KR101768281B1 - Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same - Google Patents

Abstract

(상기 화학식 1에서, R₁, R₂, R₃, 및 R₄ 는 각각 독립적으로 치환 또는 비치환된 C1~C30의 지방족 탄화수소기, 치환 또는 비치환된 C6~C30의 방향족 탄화수소기, 또는 헤테로 원자를 포함하는 치환 또는 비치환된 C1~C30의 탄화수소기이고, X는 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기, 치환 또는 비치환된 탄소수 3 내지 10의 사이클로 알킬렌기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬렌기이고, R₅ 는 수소, 하이드록시기, C1~C20의 알킬기, C6~C30의 아릴기, C3~C30의 헤테로아릴기, C3~C10의 시클로알킬기, C3~C10의 헤테로시클로알킬기, C7~C30의 아릴알킬기, C1~C30의 헤테로알킬기이고, m은 0~5의 정수이다).The present invention relates to a phosphonium compound represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or a hetero X is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted C1 to C30 hydrocarbon group, a substituted or unsubstituted C1 to C30 hydrocarbon group, is an alkylene group having 1 to 20, R ₅ is hydrogen, a hydroxyl group, an alkyl group of C1 ~ C20, an aryl group of C6 ~ C30, a heteroaryl group, a cycloalkyl group of C3 ~ C10 of C3 ~ C30, C3 ~ C10 A C7 to C30 arylalkyl group, a C1 to C30 heteroalkyl group, and m is an integer of 0 to 5).

Description

FIELD OF THE INVENTION [0001] The present invention relates to a phosphonium compound, an epoxy resin composition containing the same, and a semiconductor device manufactured using the same. BACKGROUND ART [0002]

The present invention relates to a phosphonium compound, an epoxy resin composition containing the same, and a semiconductor device manufactured using the same.

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.

Such an epoxy resin composition includes an epoxy resin, a curing agent, a curing catalyst and the like. As the curing catalyst, an imidazole-based catalyst, an amine-based catalyst, and a phosphine-based catalyst have usually been used.

However, due to the tendency that electronic devices gradually become smaller, lighter, and have higher performance, the high integration of semiconductors is accelerating every year, and as the demand for surface mounting of semiconductor devices increases, problems that can not be solved by conventional epoxy resin compositions are caused have. In recent years, materials used for packaging semiconductor devices are required to have fast curability for the purpose of improving productivity and storage stability for the purpose of improving handling and handling during storage.

In this regard, Japanese Patent No. 4569076 discloses an epoxy resin curing catalyst using tri-substituted phosphonio phenolate or a salt thereof.

An object of the present invention is to provide a curing catalyst compound capable of accelerating curing of an epoxy resin, exhibiting excellent flowability upon molding, exhibiting a high curing strength, and being able to be cured even in a short curing time.

Another object of the present invention is to provide a compound for a curing catalyst which can accelerate the curing of the epoxy resin even at low temperatures.

It is a further object of the present invention to provide a compound for a curing catalyst having high storage stability which catalyzes curing only when the desired curing temperature is reached and no curing catalyst activity when not the desired curing temperature.

It is still another object of the present invention to provide a semiconductor device comprising the above epoxy resin composition.

The phosphonium compound of the present invention can be represented by the following general formula (1).

[Chemical Formula 1]

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

The phosphonium-based compound may be represented by R ₁ , R ₂ , R ₃ , and R ₄ may be a C6-C30 aryl group.

_{R 1, R 2, R 3} , and R ₄ is an aryl group when the C6 ~ C30, the _{R 1, R 2, R 3} , and R ₄ one or more may be substituted with a hydroxy group.

The phosphonium compound may be represented by the following formulas (1a) to (1h).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

The phosphonium-based compound of the present invention can be prepared by a process comprising the step of reacting a phosphonium-based cation-containing compound of the following formula (2) with an anilide-based anion-containing compound of the following formula (3).

(2)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and Y are as defined in the detailed description below),

(3)

(Wherein Y, R ₅ , m, and M are as defined in the following description).

Another aspect of the present invention is an epoxy resin composition comprising an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, and the curing catalyst may include the phosphonium-based compound serving as a curing accelerator.

The epoxy resin may be at least one 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, , A biphenyl type epoxy resin, a linear aliphatic epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spirocyclic epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin and a halogenated epoxy resin .

The curing agent may comprise a phenolic resin.

The curing agent may be at least one selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolac 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 phenolic resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, Diaminodiphenylmethane, diaminodiphenylsulfone, and the like.

The curing catalyst may be contained in an amount of 0.01 to 5 wt% of the epoxy resin composition.

The phosphonium-based compound may be contained in an amount of 10 to 100% by weight of the curing catalyst.

The storage stability of the epoxy resin composition after 72 hours may be 80% or more.

The epoxy resin composition may have a curing shrinkage ratio of less than 0.4% of the following formula 1:

<Formula 1>

Cure shrinkage ratio = | 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).

The semiconductor device, which is another aspect of the present invention, can be sealed with the above epoxy resin composition.

The present invention provides a compound for a curing catalyst capable of promoting curing of an epoxy resin and capable of accelerating the curing of the epoxy resin even at a low temperature, and is useful for a mixture containing an epoxy resin, a curing agent, It is possible to provide a compound for a curing catalyst having a low storage stability due to a decrease in moldability and mechanical, electrical and chemical properties of a molded product due to a decrease in fluidity when the epoxy resin composition is cured at a high temperature by minimizing viscosity change.

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.

In the present specification, the term "substituted or unsubstituted" means that at least one hydrogen atom of the functional group is a hydroxyl group, a halogen atom, an amino group, a nitro group, a cyano group, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, Means a group substituted with an aryl group having 1 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heteroalkyl group having 1 to 30 carbon atoms, Halo " means fluorine, chlorine, iodine or bromine.

"Aryl group" means a substituent group in which all the elements of a cyclic substituent have p-orbital and p-orbital forms a conjugate, and mono or fused (i.e., a ring in which carbon atoms divide adjacent pairs) Quot; unsubstituted aryl group "means a single or fused polycyclic aryl group of C6 to C30, for example, a phenyl group, a biphenyl group, a naphthyl group, a naphthol group, an anthracenyl group, etc. , But is not limited thereto.

In the present specification, the "heteroaryl group" means that the aryl group of C6 to C30 contains 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus, and the others are carbon. Examples thereof include pyridinyl, Pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, acridinyl, quinazolinyl, cinnolinyl, phthalazinyl, thiazolyl, benzothiazolyl, Isothiazolyl, isoxazolyl, benzisoxazolyl, benzisoxazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, purinyl, thiophenyl, benzothiophenyl, furanyl, benzofuranyl, But is not limited to.

In the present specification, "hetero" in the context of "heterocycloalkyl group", "heteroaryl group", "heterocycloalkylene group" and "heteroarylene group" means nitrogen, oxygen, sulfur or phosphorus atom.

The phosphonium-based compound of the present invention includes an anion which can simultaneously contain a phosphonium-based cation, a hydroxy group and an amide group, and can be represented by the following formula (1)

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or a hetero atom And X is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted C1 to C30 hydrocarbon group, a substituted or unsubstituted C1 to C30 hydrocarbon group, an alkylene group having 1 to 20, R ₅ is a hydrogen, hydroxyl group, alkyl group of C1 ~ C20, an aryl group of C6 ~ C30, a heteroaryl group, a cycloalkyl group of C3 ~ C10 of C3 ~ C30, C3 ~ C10 A C7 to C30 arylalkyl group, a C1 to C30 heteroalkyl group, and m is an integer of 0 to 5.

R ₁ , R ₂ , R ₃ , and R ₄ in Formula 1 may be C6-C30 aryl groups.

At least one of R ₁ , R ₂ , R ₃ and R ₄ in Formula 1 may be substituted with a hydroxy group.

The phosphonium compound of the present invention may be a compound represented by the following general formulas (1a) to (1h).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

The melting point of the phosphonium-based compound may be from 100 to 130 캜, for example, from 120 to 125 캜. The phosphonium-based compound may be a water-insoluble compound. Within this range, there may be an effect of low temperature curing.

The phosphonium-based compound may be added to a composition comprising at least one of an epoxy resin, a curing agent, and an inorganic filler, and used as a latent curing catalyst.

The resulting phosphine compound reacts with the epoxide group in the epoxy resin to perform 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.

The phosphonium compound catalyzes the curing reaction between the epoxy resin and the curing agent and at the same time has a low temperature curability and a high storage stability and is capable of minimizing the change in viscosity even in a predetermined range of time and temperature conditions in a mixture containing an epoxy resin, There is an effect that an epoxy resin composition can be provided. The storage stability promotes 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 long time without viscosity change. 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 can be prepared by reacting a phosphonium-based cation-containing compound of the following formula (2) with an anilide-based anion-containing compound of the following formula (3)

(2)

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a substituted or unsubstituted C 1 -C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, or a hetero A substituted or unsubstituted C1 to C30 hydrocarbon group containing an atom, and Y is halogen),

 (3)

(Wherein X is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted C1 to C20 alkylene group, and R ₅ Is selected from the group consisting of hydrogen, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms, A C1 to C30 heteroalkyl group, and m is an integer of 0 to 5. M is an alkali metal or Ag.

The halogen is fluorine, chlorine, bromine, iodine, and the alkali metals are lithium, sodium, potassium, lumidium, cesium, francium and the like.

The phosphonium-based cation-containing compound may be prepared by bonding an alkyl halide, an aryl halide, an aralkyl halide, or the like to a phosphine-based compound in a solvent, or may be a phosphonium-based cation-containing salt, and the anilide- It can be a salt. Examples of the phosphine-based compound include triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diethylphenylphosphine and the like , But is not limited thereto.

The reaction of the general formula (2) and the general formula (3) can be carried out in an organic solvent such as methanol, methylene chloride, acetonitrile, N, N-dimethylformamide, toluene, etc., and the phosphonium cation- 1 to 1: 6. The reaction can be carried out by mixing the compounds of formulas (2) and (3), respectively, or by combining a phosphine-based compound with an alkyl halide, an aryl halide or an aralkyl halide to prepare a phosphonium-containing cation-containing compound, Containing anion-containing compound may be added.

With respect to anions, when two molecules form hydrogen bond clusters to form anions, they are excellent in fluidity. This is presumably due to the stronger formation of ionic bonds with the cations when the two molecules form hydrogen bond clusters, thereby suppressing the reactivity, and the weak hydrogen bond is rapidly broken and the cationic catalysis participates in the rapid curing.

The epoxy resin composition of the present invention may include at least one of an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst.

Epoxy resin

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, 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.

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

[Chemical Formula 4]

(In the formula (4), R is an alkyl group having 1 to 4 carbon atoms, and the average value of n is 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.

Hardener

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 may be a xylyl phenolic resin of formula 5, a phenol aralkyl phenolic resin of formula 6:

[Chemical Formula 5]

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

[Chemical Formula 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.

Inorganic filler

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. Further, 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 included as a foreign substance on the surface of silica, 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, 75 to 92% by weight. Within the above range, flame retardancy, fluidity and reliability of the epoxy resin composition can be secured.

Curing catalyst

The epoxy resin composition may include a curing catalyst containing a phosphonium compound having the above-described formula (1). The phosphonium-based compound may be contained in an amount of 0.01 to 5% by weight, for example, 0.02 to 1.5% by weight, for example, 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 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 preferable curing catalysts include organic phosphorus compounds, boron compounds, amine-based compounds, and 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 phosphonium compound of the present invention may be contained in the total curing catalyst in an amount of 10 to 100% by weight, for example, 60 to 100% by weight. In this range, the curing reaction time is not delayed, have.

The curing catalyst may be included in the epoxy resin composition in an amount of 0.01 to 5 wt%, for example, 0.02 to 1.5 wt%, for example, 0.05 to 1.5 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 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 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 90 to 120 캜. Within the above-mentioned range, the curing sufficiently proceeds even at a low temperature, and the effect of low-temperature curing may be obtained.

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 (1). Within this range, the curing shrinkage is low and can be used as an epoxy resin composition.

<Formula 1>

Cure shrinkage ratio = | 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).

Within this range, the curing shrinkage is low and can be used as an epoxy resin composition.

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 is not particularly limited, but the components contained in the composition are homogeneously mixed using a Henschel mixer or a Lodige mixer, and then melt-kneaded at 90 to 120 캜 in a roll mill or kneader , Cooling and milling processes.

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.

Semiconductor device sealing

The epoxy resin 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.

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.

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 .

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

Specific specifications of the components used in Examples and Comparative Examples are as follows.

(A) an epoxy resin

NC-3000 (Nippon Kayaku), a biphenyl type epoxy resin, was used.

(B) Curing agent

And HE100C-10 (Air Water), which is a xylock type phenol resin, was used.

(C) Curing catalyst

The curing catalysts were synthesized as shown in the following formulas (1a) to (1h).

(C1)

After adding 13.7 g of salicylamide to 21 g of 25% sodium methoxide solution and reacting at room temperature for 30 minutes, 41.9 g of tetraphenylphosphonium bromide dissolved in 50 g of methanol was slowly added to the solution, which was then reacted for 1 hour The resulting white solid compound (Ia) was filtered out to give 41 g. It was confirmed by NMR data that the compound represented by the following formula (1a).

[Formula 1a]

(1H, d), 6.72 (1H, d), 6.72 (1H,

(C2)

27.4 g of salicylamide was added to 50 g of MeOH, 21.6 g of 25% sodium methoxide solution was added, and the reaction was completed at room temperature for 30 minutes. Then, 41.9 g of tetraphenylphosphonium bromide dissolved in 50 g of methanol was slowly added thereto for 1 hour The resulting white solid (8) was filtered to give 50.8 g. NMR data show that the compound of the following formula (8) was obtained.

[Chemical Formula 1b]

(2H, d), 6.85 (2H, d), 6.77 (2H, t)

Salicylamide, which is an anion of the compound represented by Formula 1b, appears at a ratio of 1: 2 with phosphonium in the 1 H NMR spectrum integration. Even if 2 equivalents or more of salicylamide is used in the reaction, the result of integration of product NMR spectrum shows that phosphonium and salicylamide 1: 2, it is judged that the structure represented by the above formula (8) is in a stable form.

(C3)

100 g of triphenylphosphine, 60 g of 4-bromophenol and 3.7 g of NiBr 2 were placed in a 1 L round bottom flask, and 130 g of ethylene glycol was added thereto. The mixture was reacted at 180 ° C. for 6 hours to obtain a phenol-substituted phosphonium bromide salt .

[Chemical Formula 1c ']

21.0 g of salicylanilide was added to 50 g of MeOH and 21.6 g of 25% sodium methoxide solution was added thereto. The mixture was reacted at room temperature for 30 minutes to completely dissolve the reaction solution. Phosphonium bromide substituted with phenol- 43.5 g of the salt was slowly added and reacted for 1 hour, and the resulting white solid compound (1c) was filtered out to obtain 47 g. It was confirmed by NMR data that the compound of the following formula (1c).

[Chemical Formula 1c]

(1H, dt), 7.18 (1H, dt), 7.05-6.97 (3H, m), 6.71 (1H, &lt; / RTI &gt; d), 6.54 (1H, t)

(C4)

42.6 g of salicylanilide was added to 50 g of MeOH, 21.6 g of 25% sodium methoxide solution was added thereto, and the mixture was completely dissolved while being reacted at room temperature for 30 minutes. Then, phenol-substituted bromomethane salt 43.5 g was slowly added thereto, followed by further reaction for 1 hour, and the resulting white solid compound (1d) was filtered out to obtain 66 g. It was confirmed by NMR data that the compound of the formula (1d) was obtained.

&Lt; RTI ID = 0.0 &

M), 7.82-7.66 (16H, m), 7.43 (2H, dd), 7.35 (4H, t), 7.26 (2H, t), 7.08-7.03 , 6.85 (2H, dt), 6.67 (2H, dt)

Salicylanilide, which is an anion of the compound represented by the above formula (1d), appears at a ratio of 1: 2 with phosphonium in the 1 H NMR spectrum integration. Even if 2 equivalents or more of salicylanilide is used in the reaction, the result of integration of product NMR spectrum shows that phosphonium and salicylanilide 1: 2, it is judged that the structure represented by the above formula (1d) is in a stable form.

(C5)

15.0 g of salicylhydroxamic acid was added to 50 g of MeOH and 21.6 g of 25% sodium methoxide solution was added thereto. The reaction solution was completely dissolved while being reacted at room temperature for 30 minutes. Then, phenol-substituted phosphonium 41.9 g of bromide salt was slowly added and reacted for 1 hour. Then, the resulting white solid compound of formula (1e) was filtered out to obtain 49 g. It was confirmed by NMR data that the compound represented by the following formula (1e).

[Formula 1e]

(1H, dd), 7.06 (2H, dd), 6.69 (1H, dd), 7.69-7.63 -6.64 (2H, m), 6.55 (2H, dd)

(C6)

30.6 g of salicylhydroxamic acid was added to 50 g of MeOH and 21.6 g of 25% sodium methoxide solution was added thereto. The reaction solution was completely dissolved while being reacted at room temperature for 30 minutes. Then, phenol-substituted phosphonium 41.9 g of bromide salt was slowly added and reacted for 1 hour, and the resulting white solid compound of formula (1f) was filtered out to obtain 60 g of the compound. The compound was confirmed to be a compound of the following formula (1f) by NMR data.

(1f)

(2H, dd), 7.13 (2H, dd), 6.75 (2H, dd), 7.70-7.66 -6.69 (4 H, m), 6.65 (2 H, dd)

(C7)

26.3 g of 3-hydroxy-2-naphthanilide was added to 50 g of MeOH and 21.6 g of 25% sodium methoxide solution was added thereto. The resulting mixture was reacted at room temperature for 30 minutes to completely dissolve the compound. Then, phenol 43.5 g of the substituted phosphonium bromide salt was slowly added thereto, and further reacted for 1 hour. Then, 1 g of the resulting white solid compound was filtered out to obtain 49 g. NMR data confirmed that the compound was of the formula 1g.

[Formula 1g]

(1H, s), 7.87 (3H, t), 7.79-7.73 (8H, m), 7.69-7.64 (2H, d), 6.98 (1H, t), 6.82 (1H,

(C8)

26.3 g of 3-hydroxy-2-naphthanilide was added to 50 g of MeOH, and 21.6 g of 25% sodium methoxide solution was added thereto. The reaction solution was completely dissolved while being reacted at room temperature for 30 minutes. Then, 41.9 g of tetraphenylphosphonium bromide dissolved in 50 g of methanol was gradually added After further reaction, the resulting white solid 1 h was filtered out to give 53 g. It was confirmed by NMR data that the compound was of the formula (1h).

[Chemical Formula 1h]

(1H, d), 7.37-7.27 (3H, m), 7.11 (1H, t), 7.85-7.70 , 6.98 (1H, t), 6.82 (1H, t), 6.59 (1H, s)

(C9)

Triphenyl phosphine

(C10)

Addition products of triphenylphosphine and 1,4-benzoquinone

(D) Inorganic filler: A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 18 μm and spherical fused silica having an average particle diameter of 0.5 μm was used.

(E) Coupling agent

(e1) was mixed with KBM-803 (Shinetsu), which is a mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is e2) methyltrimethoxysilane.

(F) Additive

Carbon black MA-600 (Matsusita Chemical) was used as (f1) carnauba wax and (f2) colorant.

Examples and Comparative Examples

Each of the components was weighed according to the composition (unit: parts by weight) shown in the following Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition. Thereafter, the mixture was melt-kneaded at 95 DEG C using a continuous kneader, followed by cooling and pulverization, thereby preparing an epoxy resin composition for sealing semiconductor devices.

division Example Comparative Example One 2 3 4 5 6 7 8 One 2 (A) 8.6 8.6 8.6 8.6 8.6 8.6 8.6 8.6 8.6 8.6 (B) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0



(C) C1 0.4 - - - - - - - - - C2 - 0.4 - - - - - - - C3 - - 0.4 - - - - - - - C4 - - - 0.4 - - - - - - C5 - - - - 0.4 - - - - - C6 - - - - - 0.4 - - - - C7 - - - - - - 0.4 - - - C8 - - - - - - - 0.4 - - C9 - - - - - - - - 0.4 - C10 - - - - - - - - - 0.4 (D) 85 85 85 85 85 85 85 85 85 85 (E) (e1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (e2) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F) (f1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (f2) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

(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 specimen (125 × 12.6 × 6.4 mm) was obtained using a transfer molding press at 175 ° C. and 70 kgf / cm 2 using an ASTM mold for specimen preparation. 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 ratio was calculated from Equation 1 as follows.

<Formula 1>

Cure shrinkage ratio = | 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): 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 resin compositions prepared in the above Examples and Comparative Examples were heated at a mold temperature of 170 to 180 占 폚, a clamp pressure of 70 kgf / cm2, a feed pressure of 1,000 psi, a feed rate of 0.5 to 1 cm / 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 at 85 ° C. and 85 RH% relative humidity for 168 hours. The weight change due to moisture absorption was measured The moisture absorption rate was calculated by Equation (2).

<Formula 2>

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 in accordance with the standard for the application mold on the attachment side, and the resin composition prepared in the above example and the comparative example was pressed at a mold temperature of 170 to 180 DEG C and a clamp pressure of 70 kgf / , A feed pressure of 1,000 psi, a feed rate 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) Shore-D: Using an MPS (Multi Plunger System) molding machine equipped with a mold for an 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 hardening the epoxy resin composition to be evaluated at 175 ° C for 40, 50, 60, 70 and 80 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.

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

Evaluation items Example Comparative Example One 2 3 4 5 6 7 8 One 2 group
example
water
castle Flowability (inch) 63 68 71 77 68 73 69 75 51 61 Cure shrinkage (%) 0.35 0.34 0.40 0.33 0.34 0.37 0.38 0.34 0.41 0.42 Glass transition temperature (캜) 122 126 122 124 124 121 124 127 122 124 Moisture absorption rate (%) 0.24 0.20 0.25 0.22 0.30 0.24 0.24 0.23 0.26 0.26 Adhesion (kgf) 77 74 73 75 72 75 74 75 74 76
tile
key
G

Flat
end
Cure Time (Shore-D) 40 seconds 67 66 72 74 75 72 74 69 51 66 50 seconds 72 72 74 75 77 74 76 74 56 68 60 seconds 74 75 76 76 77 76 76 75 58 69 70 seconds 75 76 77 76 77 76 76 77 62 72 80 seconds 75 76 78 78 78 78 77 78 63 74 Save
stability 24hr 94% 96% 96% 97% 95% 97% 94% 96% 85% 89% 48hr 90% 91% 93% 95% 91% 96% 90% 93% 72% 79% 72hr 85% 87% 90% 94% 87% 93% 85% 88% 58% 68%

Compared with the comparative examples, Examples 1 to 8 exhibit high fluidity, and when compared with the curing time by the curing time, it can be confirmed that a higher degree of curing is exhibited even in a short curing time. Also, it can be confirmed that the difference in fluidity is small even in the case of storage stability after 72 hours.

In Examples 1 to 6, when one molecule forms an anion and when two molecules form a hydrogen bond cluster to form an anion, the two molecules are equivalent in curing strength per curing time, but two molecules in terms of fluidity It can be confirmed that anions forming hydrogen bond clusters are more prevalent. This is presumably due to the stronger formation of ionic bonds with the cations when the two molecules form hydrogen bond clusters, thereby suppressing the reactivity, and the weak hydrogen bond is rapidly broken and the cationic catalysis participates in the rapid curing.

Comparing Examples 7 and 8, it was found that the structure in which tetraphenylphosphonium cations in which all four substituents are phenyl groups were introduced (Example 7) when a cation having a phenol group was introduced on one side of the phosphonium Example 8) It can be seen that the curing strength drops sharply at shorter curing times. This is because not only the structure in which the phenolic group is introduced acts as Lewis acid but also the general acid which acts as a weak acid in the phenol moiety or the general base in which the proton moiety is released can act as a general base, The effect of activating the reaction part of the reaction product is more significant.

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

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (17)

A phosphonium compound represented by any one of the following formulas (1a) to (1h):
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

delete delete delete A process for producing a phosphonium compound represented by any of the following formulas (1a) to (1h), comprising the step of reacting a phosphonium-based cation-containing compound represented by the following general formula (2) with an anilide-
(2)

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydroxyl group-substituted or unsubstituted C6-C30 aromatic hydrocarbon group and Y is halogen)
(3)

(Wherein X is an arylene group having 6 to 30 carbon atoms, R ₅ is hydrogen, a hydroxyl group, or an aryl group having 6 to 30 carbon atoms, and m is an integer of 0 to 5. M is an alkali metal or an Ag to be),
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

&Lt; RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Chemical Formula 1h]

An epoxy resin, a curing agent, an inorganic filler, and a curing catalyst,
Wherein the curing catalyst comprises the phosphonium compound of claim 1.
The epoxy resin composition according to claim 6, 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 &Lt; / RTI &gt;
7. The epoxy resin composition according to claim 6, wherein the curing agent comprises a phenol resin.
The curing agent according to claim 6, wherein the curing agent is selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolac 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 6, wherein the curing catalyst is contained in an amount of 0.01 to 5 wt% of the epoxy resin composition.
7. The epoxy resin composition according to claim 6, wherein the phosphonium compound is contained in an amount of 10 to 100% by weight of the curing catalyst.
[7] The method according to claim 6, wherein the epoxy resin composition is stored in a thermostatic hygrostat set at 25 [deg.] C / 50RH% for 1 week while measuring the flow length after 72 hours and the storage stability as a percentage of the flow length immediately after preparation is 80% Epoxy resin composition.
The epoxy resin composition according to claim 6, wherein the epoxy resin composition has a curing shrinkage ratio of less than 0.4%
<Formula 1>
Cure shrinkage ratio = | 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).
A semiconductor device sealed with the epoxy resin composition of claim 6. The epoxy resin composition according to claim 6, further comprising a modified silicone oil.
16. The method of claim 15,
The modified silicone oil is a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, a silicone oil having a carboxyl functional group, or a combination thereof.
16. The method of claim 15,
Wherein the modified silicone oil is contained in an amount of 0.05 to 1.5% by weight based on the whole epoxy resin composition.

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