KR101549742B1 - Epoxy resin composition and apparatus prepared from using the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition comprising an epoxy resin, a curing agent, and a curing catalyst, wherein the curing catalyst comprises a phosphonium compound of formula (I), and an apparatus manufactured using the same.

Description

[0001] EPOXY RESIN COMPOSITION AND APPARATUS PREPARED FROM USING THE SAME [0002]

The present invention relates to an epoxy resin composition and an apparatus manufactured using the same.

Epoxy resins are excellent in electrical and mechanical properties, and have excellent processability and chemical resistance. They are used in matrices and coatings for electrical, electronic, architectural and composite materials. For example, epoxy resins are used for sealing semiconductor devices, insulating resin sheets such as adhesive films, prepregs, circuit boards, solder resists, underfill materials, die bonding materials, and component replenishment resins.

The epoxy resin is mixed with a curing agent rather than being used alone, and is used after being cured with a thermosetting material. In this case, since the performance of the epoxy resin depends on the three-dimensional structure generated after curing, selection of a curing agent is important. Although many conventional epoxy resin hardeners have been developed, curing catalysts are used together to catalyze the curing reaction. In an apparatus in which an epoxy resin composition is used, curing is catalyzed only at a desired curing temperature for the purpose of improving low-temperature curability enabling curing at low temperatures for the purpose of improving productivity and improving handling properties during storage, , There is a demand for a curing catalyst having high storage stability without curing catalyst activity. The curing catalyst, which is an addition product of triphenylphosphine and 1,4-benzoquinone, exhibits a curing accelerating effect even at a relatively low temperature, so that heat generated when mixing with an epoxy resin or the like before curing, The curing of the epoxy resin composition can be partially progressed, and even when the epoxy resin composition is stored at room temperature after mixing the respective components of the resin composition, the curing is promoted and the storage stability is deteriorated. The progress of the curing reaction may lead to an increase in viscosity and a decrease in fluidity when the epoxy resin composition is a liquid, and when the epoxy resin composition is solid, it may manifest viscous property, and such a change in state may occur uniformly in the epoxy resin composition It does not appear. Therefore, when the epoxy resin composition is actually subjected to a curing reaction at a high temperature, the moldability may deteriorate due to the lowering of fluidity, and the mechanical, electrical and chemical properties of the molded product may be deteriorated.

In this regard, Korean Patent No. 10-0290448 discloses an epoxy resin curing catalyst which is a carboxylic acid salt of bicyclic amidine.

An object of the present invention is to provide an epoxy resin composition which can be cured even at a low temperature.

Another object of the present invention is to provide an epoxy resin composition having high storage stability which catalyzes curing only when a desired curing temperature is reached and no curing catalyst activity when the curing temperature is not a desired curing temperature.

It is another object of the present invention to provide an epoxy resin composition which minimizes viscosity change even under a predetermined range of time and temperature conditions and exhibits reduced moldability due to lowering of fluidity when subjected to a curing reaction at a high temperature and mechanical, To provide a composition.

An epoxy resin composition according to one aspect of the present invention comprises an epoxy resin, a curing agent, and a curing catalyst, and the curing catalyst may include a phosphonium-based compound represented by the following formula (1)

≪ Formula 1 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are as defined in the following description).

An apparatus which is another aspect of the present invention can be produced by using the above epoxy resin composition.

The present invention provides a high storage stability epoxy resin composition which is curable at a low temperature, catalyzes curing only when the desired curing temperature is reached, and eliminates the curing catalyst activity when not the desired curing temperature. The present invention also provides a method for producing epoxy resin composition, which minimizes viscosity change even under a predetermined time and temperature condition to cause degradation of moldability due to lowered fluidity when the epoxy resin composition is cured at a high temperature, To give a resin composition.

The epoxy resin composition of the present invention comprises an epoxy resin, a curing agent, and a curing catalyst, and the curing catalyst may include a phosphonium-based compound represented by the following formula:

≪ Formula 1 >

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1-10 carbon atoms, a substituted or unsubstituted group having 6-20 A substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms). As used herein, the term "substituted or unsubstituted" means that a hydrogen atom is replaced by an amino group, a nitro group, an alkyl group having 1-10 carbon atoms, a halogen, an aryl group having 6-20 carbon atoms, or a cycloalkyl group having 3-10 carbon atoms .

For example, R ₁ , R ₂ , R ₃ and R ₄ are substituted or unsubstituted aryl groups having 6 to 10 carbon atoms or substituted or unsubstituted arylalkyl groups having 7 to 12 carbon atoms, and R ₅ and R ₆ are hydrogen , An alkyl group having 1-10 carbon atoms, or an aryl group having 6-10 carbon atoms.

The phosphonium-based compound contains a phosphonium-based cation and a dithiocarbamate anion and may be added to a composition containing at least one of an epoxy resin and a curing agent to be used as a latent curing catalyst. That is, when the phosphonium-based compound receives external energy such as heat, it decomposes into a phosphine-based compound and an anion / cation compound at 100 to 120 ° C as shown in the following reaction formula 1:

<Reaction Scheme 1>

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are as defined in Formula 1).

The resulting phosphine-based compound reacts with the epoxide group in the epoxy resin to effect a ring-opening reaction. After the ring-opening reaction, the ring-opening reaction of the epoxide group by reaction with the hydroxyl group in the epoxy resin, the chain terminal of the activated epoxy resin and the epoxide Reaction and so on.

In particular, the phosphonium-based compound has the advantage of being capable of catalyzing the curing reaction between the epoxy resin and the curing agent, and having high curability at low temperature and high storage stability. Said "storage stability" catalyzes curing only when the desired curing temperature is reached, and when not the desired curing temperature, there is no curing catalytic activity, so that the epoxy resin composition can be stored for a prolonged period of time without viscosity changes. In general, the progress of the curing reaction may lead to an increase in the viscosity and a decrease in the fluidity when the epoxy resin composition is a liquid, and to develop viscosity when the epoxy resin composition is solid.

The phosphonium-based compound may have a glass transition temperature of 100 to 130 캜, for example, 120 to 125 캜. The phosphonium-based compound may be a water-insoluble compound. The phosphonium-based compound may have a starting temperature of 80 to 120 ° C and a peak temperature of 120 to 180 ° C by differential scanning calorimetry (DSC). Within this range, there may be effects of low temperature curing with low starting and peak temperatures.

The phosphonium compound can be prepared by a conventional method. Can be prepared, for example, by reacting a phosphonium-based cation-containing compound represented by the following formula (2) with a dithiocarbanate anion-containing compound represented by the following formula (3)

(2)

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ are as defined in Formula 1, and X is halogen).

(3)

(Wherein R ₅ and R ₆ are as defined in Formula 1, and M is an alkali metal or Ag).

The halogen may be fluorine, chlorine, bromine, or iodine, and the alkali metal may be lithium, sodium, potassium, rubidium, cesium, or francium.

The phosphonium-based cation-containing compound may be prepared by coupling an alkyl halide, an aryl halide, or an aralkyl halide with a phosphine-based compound in a solvent, or a phosphonium-based cation-containing salt may be used. The dithiocarbamate anion- The carbamate anion-containing salt may be used. Examples of the phosphine-based compound may include triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine, and the like . The dithiocarbamate anion-containing salt may be dimethyldithiocarbamate, diethyldithiocarbamate, dibutyldithiocarbamate, alkali metal salt of dibenzyldithiocarbamate anion, and the like.

The reaction of the general formula (2) and the general formula (3) can be carried out in an organic solvent such as methylene chloride, acetonitrile, N, N-dimethylformamide, toluene, etc. and is carried out at a temperature of 10 to 100 ° C, For example, 20 to 30 hours, and the phosphonium cation-containing compound: dithiocarbamate anion-containing compound can be reacted at a molar ratio of 1: 0.9 to 1: 1.5. Within this range, it is possible to synthesize a substance having a phosphonium-based cation and a dithiocarbamate anion. The reaction can be carried out by mixing a phosphonium-based cation-containing compound and a dithiocarbamate anion-containing compound, and the phosphonium-based compound is produced by bonding an alkyl halide, an aryl halide or an aralkyl halide to a phosphine- and without additional separation processes in situ with a dithiocarbamate anion-containing compound.

The phosphonium-based compound is advantageous in that when it is contained in an epoxy resin composition including an epoxy resin, a curing agent, etc., the storage stability can be secured in the salt type and the low temperature curing property is obtained due to the dithiocarbamate anion. The phosphonium-based compound may be contained in the epoxy resin composition in an amount of 0.01 to 5% by weight, specifically 0.01 to 2% by weight, more specifically 0.02 to 1.5% by weight and more particularly 0.05 to 1.5% by weight. Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.

The epoxy resin is an epoxy resin having two or more epoxy groups in the molecule, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, Epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, A halogenated epoxy resin, a phenol aralkyl type epoxy resin, and the like, which may be used alone or in combination of two or more. For example, the epoxy resin may be an epoxy resin having two or more epoxy groups in the molecule and at least one hydroxyl group. The epoxy resin may include at least one of a solid epoxy resin and a liquid epoxy resin.

In one embodiment, the epoxy resin may be a biphenyl type epoxy resin of the following formula:

&Lt; Formula 4 >

(Wherein R is an alkyl group having 1 to 4 carbon atoms and n has an average value of 0 to 7)

The epoxy resin may be included in the composition in an amount of from 2 to 17% by weight, for example, from 3 to 15% by weight, for example, from 3 to 12% by weight, based on the solid content. Within this range, the curability of the composition may not be deteriorated.

The curing agent is selected from the group consisting of phenol aralkyl type phenol resin, phenol novolac type phenol resin, xylock type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Novolak type phenol resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, di Aminodiphenylmethane, diaminodiphenylsulfone, and other aromatic amines. Preferably, the curing agent may be a phenolic resin having at least one hydroxyl group.

In one embodiment, the curing agent can be at least one of a xylyl phenolic resin of formula (5), a phenol aralkyl phenolic resin of formula (6)

&Lt; Formula 5 >

(The average value of n in the above formula (5) is 0 to 7.)

(6)

(The average value of n in Formula 6 is 1 to 7)

The curing agent may be contained in an amount of 0.5 to 13% by weight, for example, 1 to 10% by weight, for example, 2 to 8% by weight, based on the solid content in the epoxy resin composition. Within this range, the curability of the composition may not be deteriorated.

The epoxy resin composition may further include an inorganic filler.

The inorganic filler can improve mechanical properties and low stress of the composition. Examples of the inorganic filler may include at least one of fused silica, crystalline silicate, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, have.

Preferably, fused silica having a low linear expansion coefficient is used for low stress. The fused silica refers to amorphous silica having a true specific gravity of 2.3 or less and includes amorphous silica obtained by melting crystalline silica or synthesized from various raw materials. Although the shape and the particle diameter of the fused silica are not particularly limited, the fused silica containing 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and the spherical fused silica having an average particle diameter of 0.001 to 1 탆 in an amount of 1 to 50% It is preferable that the mixture is contained in an amount of 40 to 100% by weight based on the total filler. In addition, the maximum particle diameter may be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the purpose of use. The molten spherical silica may contain conductive carbon as a foreign substance on the surface of silica, It is also important to choose these fewer substances.

The amount of the inorganic filler to be used varies depending on required properties such as moldability, low stress, and high temperature strength. In an embodiment, the inorganic filler may be included in the epoxy resin composition in an amount of 70 to 95% by weight, for example, 75 to 92% by weight. Within the above range, flame retardancy, fluidity and reliability of the epoxy resin composition can be secured.

The epoxy resin composition may further include a non-phosphonium-based curing catalyst that catalyzes the reaction of the epoxy resin with the curing agent and does not contain phosphonium. As the non-phosphonium curing catalyst, tertiary amines, organometallic compounds, organic phosphorus compounds, imidazoles, and boron compounds can be used. Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris ) Phenol and tri-2-ethylhexyl acid salt. Organometallic compounds include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Organophosphorous compounds include tris-4-methoxyphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct and the like have. Imidazoles include, but are not limited to, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl- Imidazole and the like. Examples of the boron compound include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboron monoethylamine, tetrafluoroborantriethylamine, tetrafluoroborane amine, and the like . In addition, 1,5-diazabicyclo [4.3.0] non-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene: DBN), 1,8-diazabicyclo [5.4. 1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts. Particularly preferable curing accelerators include organic phosphorus compounds, boron compounds, amine-based compounds, and imidazole-based curing accelerators, either alone or in combination. As the curing accelerator, it is also possible to use an adduct formed by reacting with an epoxy resin or a curing agent. Of the total curing catalysts, the phosphonium compound of the present invention may be contained in an amount of 10 to 100% by weight, for example, 10 to 70% by weight, and the curing reaction time is not delayed in the above range, . The curing catalyst may be included in the epoxy resin composition in an amount of 0.01 to 5% by weight, specifically 0.01 to 3% by weight, more specifically 0.02 to 2.0% by weight, more particularly 0.05 to 2.0% by weight. Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.

The composition of the present invention may further include conventional additives included in the composition. In embodiments, the additive may include at least one of a coupling agent, a release agent, a stress relieving agent, a crosslinking enhancer, a leveling agent, and a colorant.

The coupling agent may be at least one selected from the group consisting of epoxy silane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto. The coupling agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.

As the releasing agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt can be used. The release agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.

The stress relieving agent may be at least one selected from the group consisting of modified silicone oil, silicone elastomer, silicone powder, and silicone resin, but is not limited thereto. The stress relieving agent is preferably contained in the epoxy resin composition in an amount of 0 to 6.5% by weight, for example, 0 to 1% by weight, for example, 0.1 to 1% by weight, and may be contained selectively or both . As the modified silicone oil, a silicone polymer having excellent heat resistance is preferable, and a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, and a silicone oil having a carboxyl functional group, or the like, 0.05 to 1.5% by weight based on the total weight of the composition. However, when the amount of the silicone oil is more than 1.5% by weight, surface contamination is liable to occur and the resin bleed may be prolonged. When the silicone oil is used in an amount of less than 0.05% by weight, a sufficient low elastic modulus may not be obtained have. The silicone powder having a median particle diameter of 15 탆 or less is particularly preferable because it does not act as a cause of degradation in moldability and may be contained in an amount of 0 to 5% by weight, for example, 0.1 to 5% by weight, based on the whole resin composition . The colorant may be carbon black or the like and may be contained in an amount of 0.1 to 1% by weight based on the total composition.

The additive may be included in the epoxy resin composition in an amount of 0.1 to 10% by weight, for example, 0.1 to 3% by weight.

The epoxy resin composition can be cured at a low temperature, for example, the curing initiation temperature can be 80 to 120 占 폚. Within this range, there is an advantage that the curing proceeds sufficiently even at a low temperature.

Since the epoxy resin composition contains a phosphonium compound as a curing catalyst, the storage stability is high, and even if stored at a predetermined temperature for a predetermined time, hardening does not proceed and the viscosity change of the epoxy resin composition is low. According to one embodiment, the epoxy resin composition may have a viscosity change rate of 20% or less, for example, 0 to 20%, for example, 7 to 18.5% in the following formula 1:

<Formula 1>

Viscosity change rate = | B-A | / A x 100

(Unit: cPs), B is the viscosity (unit: cPs) measured at 25 占 폚 after the epoxy resin composition is allowed to stand at 25 占 폚 for 48 hours under the condition of 25 占 폚, to be).

In the above range, the curing is catalyzed only when the curing temperature is high due to high storage stability. When the curing temperature is not the desired curing temperature, there is no curing catalyst activity, and when the curing reaction is actually carried out at a high temperature, , There may be no deterioration in electrical and chemical properties. In embodiments, A may be between 100 and 3000 cPs, and B may be between 100 and 3000 cPs.

The epoxy resin composition can have a flow length of 59-75 inches by transfer molding press at 175 ° C and 70 kgf / cm ² in EMMI-1-66. Within this range, it can be used for the use of epoxy resin composition.

The epoxy resin composition may have a curing shrinkage of less than 0.4%, for example, from 0.01 to 0.39%, as measured by the following formula 2:

[Formula 2]

Cure shrinkage rate = | C - D | / C x 100

C is the length of the specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; ² &gt;, D is the specimen after curing at 170 to 180 DEG C for 4 hours, Lt; / RTI &gt; Within this range, the curing shrinkage is low and can be used as an epoxy resin composition.

The use of the resin composition of the present invention is not limited to the use of the epoxy resin composition such as an insulating resin sheet such as an adhesive film or prepreg, a circuit board, a solder resist, an underfill, a die bonding material, But it is not limited thereto.

(1) Sealing for semiconductor devices

The composition of the present invention can be used for sealing semiconductor devices and can include an epoxy resin, a curing agent, a curing catalyst containing a phosphonium compound, an inorganic filler, and an additive.

According to one embodiment, the epoxy resin may be contained in an amount of 2 to 17% by weight, for example, 3 to 12% by weight, and the flowability, flame retardancy and reliability of the epoxy resin composition may be good within the above range, 0.01 to 5% by weight, for example, 0.05 to 1.5% by weight. In this range, unreacted epoxy groups and phenolic hydroxyl groups are not generated in a large amount and reliability can be excellent. The amount of the inorganic filler may be 70 to 95% by weight, for example, 75 to 92% by weight, and preferably 2 to 8% by weight. And the flame retardancy, fluidity and reliability of the epoxy resin composition can be ensured within the above range, and 0.1 to 10% by weight, for example, 0.1 to 3% by weight of additives can be contained have.

The epoxy resin in the epoxy resin composition may be used alone or as an additive compound prepared by a linear reaction such as a curing agent, a curing catalyst, an additive such as a releasing agent, a coupling agent, a stress relaxation agent, and a melt master batch have. The method for producing the epoxy resin composition of the present invention is not particularly limited, but it is preferable that the components contained in the composition are homogeneously mixed using a Henschel mixer or a Loedige mixer, Melt-kneading, cooling, and pulverizing processes.

A method of sealing a semiconductor device using the composition of the present invention is most commonly used for a low pressure transfer molding method. However, it can also be formed by a method such as an injection molding method or a casting method. According to the above method, a lead frame pre-plated with a copper lead frame, an iron lead frame, or at least one material selected from the group consisting of nickel and palladium on the lead frame, or a semiconductor element of an organic laminate frame is manufactured .

(2) Adhesive film

The epoxy resin composition can be applied on a support film and cured to be used for an adhesive film for a printed wiring board. The adhesive film can be formed by a method known to a person skilled in the art, for example, by dissolving the organic solvent composition, applying the composition using the support film as a support, and drying the organic solvent by heating or hot air blowing, Ketones such as acetone and methyl ethyl ketone, acetic acid esters such as ethyl acetate and butyl acetate, carbohydrates such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene, and amide solvents such as dicetylformamide And may be used alone or in combination of two or more. The drying conditions are not particularly limited, but they can be dried at 50 to 100 ° C for 1 to 10 minutes by drying to make the content of the organic solvent in the coating layer 10% or less. The support film may be a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, a polycarbonate, or a polyimide. The thickness of the support film may be 10 to 150 mu m.

(3) Prepreg

The epoxy resin composition can be used as a prepreg by impregnating the sheet-like reinforcing base material and heating it to half-harden. As the reinforcing base material, there is no particular limitation, and it is commonly used in prepregs and includes fibers for prepregs such as glass cloths and aramid fibers .

The apparatus of the present invention can be manufactured using the above epoxy resin composition. For example, the device may be a semiconductor device sealed with an epoxy resin composition, a multilayer wiring board including an adhesive film formed from an epoxy resin composition, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example  One

 2.6 g of triphenylphosphine and 2.2 g of 4-nitrobenzyl bromide were dissolved in 30 ml of toluene, and the reaction was carried out at 110 ° C for 3 hours. The resulting precipitate was filtered and dried to obtain 3.0 g of a solid. 3.0 g of the obtained solid was dissolved in 50 ml of methylene chloride, and 1.2 g of sodium diethyldithiocarbamate was reacted at room temperature for 24 hours. The precipitate was filtered out and the liquid obtained was evaporated under reduced pressure to obtain 1.0 g of a solid. 7. &Lt; / RTI &gt;

&Lt; Formula 7 >

^{1 H NMR (400 MHz, DMSO} ) 8.10 (d, J = 7.4Hz, 2H), 7.93 (m, 3H), 7.82-7.65 (m, 12H), 7.27 (d, J = 7.4Hz, 2H), 5.40 (d, J = 5.2 Hz, 2H), 4.05 (q, J = 7.4 Hz, 4H), 1.20 (t, J = 7.4 Hz, 6H) ppm; ¹³ C NMR (100 MHz, DMSO) 207.3, 145.5, 135.1, 134.4, 131.2, 130.2, 130.1, 129.9, 129.8, 128.1, 128.0, 122.8, 122.4, 48.0, 41.4, 12.7, ppm; ³¹ P NMR (166 MHz, DMSO) 24.1 ppm; LC-MS m / z = 546 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₀ H ₃₁ N ₂ O ₂ PS ₂ : C, 65.91; H, 5.72; N, 5.12; S, 11.73. Found: C, 65.94; H, 5.56; N, 5.43; S, 11.84.

Example  2

2.6 g of triphenylphosphine and 1.7 g of benzyl bromide were dissolved in 30 ml of toluene, and the reaction was carried out at 110 ° C. for 3 hours. The resulting precipitate was filtered and dried to obtain 3.0 g of a solid. 3.0 g of the obtained solid was dissolved in 50 ml of methylene chloride, and 1.2 g of sodium diethyldithiocarbamate was reacted at room temperature for 24 hours. The precipitate was filtered out and the liquid obtained was evaporated under reduced pressure to obtain 1.0 g of a solid. 8 &lt; / RTI &gt;

(8)

^{1 H NMR (400 MHz, DMSO} ) 7.91-6.94 (m, 20H), 5.40 (d, J = 5.4Hz, 2H), 4.04 (q, J = 7.4Hz, 4H), 1.21 (t, J = 7.4Hz , 6H) ppm; ¹³ C NMR (100 MHz, DMSO) 207.2, 135.5, 134.5, 134.4, 131.2, 129.9, 129.8, 129.7, 128.2, 128.1, 127.8, 118.2, 118.0, 47.8, 41.0, 12.6 ppm; ³¹ P NMR (166 MHz, DMSO) 24.5 ppm; LC-MS m / z = 501 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₀ H ₃₂ NPS ₂ : C, 71.82; H, 6.43; N, 2.79; S, 12.78. Found: C, 71.86; H, 6.67; N, 2.30; S, 12.54.

Example  3

Tetraphenylphosphonium bromide (4.3 g) was dissolved in 50 ml of methylene chloride, and 1.2 g of sodium dipropyldithiocarbamate was reacted at room temperature for 24 hours. The precipitate was filtered out and the obtained liquid was evaporated under reduced pressure to obtain 2.0 g of a solid. 9. &Lt; / RTI &gt;

&Lt; Formula 9 >

¹ H NMR (400 MHz, DMSO) 8.05-7.65 (m, 20H) 4.04 (t, J = 7.4 Hz, 4H), 1.45 (m, 4H), 0.93 (t, J = 7.4 Hz, 6H) ppm; ¹³ C NMR (100 MHz, DMSO) 203.6, 135.5, 134.2, 134.0, 130.1, 130.0, 129.9, 118.8, 118.3, 53.4, 21.3, 11.9 ppm; ³¹ P NMR (166 MHz, DMSO) 24.30 ppm; LC-MS m / z = 515 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₁ H ₃₄ NPS ₂ : C, 72.20; H, 6.65; N, 2.72; S, 12.44. Found: C, 71.88; H, 6.44; N, 2.53; S, 12.46.

Example  4

 2.6 g of triphenylphosphine and 2.2 g of 4-nitrobenzyl bromide were dissolved in 30 ml of toluene, and the reaction was carried out at 110 ° C for 3 hours. The resulting precipitate was filtered and dried to obtain 3.0 g of a solid. 3.0 g of the obtained solid was dissolved in 50 ml of methylene chloride, and 1.2 g of sodium dipropyldithiocarbamate was reacted at room temperature for 24 hours. After precipitation was filtered out, the liquid obtained was evaporated under reduced pressure to obtain 1.0 g of a solid. 10. &Lt; / RTI &gt;

&Lt; Formula 10 >

^{1 H NMR (400 MHz, DMSO} ) 8.12 (d, J = 7.4Hz, 2H), 7.94 (m, 3H), 7.82-7.60 (m, 12H), 7.24 (d, J = 7.4Hz, 2H), 5.40 (d, J = 5.2 Hz, 2H), 4.06 (t, J = 7.4 Hz, 4H), 1.47 (m, 4H), 0.94 (t, J = 7.4 Hz, 6H) ppm; ¹³ C NMR (100 MHz, DMSO) 203.3, 145.5, 135.1, 134.4, 131.2, 130.2, 130.1, 129.9, 129.8, 128.1, 128.0, 122.5, 122.1, 53.4, 41.4, 21.3, 11.9 ppm; ³¹ P NMR (166 MHz, DMSO) 24.5 ppm; LC-MS m / z = 574 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₂ H ₃₅ N ₂ O ₂ PS ₂ : C, 66.87; H, 6.14; N, 4.87; S, 11.16. Found: C, 66.80; H, 6.25; N, 4.78; S, 11.50.

Example  5

2.6 g of triphenylphosphine and 2.2 g of benzyl bromide were dissolved in 30 ml of toluene, and the reaction was carried out at 110 ° C. for 3 hours. The resulting precipitate was filtered and dried to obtain 3.0 g of a solid. 3.0 g of the obtained solid was dissolved in 50 ml of methylene chloride, and 1.2 g of sodium dipropyldithiocarbamate was reacted at room temperature for 24 hours. After precipitation was filtered out, the liquid obtained was evaporated under reduced pressure to obtain 1.0 g of a solid. 11. &Lt; / RTI &gt;

&Lt; Formula 11 >

^{1 H NMR (400 MHz, DMSO} ) 7.91-6.94 (m, 20H), 5.40 (d, J = 5.4Hz, 2H), 4.02 (t, J = 7.5Hz, 4H), 1.46 (m, 4H), 0.93 (t, J = 7.2 Hz, 6 H) ppm; ¹³ C NMR (100 MHz, DMSO) 203.5, 135.6, 134.4, 134.3, 131.3, 129.9, 129.8, 129.7, 128.2, 128.1, 127.8, 118.3, 118.1, 53.3, 41.0, 21.3, 11.8 ppm; ³¹ P NMR (166 MHz, DMSO) 24.1 ppm; LC-MS m / z = 529 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₂ H ₃₆ NPS ₂ : C, 72.55; H, 6.85; N, 2.64; S, 12.11. Found: C, 72.56; H, 6.65; N, 2.41; S, 12.73.

Example  6

Tetraphenylphosphonium bromide (4.3 g) was dissolved in 50 ml of methylene chloride, and 1.2 g of sodium diethyldithiocarbamate was reacted at room temperature for 24 hours. After precipitation was filtered out, the obtained liquid was evaporated under reduced pressure to obtain 2.0 g of a solid. 12. &Lt; / RTI &gt;

&Lt; Formula 12 >

¹ H NMR (400 MHz, DMSO) 8.05-7.65 (m, 20H) 4.07 (q, J = 7.2 Hz, 4H), 1.21 (t, J = 7.2 Hz, 6 H) ppm; ¹³ C NMR (100 MHz, DMSO) 207.3, 135.5, 134.2, 134.0, 130.1, 130.0, 129.9, 118.7, 118.3, 47.9, 12.5 ppm; ³¹ P NMR (166 MHz, DMSO) 24.0 ppm; LC-MS m / z = 487 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₂₉ H ₃₀ NPS ₂ : C, 71.42; H, 6.20; N, 2.87; S, 13.15. Found: C, 71.49; H, 6.42; N, 2.43; S, 13.28.

Example  7

, 8.2 parts by weight of a biphenyl type epoxy resin (NC-3000, Nippon Kayaku), 4.4 parts by weight of a xylylene type phenol resin (HE100C-10, Air Water), 0.3 part by weight of the compound of Example 1, 86 parts by weight of an inorganic filler which is a mixture of spherical fused silica having an average particle diameter of 0.5 m and a mixture of spherical fused silica having an average particle diameter of 0.5 m, 0.2 part by weight of mercaptopropyltrimethoxysilane (KBM-803, Shinetsu) and methyl trimethoxysilane (SZ- , 0.4 parts by weight of a coupling agent which is a mixture of 0.2 parts by weight of a coloring agent (Dow Corning Chemical), 0.3 parts by weight of carnauba wax as a release agent, and 0.4 parts by weight of carbon black (MA-600, manufactured by Matsusita Chemical) The mixture was homogeneously mixed to obtain a powdery composition. Then, the mixture was melt-kneaded at 95 ° C using a continuous kneader, and then cooled and pulverized to prepare an epoxy resin composition for sealing a semiconductor device.

Example  8

In Example 7, a composition was prepared in the same manner except that the compound of Example 2 was used in place of the compound of Example 1.

Example  9

In Example 7, a composition was prepared in the same manner except that the compound of Example 3 was used in place of the compound of Example 1.

Example  10

In Example 7, a composition was prepared in the same manner except that the compound of Example 4 was used in place of the compound of Example 1.

Example  11

In Example 7, a composition was prepared in the same manner except that the compound of Example 5 was used in place of the compound of Example 1.

Example  12

In Example 7, a composition was prepared in the same manner except that the compound of Example 6 was used in place of the compound of Example 1.

Example  13

A composition was prepared in the same manner as in Example 7 except that phenol aralkyl type epoxy resin was used instead of biphenyl type epoxy resin.

Example  14

A composition was prepared in the same manner as in Example 7, except that a cresol novolak type epoxy resin was used instead of the biphenyl type epoxy resin.

Example  15

The composition was prepared in the same manner as in Example 7, except that phenol novolak type phenol resin was used instead of xylock type phenol resin.

Example  16

The composition was prepared in the same manner as in Example 7, except that phenol aralkyl type phenol resin was used instead of xylo type phenol resin.

Example  17

In Example 7, a composition was prepared in the same manner, except that 0.3 part by weight of the compound of Example 1 was replaced by 0.2 part by weight of the compound of Example 1 and 0.1 part by weight of triphenylphosphine.

Comparative Example  One

In Example 7, a composition was prepared in the same manner except that triphenylphosphine was used in place of the compound of Example 1.

Comparative Example  2

In Example 7, a composition was prepared in the same manner, except that the adduct of triphenylphosphine and 1,4-benzoquinone was used in place of the compound of Example 1.

<Table 1>

(1) Fluidity (inch): The flow length was measured using a transfer molding press at 175 ° C and 70 kgf / cm ² using an evaluation mold according to EMMI-1-66. The higher the measured value, the better the fluidity.

(2) Curing shrinkage (%): Flexural strength A molded specimen (125 mm x 12.6 mm x 6.4 mm) was obtained using a transfer molding press at 175 ° C and 70 kgf / cm ² using a mold for sample preparation . The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours, cooled, and then the length of the specimens was measured with a caliper. The hardening shrinkage ratio was calculated from Equation 2 as follows.

[Formula 2]

Cure shrinkage rate = | C - D | / C x 100

C is the length of the specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; ² &gt;, D is the specimen after curing at 170 to 180 DEG C for 4 hours, Lt; / RTI &gt;

(3) Glass transition temperature (占 폚): The resin composition was measured using a thermomechanical analyzer (TMA). At this time, the TMA was set to a condition of measuring up to 300 DEG C by raising the temperature by 10 DEG C per minute at 25 DEG C. [

4, the moisture absorption rate (%): Example and Comparative Example The resin composition for a mold temperature of 170 ~ 180 ℃, the clamp pressure 70kgf / cm ^2, feed pressure 1000psi, feed rate 0.5 ~ 1cm / s, the curing time of 120 manufactured by Sec to obtain a disk-shaped cured specimen having a diameter of 50 mm and a thickness of 1.0 mm. The obtained specimens were placed in an oven at 170 to 180 ° C. and post-cured for 4 hours. The samples were allowed to stand for 168 hours at 85 ° C. and 85 RH% relative humidity, and the weight change due to moisture absorption was measured. 3, the moisture absorption rate was calculated.

[Formula 3]

Moisture absorption rate = (weight of test piece after moisture absorption - weight of test piece before moisture absorption) ÷ (weight of test piece before moisture absorption)

(5) Hardness (shore-D): Using an MPS (Multi Plunger System) molding machine equipped with a mold for eTQFP (exposed Thin Quad Flat Package) package having a width of 24 mm, a length of 24 mm and a thickness of 1 mm including a copper metal element After curing the epoxy resin composition to be evaluated at 175 ° C for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product was measured by a Shore-D type hardness meter directly on the lap on the mold. The higher the value, the better the degree of cure.

(6) Adhesive force (kgf): A copper metal element was prepared in accordance with the mold for measurement of attachment, and the resin composition prepared in the above-mentioned Examples and Comparative Examples was pressed at a mold temperature of 170 to 180 DEG C and a clamp pressure of 70 kgf / cm ² , a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / s, and a curing time of 120 seconds to obtain cured specimens. The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C. for 4 hours. In this case, the area of the epoxy resin composition contacting the specimen was 40 ± 1 mm ² , and the adhesion was measured by using a universal testing machine (UTM) for 12 specimens per each measuring step, and then the average value was calculated.

(7) Reliability: The eTQFP package for evaluating the flexural characteristics was dried at 125 DEG C for 24 hours, and then subjected to 5 cycles (one cycle was to leave the package at -65 DEG C for 10 minutes, 25 DEG C for 10 minutes, ) Were subjected to a thermal shock test. After the pre-conditioning condition in which the package is left for 168 hours at 85 ° C and 60% relative humidity and then passed once through the IR reflow for 30 seconds at 260 ° C, And observed with a microscope. Then, the occurrence of peeling between the epoxy resin composition and the lead frame was evaluated using a non-destructive inspection C-SAM (Scanning Acoustic Microscopy). When the appearance of the package is cracked or the peeling between the epoxy resin composition and the lead frame occurs, the reliability of the package can not be secured.

(8) Storage stability: The flow length was measured at the intervals of 24 hours in the same manner as in the flowability measurement of the above (1) while keeping the epoxy resin composition in a thermostatic hygrostat set at 25 ° C / 50RH% for 1 week, (%) Was obtained. The larger this percentage value, the better the storage stability.

(9) Viscosity change rate: The viscosity of the epoxy resin composition was measured at 25 占 폚, and the epoxy resin composition was allowed to stand at 25 占 폚 for 48 hours, and the viscosity was measured and calculated according to the following formula (1). The lower the viscosity change rate, the higher the storage stability because the epoxy resin composition is not cured.

<Formula 1>

Viscosity change rate = | B-A | / A x 100

(Unit: cPs) measured at 25 占 폚 after the epoxy resin composition is allowed to stand at 25 占 폚 for 48 hours, and B is the viscosity measured at 25 占 폚 )to be).

As shown in Table 1, the composition containing the phosphonium compound of the present invention has high fluidity, low curing shrinkage rate, and high curing rate even at short curing time when curing time is compared. Also, there was no difference in fluidity after 72 hours and the rate of change of viscosity was low, indicating that storage stability was high. Further, it was confirmed that appearance cracks did not occur, crack resistance was good, and peeling did not occur.

On the other hand, it was confirmed that the composition of the comparative example not containing the phosphonium compound of the present invention has low storage stability, high shrinkage ratio, low fluidity and can not achieve the effect of the present invention when used in a package.

Claims (14)

An epoxy resin, a curing agent, and a curing catalyst,
Wherein the curing catalyst comprises a phosphonium compound represented by the following Formula 1:
&Lt; Formula 1 >

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1-10 carbon atoms, a substituted or unsubstituted group having 6-20 A substituted or unsubstituted arylalkyl group having 7 to 21 carbon atoms). The epoxy resin composition according to claim 1, wherein the epoxy resin comprises an epoxy resin having at least two epoxy groups and at least one hydroxyl group in the molecule. The epoxy resin composition according to claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin , A phenol aralkyl type epoxy resin. The epoxy resin composition according to claim 1, wherein the curing agent comprises a phenol resin. The curing agent according to claim 1, wherein the curing agent is selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylock type phenol resin, a cresol novolac type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, A chloropentadiene-based phenol resin, a novolak-type phenol resin synthesized from bisphenol A and resole, a polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride , Metaphenylene diamine, diaminodiphenyl methane, and diaminodiphenyl sulfone. The epoxy resin composition according to claim 1, wherein the phosphonium compound 0.01 to 5% by weight. 6. The epoxy resin composition according to claim 5, wherein the phosphonium compound is contained in the curing catalyst in an amount of 10 to 100% by weight. The epoxy resin composition according to claim 1, wherein the epoxy resin composition further comprises an inorganic filler. The epoxy resin composition according to claim 1, wherein the epoxy resin composition has a curing initiation temperature of 80 to 120 캜. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin composition has a viscosity change rate of 20%
<Formula 1>
Viscosity change rate = | BA | / A x 100
(Unit: cPs), B is the viscosity (unit: cPs) measured at 25 占 폚 after the epoxy resin composition is allowed to stand at 25 占 폚 for 48 hours under the condition of 25 占 폚, to be). The epoxy resin composition according to claim 1, wherein the epoxy resin composition has a flow length of 59 to 75 inches by a transfer molding press at 175 ° C and 70 kgf / cm ² by EMMI-1-66. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin composition has a curing shrinkage of less than 0.4% as measured by the following formula (2): &
[Formula 2]
Cure shrinkage rate = | C - D | / C x 100
C is the length of the specimen obtained by transfer molding pressing the epoxy resin composition at 175 ° C and 70 kgf / cm 2, D is the specimen obtained after curing the specimen at 170 to 180 ° C for 4 hours, Length). An epoxy resin composition for encapsulating semiconductor devices, comprising the epoxy resin composition of any one of claims 1 to 12. An apparatus produced using the epoxy resin composition of any one of claims 1 to 12.