10% benzene + toluene mixture) 100 After adding at 102 degreeC and adding 102 g of aliphatic epoxy resins (made by Nagase Corporation, EX321 (equivalent 140 g / eq)), it reacted at 160-170 degreeC for about 5 hours, and obtained the aliphatic modified epoxy resin. Physical properties of the resin are as follows.

Epoxy equivalent: 800g / eq, Melt viscosity: R (Butylcalbitol NV = 40%)

Production Example  3

600 g of polyepoxide diglycidyl ether mixture (equivalent 190 g / eq) was added to a flask, and the temperature was raised to 120 to 130 ° C., 347 g of 2,2-bisphenol A and 0.4 g of 2-ethyl-4-methylimidazole ( 10% methanol dilution) was added at 100 ° C., and 110 g of an aliphatic epoxy resin (manufactured by AIR PRODUCT, EPODIL 750 (equivalent to 130 g / eq)) was added thereto, and reacted at 160 to 170 ° C. for about 5 hours to obtain an aliphatic modified epoxy resin. Physical properties of the resin are as follows.

Epoxy equivalent: 900g / eq, Melt viscosity: R (Butylcalbitol NV = 40%)

Production Example  4

600 g of a polyepoxide diglycidyl ether mixture (equivalent 190 g / eq) was heated up to 120-130 degreeC, and 269.3 g of 2, 2-bisphenol A and a novolak-type epoxy resin N-8470 (equivalent 207 g / eq, KCC) Co., Ltd.) 86 g and ethyl triphenylphosphonium bromide 1.34 g (10% methanol dilution) were added at 120 ° C., and 119 g of an aliphatic epoxy resin (manufactured by AIR PRODUCT, EPODIL 748 (equivalent to 140 g / eq)) was added thereto. The mixture was reacted at about 5 hours for an aliphatic modified epoxy resin. Physical properties of the resin are as follows.

Epoxy equivalent: 810g / eq, Melt viscosity: V (Butylcarbitol NV = 40%)

Production Example  5

Poly (butadiene) core / poly (methyl) to resin which mixed 600 g of polyepoxide diglycidyl ether mixture (equivalent 189 g / eq) and 47 g of aliphatic epoxy resin EX-252 (equivalent 215 g / eq, Nagase Chemical Co., Ltd. make) Methacrylate) 121 g of carboxyl shell (EXL-2611, manufactured by Rohm & Haas Co.) was dispersed at 80 to 90 ° C. for about 2 hours, then heated to 120 to 130 ° C. and held for 2 hours to maintain the epoxy equivalent. 220 g / After making it eq, 277 g of 2, 2-bisphenol A and 0.2 g of triphenylphosphine catalysts were added at 120 degreeC, and it reacted at 170-180 degreeC for about 4 hours, and obtained core shell rubber modified epoxy resin. Physical properties of the resin are as follows.

Epoxy equivalent: 990g / eq, Melt viscosity: U (Butylcarbitol NV = 40%)

Softening point: 111 ℃ (mettler, 2 ℃ .min / 90 ℃), color: 1.0 ↓

Example  And Comparative example

After mixing each component in the compounding ratio (weight ratio) shown in following Table 1 (Example) and Table 2 (comparative example), the epoxy resin composition was manufactured, and the physical property evaluation test was done by the following method.

Evaluation

1) Storage stability

Viscosity change at room temperature of the one-component composition was measured. A curing exotherm curve of time-temperature was obtained. In this curve, storage stability was made into the time below the time point which increases 2 times of an initial viscosity.

2) B-Stage storage stability

It means storage stability in the process for bonding chips after curing under B-Stage conditions, and if it is possible to bond chips based on 2 hours when stored at room temperature after B-stage curing, it is marked as bad.

3) Workability

The thing suitable for the viscosity and thixotropy standard value (viscosity: 30000-60000 mPa, thixotropy: 3-6) was made favorable for the workability evaluation suitable for spraying or the screen-printing system by the application | coating method of an epoxy resin composition.

4) Shear Strength

Five samples were tested at 20 ° C. by the ISO 4587 method. Samples are usually metals connected by aluminum plates

It is a bad condition that the adhesive site is destroyed when broken, and it is a good condition that the adhesive itself is broken.

5) Tensile modulus of film made of material

Tensile curves reveal the maximum tensile modulus when the sample breaks. The good condition of the tensile modulus is 1.5 ± 0.5 MPa.

Measuring conditions

Crosshead Speed: 25mm / min

Curing condition: 175 ℃ × 30 minutes curing

Measuring Temperature: 25 ℃

6) THB (Temperature High Bias)

Temperature: 85 ° C / humidity: Good or poor was judged by peeling after 116 hours storage at 85% RH / vacuum state.

7) T / C (Thermo cycle)

Good and inferiority were judged by peeling after 116 hours of temperature -55 degreeC-125 degreeC repeated test.

8) Pressure cycle test (PCT)

Good or poor was judged by peeling after 116 hours storage at a temperature of 121 DEG C / pressure 0.2 MPa / humidity 100% RH.

9) Highly Accelerated Temperature and humidity stress test (HAST)

Good and poor were judged by peeling after 45 hours storage at a temperature of 130 ° C./humidity of 85% RH / Vcc.

The results of the above test are shown in Table 3 (Example) and Table 4 (Comparative Example).

                                                               (Unit: weight part) Example One 2 3 4 5 6 Epoxy resin ¹⁾ N8470 100 50 50 100 80 70 Epoxy resin ²⁾ R8828 0 50 50 0 20 30 Aliphatic modified epoxy resin Preparation Example 1 10 10 30 30 Preparation Example 2 10 Preparation Example 3 30 Butadiene Copolymer ³⁾ CTBN 100 100 500 500 500 500 Silane compound ⁴⁾ A-187 5 5 5 5 5 5 solvent acetate 200 200 200 200 200 200 Latent curing catalyst Preparation Example 1 20 50 Preparation Example 2 20 50 Preparation Example 3 20 50 Silica ⁵⁾ R972 50 50 50 50 50 50 Ion absorbers ⁶⁾ antimony 50 50 50 50 50 50 Antifoam ⁷⁾ BYK-A501 One One One One One One Humectant ⁸⁾ BYK-110 5 5 5 5 5 5

1) N8470: cresol novolac epoxy resin (manufactured by KCC, equivalent 250 g / eq)

2) R8828 bisphenol A epoxy resin (manufactured by KCC, Equivalent 190g / eq)

3) CTBN: carboxylate butadiene acrylonitrile (EMELARD company (USA))

4) A-187: γ-glycidoxypropyltrimethoxysilane (manufactured by OSI)

5) R972: Silica (manufactured by DAGGUSA-HULTS)

6) Antimony: manufactured by Nihon Seiko Corporation

7) BYK-A501: made by BYK

8) BYK-110: manufactured by BYK

                                                                (Unit: weight part) Comparative example One 2 3 4 5 6 Epoxy resin N8470 0 30 100 100 100 100 Epoxy resin R8828 100 70 0 0 0 0 Aliphatic modified epoxy resin Preparation Example 4 80 70 Preparation Example 5 10 70 Butadiene Copolymer CTBN 100 200 200 0 800 200 Silane compound A-187 5 5 5 5 5 0 solvent acetate 200 200 200 200 200 200 Latent curing catalyst Preparation Example 3 30 0 30 30 0 70 ¹⁾ 2PZ 0 30 0 0 0 0 Silica R972 50 50 50 50 50 50 Ion absorbers antimony 50 50 50 50 50 50 Antifoam BYK-A501 One One One One One One Humectant BYK-110 5 5 5 5 5 5

1) 2PZ: 2-phenyl imidazole (manufactured by Shikoku Chemical Co., Ltd.)

Example One 2 3 4 5 6 Storage stability Good Good Good Good Good Good B-Stage storage stability Good Good Good Good Good Good Workability Good Good Good Good Good Good Shear bond strength Good Good Good Good Good Good Tensile modulus 1.5 1.5 1.6 One One 1.2 THB Good Good Good Good Good Good T / C Good Good Good Good Good Good PCT Good Good Good Good Good Good HAST Good Good Good Good Good Good

Comparative example One 2 3 4 5 6 Storage stability Good Bad Good Good Good Bad B-Stage storage stability Good Bad Good Good Good Bad Workability Good Good Good Good Bad Good Shear bond strength Bad Bad Good Good Good Good Tensile modulus 1.3 1.1 3.6 1500 0 5 THB Bad Bad Bad Bad Bad Bad T / C Bad Bad Bad Bad Bad Bad PCT Bad Bad Bad Bad Bad Bad HAST Bad Bad Bad Bad Bad Bad

According to the present invention, an epoxy resin composition used in a semiconductor mounting process having a large difference in coefficient of thermal expansion due to characteristics of an adhesive material to absorb internal stress generated therein and having excellent storage stability and storage stability and reliability in the B-stage step is provided. Can provide.

Claims (12)

Aliphatic modification produced by reacting a polyhydric phenol compound or a mixture of this and an aliphatic epoxy resin with a bisphenol-type epoxy resin having a molecular weight of 200 to 3,000 or a mixed resin of this and a novolac epoxy resin in the presence of a catalyst with respect to 100 parts by weight of the epoxy resin. 10 to 50 parts by weight of a latent curing catalyst prepared by reacting 10 to 50 parts by weight of an epoxy resin, 100 to 600 parts by weight of a butadiene copolymer, 0.1 to 20 parts by weight of a silane compound and an epoxy resin having a molecular weight of 200 to 3,000, and An epoxy resin composition comprising 50 to 200 parts by weight of a pigment. According to claim 1, wherein the epoxy resin is a bisphenol epoxy resin, glycidyl ether epoxy resin, glycidyl amine epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin and dimer acid-modified epoxy resin It is 1 type, or 2 or more types chosen from the epoxy resin composition characterized by the above-mentioned. The epoxy resin composition according to claim 2, wherein the epoxy resin has an epoxy equivalent of 100 to 500 g / eq. The epoxy resin composition according to claim 2, wherein the epoxy resin has a mixing ratio of bisphenol A epoxy resin and cresol novolac epoxy resin in a weight ratio of 0.1 to 50: 99.9 to 50. delete The epoxy resin composition according to claim 1, wherein the aliphatic epoxy resin is used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the bisphenol type epoxy resin having a molecular weight of 200 to 3,000. The epoxy resin composition of claim 1, wherein the aliphatic modified epoxy resin has an epoxy equivalent of 200 to 2000 g / eq. The epoxy resin composition according to claim 1, wherein the butadiene copolymer is a liquid butadiene acrylonitrile copolymer containing a carboxy, hydroxy or amino group. The epoxy resin composition according to claim 1, wherein the silane compound is an alkoxy silane compound. delete The method of claim 1, wherein the amine compound is diethyltriamine, ethylenediamine, triethylenetetraamine, tetraethylenepentaamine, diethylaminopropylamine, methanediamine, N-aminoethylpiperadine, m-xylenediamine, 1,3-bisamino methyl cyclohexane (1,3-AC) isophoronediamine, diaminocyclohexane, 4,4-bisparaamino-cyclohexylmethane, diethylpropanediamine, hydroxyethylpentanediamine, dibutyl Epoxy resin composition, characterized in that selected from propanediamine and derivatives thereof. The epoxy resin of claim 1, wherein the epoxy resin having a molecular weight of 200 to 3,000 is bisphenol type epoxy resin, glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Epoxy resin composition, characterized in that selected from dimer acid-modified epoxy resin.