KR101706822B1 - Curing catalyst, epoxy resin composition comprising the same for encapsulating semiconductor device and semiconductor device prepared from using the same - Google Patents

Abstract

The present invention relates to a curing catalyst of formula (1), an epoxy resin composition for sealing semiconductor devices comprising the same, and a semiconductor device sealed using the composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a curing catalyst, an epoxy resin composition for sealing a semiconductor device comprising the same, and a semiconductor device encapsulated using the same. BACKGROUND ART [0002]

TECHNICAL FIELD The present invention relates to a curing catalyst, an epoxy resin composition for sealing a semiconductor device comprising the same, and a semiconductor device sealed using the composition.

BACKGROUND ART [0002] Transfer molding using an epoxy resin composition is widely used as a method of packaging semiconductor devices such as an IC (integrated circuit) and an LSI (large scale integration) and obtaining a semiconductor device because of its low cost and suitable for mass production. Improvement of the characteristics and reliability of the semiconductor device can be achieved by improving the phenolic resin which is an epoxy resin or a curing agent. The epoxy resin composition may include an epoxy resin, a curing agent, a curing catalyst and the like.

As the curing catalyst, imidazole, amine, and phosphine are used, and they reach a relatively low temperature range in which the curing accelerating effect is exhibited. Therefore, the curing reaction progresses partially due to heat generated when mixing the epoxy resin composition before curing with other components or heat from the outside, and even when the epoxy resin composition is stored at room temperature after completion of the mixing, the curing reaction can be further advanced . The progress of the partial curing reaction causes a decrease in viscosity or fluidity of the composition. In addition, the change in the state is not uniform in the epoxy resin composition, so that the properties of the composition during curing can be varied. This partial change leads to a decrease in the mechanical, electrical, or chemical properties of the molded article when the thermosetting epoxy resin composition is formed by advancing the curing reaction to a high temperature. Therefore, when such a curing catalyst is used, strict quality control of each component mixing time, storage and transportation at a low temperature, and strict control of molding conditions are essential, which makes the operation extremely troublesome. Further, when the range of the temperature range where the curing occurs is wide, the productivity and the fairness may deteriorate as the curing proceeds at a wide range of curing temperatures.

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 a curing catalyst capable of catalyzing the curing of an epoxy resin even at a low temperature since the curing start temperature is low.

It is another object of the present invention to provide a curing catalyst that catalyzes curing only when the desired curing temperature is reached, and eliminates the curing catalyst activity when not the desired curing temperature.

The curing catalyst of the present invention can be represented by the following formula (1)

≪ Formula 1 >

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , W, R ₅ , and n are as defined in the detailed description below).

The epoxy resin composition for semiconductor device encapsulation of the present invention comprises an epoxy resin, a curing agent, a curing catalyst and an inorganic filler, and the curing catalyst may include the curing catalyst of the above formula (1).

The semiconductor device of the present invention can be sealed using the above epoxy resin composition.

The present invention provides a curing catalyst capable of promoting curing of epoxy resin even at low temperatures. The present invention provides a cured catalyst with high storage stability that catalyzes curing only when the desired curing temperature is reached and no curing catalyst activity when not the desired curing temperature.

1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention.
2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention.
3 is a DSC graph of the epoxy resin composition of Example 12 of the present invention measured using a DSC calorimeter.

The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

The curing catalyst of one embodiment of the present invention can be represented by the following Formula 1:

≪ Formula 1 >

Wherein R ₁ , R ₂ , R ₃ , and R ₄ 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 aryl group having 6-20 carbon atoms, Or an unsubstituted arylalkyl group having 7 to 21 carbon atoms,

The ring W is a nitrogen-containing monocyclic or heterocyclic hydrocarbon group having 2 to 36 carbon atoms, and one or more -CH ₂ - included in the hydrocarbon group is -C (= O) -, -O-, -S- or -NR- Wherein R is hydrogen, a hydroxyl group, a halogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 11 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,

R ₅ is a hydroxyl group, a halogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 11 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,

and n is an integer of 0 to 10).

In the present specification, the term "substituted or unsubstituted" means that hydrogen is substituted with a substituent selected from the group consisting of a hydroxyl group, a halogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 11 carbon atoms, Substituted by a cycloalkyl group. For ring W, the "hydrocarbon group" may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The ring W may be a nitrogen-containing monocyclic or heterocyclic hydrocarbon group having 5 to 20 carbon atoms, and may have an effect of low-temperature curing and high fluidity.

The ring W may be a monocyclic hydrocarbon group or a heterocyclic hydrocarbon group, preferably a heterocyclic hydrocarbon group, so that the effect of low temperature curing and high fluidity may be further obtained.

The ring W may be substituted with one or more -CH ₂ - included in the hydrocarbon group by -C (= O) -, -O-, -S- or -NR-, preferably one or more, The three substituents -CH ₂ - are replaced by -C (═O) -, whereby the ring W is aromatic-cyclized and the -C (═O) - is replaced with a -C-OH group, whereby an epoxy resin, The reactivity with the epoxy resin is improved and the catalytic activity can be good.

Specifically, the ring W includes a lactam group including a? -Lactam, a? -Lactam, a? -Lactam, an? -Lactam, an ethyleneimine, a pyrrole, a pyrrolidine, a piperidine, an imidazole, A cyclic amine group having 2 to 36 carbon atoms, an imidazolyl group, an oxazolyl group, an indole group, an indolinyl group, an indolin group, a quinolinone group, an isoquinolinone group, a tetrahydroquinoline group, an octahydroquinoline group, (1H) -quinolinone group and the like, including a tetrahydroquinolinone group, an octahydro-2 (1H) -quinolinone group, an octahydro-4 And the like, but the present invention is not limited thereto.

Preferably, each of R ₁ , R ₂ , R ₃ and R ₄ independently represents a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 11 carbon atoms, There may be more effects with hardening and high fluidity.

When the compound of formula (1) receives external energy such as heat, it is decomposed at 80 to 105 ° C to form a phosphonium cation and a sulfonamide anion, and the resulting phosphonium cation and sulfonamide anion can catalyze the curing of the epoxy resin Therefore, the compound of formula (I) can be used as a latent curing catalyst in an epoxy resin composition containing an epoxy resin and a curing agent. In particular, the sulfonamide anion enables low-temperature curing and has an effect of enhancing fluidity.

The compound of formula (1) may improve the storage stability of a composition comprising the compound of formula (1). 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. As a result, the epoxy resin composition comprising the compound of formula (1) may have a viscosity change rate of 1 to 20% in the following formula (1)

<Formula 1>

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

(In the formula 1, A represents the viscosity (unit: cPs) measured at 25 ° C of the epoxy resin composition and B represents the viscosity (unit: cPs) measured at 25 ° C after the epoxy resin composition was allowed to stand at 25 ° C for 48 hours ).

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 20,000 to 50,000 cPs, and B may be 20,000 to 80,000 cPs.

The epoxy resin composition comprising the compound of Formula 1 may have a curing initiation temperature To and a peak temperature Tmax of 80 to 105 ° C and 120 to 140 ° C, respectively, as measured by differential scanning calorimetry (DSC). Within this range, there may be effects of low temperature curing with low starting and peak temperatures. The term "curing initiation temperature" refers to the temperature at which the epoxy resin composition was maintained at an initial temperature of 30 ° C for 1 minute and then increased to 250 ° C at a rate of 10 ° C / min, and the reaction heat was measured by differential scanning calorimetry (DSC) The temperature at which the line joining the slope of the reaction heat curve reaching the peak temperature and the temperature at which the solidification starts and the temperature at which the solidification ends is obtained. The "peak temperature" may be 120-140 &lt; 0 &gt; C.

The compound of formula (1) may be of the salt type.

As described above, the compound of formula (I) can catalyze an epoxy resin composition comprising an epoxy resin and a curing agent. According to one embodiment, the epoxy resin has two or more epoxy groups in the molecule. Examples thereof include bisphenol A type epoxy resins, A phenol novolak type epoxy resin, a tertiary butyl catechol type epoxy resin, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, a cresol novolak type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin , Alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins 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 phase epoxy resin and a liquid phase epoxy resin, and preferably a solid phase epoxy resin may be used.

According to one embodiment, 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 novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, Novolac phenol resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, And aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Preferably, the curing agent may be a novolak type resin having at least one hydroxyl group.

The compound of the formula (1) may be contained 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, more particularly 0.05 to 1.5% by weight in the epoxy resin composition. Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.

The compound of formula (1) can be prepared by a conventional method. For example, it can be prepared by reacting a compound containing a phosphonium ion of the following formula 2 with a compound of 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 W, R ₅ and n are the same as defined in the above formula (1), and M is an alkali metal)

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

The phosphonium ion-containing compound may be prepared by coupling a phosphine-based compound with an alkyl halide, an aryl halide, or an aralkyl halide in a solvent, or may use a phosphonium cation-containing salt, and the compound of formula (3) may be a difluoromethanesulfonate salt Can be used.

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 or the like and is carried out at 10 to 100 ° C, for example, at 20 to 80 ° C for 1 to 30 hours For example 10 to 24 hours, and the compound of formula (2): the compound of formula (3) may be reacted in a molar ratio of 1: 0.9 to 1: 1.5. Within this range, the synthesis of the compound of formula (1) may be possible. 　 Without the reaction to prepare a compound of formula II by combining the formula (2) of the compounds and may be carried out by mixing a compound of formula (3), a phosphonium-containing compound with an alkyl halide, aryl halide or an aralkyl halide, etc., and additional separation processes in situ to the compound of formula (3).

The epoxy resin composition for semiconductor device encapsulation according to one embodiment of the present invention comprises an epoxy resin, a curing agent, a curing catalyst, and an inorganic filler, and may contain a compound of the formula (1) as a curing catalyst.

Examples of the epoxy resin 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, glycidylamine type epoxy resin, Biphenyl type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins and the like. They may be included singly or in combination of two or more. Specifically, the epoxy resin may include an epoxy resin having at least two epoxy groups and at least one hydroxyl group in the molecule.

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

&Lt; Formula 4 >

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

Preferably, the average value of n is 1 to 5.

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.

In one embodiment, the curing agent may be a xylo-type phenolic resin of formula 5:

&Lt; Formula 5 >

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

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

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. The maximum particle diameter can be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the application. In the spherical fused silica, conductive carbon may be contained on the surface of the silica as a foreign substance, but it is also important to select a substance having a small amount of polar foreign 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 70 to 90% by weight. Within the above range, flame retardancy, fluidity and reliability of the epoxy resin composition can be secured.

The compound of formula (I) may be contained in the curing catalyst in an amount of 10 to 100% by weight, and may be 0.01 to 5% by weight, specifically 0.01 to 2% by weight, more specifically 0.02 to 1.5% 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 composition may further comprise a non-phosphonium-based curing catalyst that 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. Organic phosphorus compounds include tris-4-methoxyphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct, and the like. 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 preferred curing catalysts include organic phosphorus compounds, boron compounds, amine-based or imidazole-based curing accelerators, either alone or in combination. As the curing catalyst, it is also possible to use an adduct formed by the reaction with an epoxy resin or a curing agent.

The curing catalyst may be included in the epoxy resin composition in an amount of 0.01 to 5 wt%, for example, 0.01 to 3 wt%, for example, 0.05 to 1.0 wt%. 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 comprise conventional additives included in the epoxy resin composition for sealing a semiconductor device. 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 epoxy resin 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 has high storage stability by containing the compound of formula (1) as a curing catalyst, so that 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 1 to 20%, for example, 3 to 10% in the above formula 1. In the above range, There is no curing catalytic activity when the curing temperature is not the desired curing temperature, and when the curing reaction is actually carried out at a high temperature, the moldability may be deteriorated due to the decrease of fluidity, and mechanical, electrical and chemical properties of the molded product may not be deteriorated. In embodiments, A may be 20,000 to 50,000 cPs, and B may be 20,000 to 80,000 cPs.

The epoxy resin composition may have a flow length of 55 to 80 inches, specifically 63 to 80 inches by transfer molding press at 175 占 폚 and 70 kgf / cm2 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 ° C and 70 kgf / cm 2, D is the specimen obtained after curing the specimen at 170 to 180 ° C for 4 hours, Length). Within this range, the curing shrinkage is low and can be used as an epoxy resin composition.

The semiconductor device of the present invention can be sealed using the above epoxy resin composition.

1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. 1, a semiconductor device 100 according to an embodiment of the present invention includes a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30, The gap between the wiring board 10 and the semiconductor chip 20 can be sealed with the epoxy resin composition 40 and the epoxy resin composition can be the epoxy resin composition of the embodiment of the present invention.

2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention. 2, a semiconductor device 200 according to another embodiment of the present invention includes a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30, The gap between the wiring substrate 10 and the semiconductor chip 20 and the entire upper surface of the semiconductor chip 30 can be sealed with the epoxy resin composition 40. The epoxy resin composition can be used as the epoxy resin composition for sealing semiconductor devices . &Lt; / RTI &gt;

In Figs. 1 and 2, the size of each of the wiring board, the bump, and the semiconductor chip, and the number of bumps are arbitrary and can be changed.

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 1

Nortropinone hydrochloride (4.00 g) and triethylamine (3.45 mL) were dissolved in dichloromethane (31 mL), and 3,3,4,4-tetrafluoro-1 , 2-oxathietane-2,2-dioxide (2.63 mL) was added slowly for 1 hour, and then the mixture was stirred at room temperature The reaction was carried out for about 1 hour. After the reaction was completed, the reaction mixture was diluted with an excess amount of water and washed with an appropriate amount of water. The solvent of the obtained reaction product was removed under reduced pressure, and the product was purified by column chromatography (ethylacetate: hexane = 1: 4). 71%)

Water (17.7 mL) was added to the obtained product (1-nortropinone amide difluoromethane sulfonylfluoride) (5.001 g) and sodium hydroxide (1.403 g) And the mixture was refluxed for 16 hours. After the reaction was completed, water in the reaction mixture was removed at low pressure, and then redissolved in ethanol (44 mL) and stirred for about 15 minutes. The insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at low pressure to obtain the product. (Yield: 65%)

The resulting product (sodium 1-nortropinone amide difluoromethanesulfonate) (0.553 g) was dissolved in water (2.0 mL) and a solution of Tetraphenylphosphonium bromide (0.43 g) (MeOH) 2.0 mL), and the mixture was reacted at room temperature for about 3 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a product of the following formula (6) and confirmed by NMR data (yield: 85%).

1H NMR (300 MHz, DMSO): 7.97 (t, J = 2.6 Hz, 4H), 7.84-7.81 (m, 8H), 7.76-7.72 1H), 2.9 (m, 1H), 2.7 (m, 1H), 2.4 (m, 2H), 2.3 (m, 1H), 2.1 (m, 1H), 1.7 (m, 2H) ppm; LC-MS m / z = 622 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₃ H ₃₁ F ₂ NO ₅ PS: C, 63.66; H, 5.02; N, 2.25; S, 5.15. Found: C, 63.44; H, 5.36; N, 2.43; S, 4.94.

(6)

The product of Formula 6 according to Example 1 was produced according to the following Reaction Scheme 1.

<Reaction Scheme 1>

Example 2

3.6 g of triphenylphosphine, 2.2 g of 4-bromophenol and 0.8 g of Nickel (II) chloride were dissolved in 50 ml of ethylene glycol, reacted at 180 ° C. for 12 hours, and 4.5 g of 4-hydroxy-phenyl-triphenylphosphonium bromide Respectively. The sodium intermediate (sodium 1-nortropinone amide difluoromethanesulfonate) (0.553 g) synthesized in Example 1 was dissolved in water (2.0 mL) and the resulting (4-Hydroxy- phenyl) -triphenyl-phosphonium bromide (0.45 g) was dissolved in MeOH (2.0 mL) and reacted at room temperature for about 3 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a product of the following formula (7), which was confirmed by NMR data (yield: 78%).

- 1H-NMR (300 MHz, DMSO): 7.97-7.90 (m, 3H), 7.78-7.65 (m, 12H), 7.38 (d, J = 8.6 Hz, 2H), 6.97 (d, J = 8.6 Hz, 2H), 5.54 (s, IH), 5.3 (m, IH), 5.0 (m, IH), 2.9 ), 2.1 (m, 1H), 1.7 (m, 2H) ppm; LC-MS m / z = 638 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₃ H ₃₁ F ₂ NO ₆ PS: C, 62.06; H, 4.89; N, 2.19; S, 5.02. Found: C, 62.39; H, 5.21; N, 2.34; S, 4.99.

&Lt; Formula 7 >

The product represented by the above formula (7) according to Example 2 was produced by the following reaction formula (2).

<Reaction Scheme 2>

Example 3

Octahydro-4 (1H) -quinolinone (1.00 g) and triethylamine (0.91 mL) were dissolved in dichloromethane (8.3 mL) 3,3,4,4-tetrafluoro-1,2-oxathietane-2,2-dioxide) (0.69 g of tetrachloro-2,2- mL) was added slowly for 1 hour and then reacted at room temperature for about 1 hour. After the reaction was completed, the reaction mixture was diluted with excess water and washed with an appropriate amount of water. The solvent of the obtained reaction product was removed under reduced pressure, and the product was purified by column chromatography (ethylacetate: hexane = 1: 9). (Yield: 70%)

The obtained product (octahydro-4 (1H) -quinolinonamide difluoromethane sulfonylfluoride (octahydro-4 (1H) -quinolinone amide difluoromethane sulfonylfluoride) (0.621 g) and sodium hydroxide ) (0.159 g) was dissolved in water (2.0 mL), followed by reflux stirring for 16 hours. After the reaction was completed, water in the reaction mixture was removed at a low pressure, and then redissolved in ethanol (5 mL) and stirred for about 15 minutes. The insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at low pressure to obtain the product. (Yield: 65%).

To the resulting product (sodium octahydro-4 (1H) -quinolinonamide difluoromethanesulfonate) (0.468 g) was added water (2.0 mL) Dissolved in Tetraphenylphosphonium bromide (0.43 g) solution (MeOH) (2.0 mL) and reacted at room temperature for about 3 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a product of the following formula (8) and confirmed by NMR data (yield: 83%).

- 1H-NMR (300 MHz, DMSO): 7.97 (t, J = 2.6 Hz, 4H), 7.84-7.81 (m, 8H), 7.76-7.72 (m, 8H), 4.1 (m, 2H), 3.8 ( 1H, m, 1H), 2.7 (m, 1H), 2.6 (m, 2H), 2.4 (m, 1H), 2.1 (m, 1H), 1.8 (m, 2H), 1.4 (m, 4H) ppm; LC-MS m / z = 649 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₅ H ₃₄ F ₂ NO ₅ PS: C, 64.70; H, 5.27; N, 2.16; S, 4.94. Found: C, 64.49; H, 5.21; N, 2.33; S, 4.95.

(8)

The product of formula (8) according to example 3 was produced according to the following reaction formula (3).

<Reaction Scheme 3>

Example 4

3.6 g of triphenylphosphine, 2.2 g of 4-bromophenol and 0.8 g of Nickel (II) chloride were dissolved in 50 ml of ethylene glycol, reacted at 180 ° C. for 12 hours, and 4.5 g of 4-hydroxy-phenyl-triphenylphosphonium bromide Respectively. (Sodium octahydro-4 (1H) -quinolinone amide difluoro-methanesulfonate) (0.468 g) synthesized in Example 3 was dissolved in water (2.0 mL), and 0.45 g of (4-Hydroxy-phenyl) -triphenyl-phosphonium bromide was dissolved in 2.0 mL of MeOH, followed by reaction at room temperature for about 3 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a product of the following formula (9) and confirmed by NMR data (yield: 81%).

- 1H-NMR (300 MHz, DMSO): 7.97-7.90 (m, 3H), 7.78-7.65 (m, 12H), 7.38 (d, J = 8.6 Hz, 2H), 6.97 (d, J = 8.6 Hz, 1H), 1.8 (m, 2H), 4.1 (m, 2H), 3.8 (m, ), 1.4 (m, 4 H) ppm; LC-MS m / z = 665 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₅ H ₃₄ F ₂ NO ₆ PS: C, 63.15; H, 5.15; N, 2.10; S, 4.82. Found: C, 63.30; H, 5.23; N, 2.13; S, 4.49.

&Lt; Formula 9 >

The product represented by the above formula (9) according to Example 4 was produced according to the following reaction formula (4).

<Reaction Scheme 4>

Example 5

3.5 g of triphenylphosphine and 2.3 g of benzyl bromide were dissolved in 50 ml of toluene and the reaction was carried out at 110 ° C. for 3 hours. The resulting precipitate was filtered and dried to obtain 5.0 g of solid benzyltriphenyl phosphonium bromide. The intermediate product (sodium 1-nortropinone amide difluoromethanesulfonate) (0.553 g) synthesized in Example 1 was dissolved in water (2.0 mL), and 0.40 g of the obtained benzyltriphenylphosphonium bromide Solution (MeOH) (2.0 mL), and the mixture was reacted at room temperature for about 3 hours. After the completion of the reaction, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a product of the following formula (10) and confirmed by NMR data (yield: 75%).

1H NMR (300 MHz, DMSO): 7.84-7.70 (m, 15H), 7.31-7.05 (m, 5H), 5.4 2.9 (m, 1H), 2.7 (m, 1H), 2.4 (m, 2H), 2.3 (m, 1H), 2.1 (m, 1H), 1.7 (m, 2H) ppm; LC-MS m / z = 636 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₄ H ₃₃ F ₂ NO ₅ PS: C, 64.14; H, 5.22; N, 2.20; S, 5.04. Found: C, 64.43; H, 5.46; N, 2.37; S, 5.28.

&Lt; Formula 10 >

The product of Formula 10 according to Example 5 was produced according to the following Reaction 5.

<Reaction Scheme 5>

Example 6

9 (10H) -Acridone (1.95 g) and triethylamine (0.91 mL) were dissolved in dichloromethane (8.3 mL), and 3,3,4, (3,3,4,4-tetrafluoro-1,2-oxathietane-2,2-dioxide) (0.69 mL) was slowly added to the solution for 1 hour And reacted at room temperature for about 1 hour. After the reaction was completed, the reaction mixture was diluted with excess water and washed with an appropriate amount of water. The solvent of the obtained reaction product was removed under reduced pressure, and the product was purified by column chromatography (ethylacetate: hexane = 1: 9). (Yield: 65%).

The obtained product (9 (10H) -acridonamide difluoromethane sulfonyl fluoride) (9 (10H) -acridone amide difluoromethane sulfonylfluoride) (0.650 g) and sodium hydroxide (0.159 g) Was dissolved in water (2.0 mL), and the mixture was refluxed with stirring for 16 hours. After the reaction was completed, water in the reaction mixture was removed at a low pressure, and then redissolved in ethanol (5 mL) and stirred for about 15 minutes. The insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at low pressure to obtain the product. (Yield: 65%).

The obtained product (sodium 9 (10H) -acridonamide difluoromethanesulfonate) (0.60 g) was dissolved in water (2.0 mL) and treated with Tetraphenylphosphonium bromide ( 0.43 g) in MeOH (2.0 mL), and the mixture was reacted at room temperature for about 3 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a product of the following formula (11) and confirmed by NMR data (yield: 74%).

J = 8.6 Hz, 2H), 7.97 (t, J = 2.6 Hz, 4H), 7.84-7.81 (m, 8H), 7.76-7.70 (m, 10H), 7.58 (d, J = 8.6 Hz, 2H), 7.25 (m, 2H); LC-MS m / z = 691 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₃₉ H ₂₈ F ₂ NO ₅ PS: C, 67.72; H, 4.08; N, 2.03; S, 4.64. Found: C, 67.40; H, 4.21; N, 2.38; S, 4.91.

&Lt; Formula 11 >

The product of Formula 11 according to Example 6 was produced according to the following Reaction Scheme 6.

<Reaction Scheme 6>

Examples 7 to 12

A biphenyl type epoxy resin (NC-3000, Nippon Kayaku) as an epoxy resin, a xylock type phenol resin (HE100C-10, Air Water) as a curing agent and a curing accelerator A 9: 1 weight ratio mixture of fused silica and spherical fused silica having an average particle diameter of 0.5 占 퐉 was mixed in the contents shown in Table 1 below, and 0.3 parts by weight of carnauba wax and 0.3 parts by weight of carbon black (MA-600, manufactured by Matsusita Chemical Co., ), 0.3 part by weight of coupling agent, 0.2 part by weight of coupling agent capto propyltrimethoxysilane (KBM-803, Shinetsu, coupling agent 1) and 0.2 part by weight of methyltrimethoxysilane (SZ-6070, Dow Corning Chemical, coupling agent 2) And 0.4 part by weight of the mixture of the above components were mixed and homogeneously mixed using a Hensel mixer 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.

Comparative Examples 1 to 3

An epoxy resin composition for encapsulating semiconductor devices was prepared in the same manner as in Example 7, except that the types of curing catalysts were changed as shown in Table 1 below.

division Example Comparative Example 7 8 9 10 11 12 One 2 3 Epoxy resin 7.4 7.4 7.4 7.4 7.4 7.4 7.4 7.4 7.4 Hardener 4.3 4.3 4.3 4.3 4.3 4.3 4.6 4.3 4.3



Hardening
catalyst Example 1 0.3 - - - - - - - - Example 2 - 0.3 - - - - - - - Example 3 - - 0.3 - - - - - - Example 4 - - - 0.3 - - - - - Example 5 - - - - 0.3 - - - - Example 6 - - - - - 0.3 - - - Triphenyl
Phosphine
-
-
-
-
-
-
-
0.3
- Addition products of triphenylphosphine and 1,4-benzoquinone
-
-
-
-
-
-
-
-
0.3 Inorganic filler 87 87 87 87 87 87 87 87 87 Release agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 coloring agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Coupling agent Coupling agent 1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Coupling agent 2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

The following properties of the epoxy resin compositions of Examples and Comparative Examples were evaluated, and the results are shown in Table 2 below.

Evaluation items Example Comparative Example 7 8 9 10 11 12 One 2 3

group
example

water
castle Flowability (inch) 71 74 72 72 72 71 89 50 54 Cure shrinkage (%) 0.34 0.33 0.35 0.35 0.35 0.34 - 0.44 0.43 Glass transition temperature (캜) 124 124 123 123 123 123 185 121 122 Moisture absorption rate (%) 0.24 0.25 0.24 0.24 0.25 0.24 - 0.25 0.25 Adhesion (kgf) 76 74 75 75 74 73 - 73 74
DSC To (占 폚) 98 96 95 98 100 94 - 115 110 Tmax
(° C) 129 127 128 125 130 137 - 145 142 H (J / g) 109 112 121 107 109 87 - 110 103 tile
key
G
Flat
end Cure Time (Shore-D) 50 seconds 69 70 71 72 72 68 25 52 60 60 seconds 71 72 73 74 74 70 27 60 64 70 seconds 72 73 74 76 76 73 28 64 66 80 seconds 73 75 74 76 76 75 28 67 70 90 seconds 73 75 74 76 76 75 28 67 71 Save
stability
(%) 24 hours 99 98 99 98 98 97 - 95 93 48 hours 98 98 97 97 96 96 - 88 83 72 hours 96 96 95 96 95 95 - 65 62

As shown in Table 2, it was confirmed that the epoxy resin composition for sealing semiconductor devices of the present invention had low curing start temperature and low fluidity reduction ratio even after 72 hours and high storage stability.

On the other hand, Comparative Example 1 not including the catalyst had a problem that the curing reaction did not proceed, and Comparative Example 2 and Comparative Example 3 including the conventional phosphine-based catalyst had low fluidity, high curing start temperature, Low.

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

(2) Cure shrinkage ratio: Flexural strength A molding specimen was obtained by using a transper molding press at 175 DEG C and 70 kgf / cm &lt; 2 &gt; The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours, cooled, and the length of the specimens was measured with a caliper. The hardening shrinkage was calculated from Equation 2.

[Formula 2]

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

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

(3) Glass transition temperature (占 폚): The epoxy 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) Moisture absorption rate (%): The epoxy resin composition was molded under the conditions of a mold temperature of 170 to 180 占 폚, a clamp pressure of 70 kgf / cm2, a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / A disk-shaped cured specimen having a thickness of 1.0 mm was obtained. 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) × 100

(5) Adhesive force (kgf): A copper metal element was prepared for the epoxy resin composition in accordance with the measurement mold, and the resin composition prepared in the above-mentioned Examples and Comparative Examples was heated to a mold temperature of 170 to 180 ° C, A clamping pressure of 70 kgf / cm 2, a conveying pressure of 1000 psi, a conveying speed of 0.5 to 1 cm / s, and a curing time of 120 seconds to obtain a cured specimen. 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.

(6) Differential Scanning Calorimeter (DSC) measurement: The difference in heat flow between the sample and the reference material is expressed as a function of temperature while changing the sample and the inert reference according to the same temperature program. The temperature program is set by the device and the heat capacity and the time dependent heat flow of the measurement sample are tracked by using the input heating rate and DSC thermal signal to measure the curing initiation temperature, curing temperature curing rate and reaction energy.

The curing rate, curing degree and reaction energy were measured after reaching 250 ° C at 10 ° C / min for 1 minute at 30 ° C using a DSC calorimeter (TA 100, TA Instrument). The curing initiation temperature (To) is the temperature at which the slope of the reaction heat curve reaching the peak temperature as the starting point of the exothermic polymerization reaction meets the line connecting the slope of the parallel section before the initiation of the curing reaction, and the peak temperature (Tmax) And ΔH is the integral of the DSC curve corresponding to the total amount of reaction heat generated from the reaction.

The results of DSC analysis of the epoxy resin composition of Example 12 measured using a DSC calorimeter are shown in Fig.

(7) 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.

(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 higher this percentage value is, the better the storage stability is.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

A curing catalyst of formula (1)
&Lt; Formula 1 >

Wherein R ₁ , R ₂ , R ₃ and R ₄ 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 aryl group having 6-20 carbon atoms, An unsubstituted arylalkyl group having 7 to 21 carbon atoms,
The ring W is a nitrogen-containing monocyclic or heterocyclic hydrocarbon group having 2 to 36 carbon atoms, and one or more -CH ₂ - included in the hydrocarbon group is -C (= O) -, -O-, -S- or -NR- Wherein R is hydrogen, a hydroxyl group, a halogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 11 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,
R ₅ is a hydroxyl group, a halogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 11 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,
and n is an integer of 0 to 10).
The curing catalyst according to claim 1, wherein at least one -CH ₂ - included in the hydrocarbon group is substituted with -C (= O) -.
The method according to claim 1, wherein the ring W is selected from the group consisting of a lactam group, an imidazolyl group, an oxazolyl group, an indole group, an indolinyl group, an indolinone group, a quinolinone group, an isoquinolinone group, a tetrahydroquinoline group, , Tetrahydroquinolinone group, octahydroquinolinone group or nortropinone group.
The curing catalyst according to claim 1, wherein the curing catalyst is represented by one of the following formulas (6) to (11):
(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

An epoxy resin, a curing agent, a curing catalyst and an inorganic filler,
Wherein the curing catalyst comprises a curing catalyst according to any one of claims 1 to 4.
6. The epoxy resin composition according to claim 5, wherein the epoxy resin comprises an epoxy resin having at least two epoxy groups and at least one hydroxyl group in the molecule.
6. The epoxy resin composition according to claim 5, wherein the curing agent comprises a novolac phenolic resin.
6. The epoxy resin composition for sealing a semiconductor device according to claim 5, wherein the curing catalyst of Formula 1 is contained in an amount of 0.01 to 5 wt% of the epoxy resin composition.
6. The epoxy resin composition for sealing a semiconductor device according to claim 5, wherein the curing catalyst of Formula 1 is contained in an amount of 10 to 100% by weight of the curing catalyst.
6. The composition of claim 5, wherein the composition comprises from 2 to 17% by weight of the epoxy resin, from 0.5 to 13% by weight of the curing agent, from 70 to 95% by weight of the inorganic filler, and from 0.01 to 5% (EN) Epoxy resin composition for sealing semiconductor devices.
A semiconductor element sealed by using the epoxy resin composition for sealing a semiconductor element according to claim 5.

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