KR20190143347A - Thermosetting resin composite for metal clad laminate and metal clad laminate using the same - Google Patents

Abstract

The present invention relates to a thermosetting resin composite for a metal clad laminate having a predetermined thermal stress factor value, and a metal clad laminate comprising the thermosetting resin composite for a metal clad laminate.

Description

Thermosetting resin composite for metal foil laminate and metal foil laminate {THERMOSETTING RESIN COMPOSITE FOR METAL CLAD LAMINATE AND METAL CLAD LAMINATE USING THE SAME}

The present invention relates to a thermosetting resin composite and a metal foil laminate for a metal foil laminate, and more particularly, has excellent flowability in the prepreg stage or the semi-cured state, can realize low glass transition temperature and modulus, low thermal expansion rate, and warpage. The present invention relates to a thermosetting resin composite for a metal foil laminate and a metal foil laminate including the same.

Copper clad laminate used in the conventional printed circuit board is a prepreg by impregnating the substrate of glass fabric (glass fabric) in the varnish of the thermosetting resin and then semi-cured, it is heated and pressed together with the copper foil again Manufacture. The prepreg is used again for the purpose of constructing a circuit pattern on the copper foil laminate and building-up thereon.

Recently, as high-performance, thin, and lightweight electronic devices, communication devices, personal computers, and smart phones are accelerated, the semiconductor package is also required to be thin, and at the same time, the necessity of thinning a printed circuit board for a semiconductor package is increasing.

However, in the thinning process, the rigidity of the printed circuit board is reduced, and at the same time, the warpage problem of the semiconductor package is generated due to the difference in thermal expansion coefficient between the chip and the printed circuit board. Such warpage is further aggravated by a phenomenon in which the printed circuit board is not rolled back through a high temperature process such as reflow.

In order to improve the warpage phenomenon, researches on lowering the coefficient of thermal expansion of the substrate are being conducted. For example, a technique of filling a prepreg with a high content of a filler has been proposed, but simply a high content of the filler in the prepreg is proposed. There was a limit in decreasing the flowability of the prepreg if only filling with.

The present invention provides a thermosetting resin composite for a metal foil laminate for a semiconductor package, which has excellent flowability in a prepreg stage or a semi-cured state, can realize low glass transition temperature, modulus, low thermal expansion rate, and minimize warpage. It is to provide.

In addition, the present invention is to provide a metal foil laminate comprising the thermosetting resin composite for the metal foil laminate.

In this specification, the thermosetting resin composite for metal foil laminated plates whose thermal stress factor of following General formula 1 is 25 Mpa or less is provided.

[Formula 1]

Thermal Stress Factor

= ∫ [Storage Modulus * Thermal expansion coefficient] dT

In Formula 1, the thermal stress factor, storage modulus and thermal expansion coefficient are values defined or measured in the range of 30 ° C. to 260 ° C., respectively.

In addition, in this specification, the said thermosetting resin composite for metal foil laminated plates which has a sheet shape; And a metal foil formed on at least one surface of the thermosetting resin composite for the metal foil laminate.

Hereinafter, a thermosetting resin composite and a metal foil laminate for a metal foil laminate according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the present invention, a thermosetting resin composite for a metal foil laminate having a thermal stress factor of 25 Mpa or less is provided.

[Formula 1]

Thermal Stress Factor

= ∫ [Storage Modulus * Thermal expansion coefficient] dT

In Formula 1, the thermal stress factor, storage modulus and thermal expansion coefficient are values defined or measured in the range of 30 ° C. to 260 ° C., respectively.

As described above, the warpage problem of the semiconductor package occurs due to the difference in thermal expansion coefficient between the semiconductor chip and the printed circuit board in the thinning process of the semiconductor package, and this warpage phenomenon is intensified through a high temperature process such as a reflow. To improve this, only a method of lowering the thermal expansion coefficient of the substrate is known.

Accordingly, the present inventors continue to study the prepreg and the thermosetting resin composite for metal foil laminate and metal foil laminate formed by curing the same, the thermal stress factor value defined by the general formula 1 in the temperature range of 30 ℃ to 260 ℃ The experiment confirmed that this thermosetting resin composite for metal foil laminates of 25 Mpa or less, or 10 to 25 Mpa, or 12 to 21 Mpa can prevent warpage, and completed the invention.

More specifically, the thermal stress factor (Thermal Stress Factor) of the general formula (1) is a numerical value obtained by multiplying the coefficient of thermal expansion and storage modulus at each temperature in units of 1 ° C from 30 ° C to 260 ° C and then adding them together.

The coefficient of thermal expansion at each temperature is related to the strain of the thermosetting resin composite for metal foil laminates, and the storage modulus at each temperature is related to the ratio of strain to strain (stress or stress) of the thermosetting resin composite for metal foil laminates. do. In addition, the value obtained by multiplying the coefficient of thermal expansion and the storage modulus at each temperature is related to the strain (stress or stress) of the thermosetting resin composite for a metal foil laminate, and thus, each temperature in units of 1 ° C. from 30 ° C. to 260 ° C. The thermal stress factor (Thermal Stress Factor) of Formula 1, which is a value obtained by multiplying the coefficient of thermal expansion and the storage modulus at and sums the total strain (stress or stress) from 30 ° C. to 260 ° C., and represents a thermosetting resin for a metal foil laminate. Since the printed wiring board made of the composite shows the deformation force (stress or stress) applied to the semiconductor package, it is a factor that directly or indirectly shows warpage of the semiconductor package.

As described above, the thermosetting resin composite for the metal foil laminate of the embodiment may be formed by curing the prepreg. For example, the resultant obtained by etching the copper foil layer of a copper foil laminated board can be called "the thermosetting resin composite for metal foil laminated boards." This is formed by curing the prepreg obtained by hot air drying the thermosetting resin composition as described above.

The thermosetting resin composite for metal foil laminates may have a thermal stress factor of 25 Mpa or less, or 10 to 25 Mpa, or 12 to 21 Mpa, in the temperature range of 30 ° C. to 260 ° C., accordingly. Warpage can be minimized.

Even if the thermosetting resin composite for metal foil laminates having the same or lower thermal expansion coefficient as the thermosetting resin composite for metal foil laminates of the above embodiment, the thermal stress factor value defined by the general formula (1) is 25 Mpa or less, or 10 It was confirmed that the semiconductor package manufactured by using this did not satisfy the conditions of 25 to 25 Mpa, or 12 to 21 Mpa, so that relatively high warpage occurred.

On the other hand, the storage elastic modulus at 30 ℃ and 180 ℃ of the thermosetting resin composite for metal foil laminates may be 16 Gpa or less, specifically, the storage modulus at 30 ℃ of the thermosetting resin composite for metal foil laminates is 12 Gpa to 16 Gpa days The storage elastic modulus at 180 ° C. of the thermosetting resin composite for the metal foil laminate may be 7 Gpa to 12 Gpa.

The thermosetting resin composite for metal foil laminates has a low storage modulus of 16 Gpa or less in a relatively low temperature range, such as 30 ° C. and 180 ° C., and thus may have a relatively low thermal stress factor at the same thermal expansion coefficient. The warpage of the semiconductor package may have a relatively low characteristic in a low temperature range such as 180 ° C.

In addition, the storage elastic modulus at 260 ° C. of the thermosetting resin composite for a metal foil laminate may have a storage modulus of 8 Gpa or less, or 5 to 8 Gpa. As the thermosetting resin composite for the metal foil laminate has the above-described storage modulus at 260 ° C., the warpage of the semiconductor package at 260 ° C. may have a relatively low thermal stress factor at the same thermal expansion coefficient. Can be.

That is, since the thermal stress factor may have a relatively low thermal stress factor in the temperature range of 30 ° C to 260 ° C, the warpage of the semiconductor package may be low in the temperature range of 30 ° C to 260 ° C. .

 The thermal expansion coefficient of the thermosetting resin composite for the metal foil laminate may be 12 ppm / ° C. or less, or 5 to 12 ppm / ° C., or 10 ppm / ° C. or less, or 4 to 10 ppm / ° C. As described above, the thermosetting resin composite for the metal foil laminate has a low coefficient of thermal expansion, and the thermal stress factor of the general formula 1 is 25 Mpa or less, so that the semiconductor package manufactured using the thermosetting resin composite for the metal foil laminate is Only relatively low levels of warpage can be seen.

On the other hand, the thermosetting resin composite for the metal foil laminate may include a thermosetting resin composition and a fiber substrate.

More specifically, the thermosetting resin composition, 1) sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a nitro group, cyano group, or halogen group; an amine compound including at least one functional group selected from the group consisting of 2) thermosetting resins, 3) thermoplastic resins, and 4 ) Inorganic fillers.

In addition, the thermosetting resin composition may have a glass transition temperature of 230 ° C or less.

The thermosetting resin composition exhibits relatively low reactivity as the amine compound including the above-mentioned strong electron withdrawing group (EWG) contains, thereby making it possible to easily control the curing reaction of the thermosetting resin composition. .

Particularly, the thermosetting resin composition includes the thermosetting resin content in an amount of 400 parts by weight or less based on 100 parts by weight of the amine compound, inducing the thermosetting resin to be uniformly curable to a more sufficient level without the effect of the filler charged in a high content. Thus, the reliability of the final product can be improved, and mechanical properties such as toughness can also be increased, and the glass transition temperature can be lowered to 230 ° C. or lower.

In the prior art, the amount of flowability and moldability decreases due to excessive curing of the thermosetting resin when the amine curing agent is added in a relatively excessive amount, such as including the thermosetting resin content of 400 parts by weight or less with respect to 100 parts by weight of the amine curing agent. There was.

However, even when an excessive amount of a specific amine curing agent having reduced reactivity, including the electron withdrawing group (EWG) as described above, is added, it is possible to suppress the rapid increase in the curing rate of the thermosetting resin due to the decrease in the reactivity of the curing agent. It is possible to exhibit high flowability even in long-term storage in the resin composition for semiconductor packages or the prepreg state obtained therefrom, and can have excellent moldability.

The thermosetting resin composition is 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight to 300 parts by weight, or 180 parts by weight to 290 parts by weight based on 100 parts by weight of the amine curing agent. Or 190 parts by weight to 290 parts by weight. When the amine curing agent or the thermosetting resin is a mixture of two or more kinds, the content of the thermosetting resin mixture is also 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight to 300 parts by weight, based on 100 parts by weight of the amine curing agent mixture. Or 180 parts by weight to 290 parts by weight, or 190 parts by weight to 290 parts by weight.

When the content of the thermosetting resin is excessively increased to more than 400 parts by weight based on 100 parts by weight of the amine curing agent, it is difficult to uniformly cure the thermosetting resin to a more sufficient level due to the increase of the curing density and the effect of the filler charged at a high content. The reliability of the product being manufactured can be reduced, and mechanical properties such as toughness can also be reduced.

Meanwhile, the thermosetting resin composition may satisfy an equivalent ratio of 1.4 or more, or 1.4 to 2.5, or 1.45 to 2.5, or 1.45 to 2.1, or 1.45 to 1.8, or 1.49 to 1.75.

[Equation 1]

Equivalent ratio = total active hydrogen equivalents contained in the amine curing agent / total curable functional group equivalents contained in the thermosetting resin

More specifically, in Equation 1, the total active hydrogen equivalent contained in the amine curing agent, the total weight (unit: g) of the amine curing agent divided by the unit equivalent of the active hydrogen of the amine curing agent (g / eq) Means.

When the amine curing agent is a mixture of two or more kinds, the value obtained by dividing the weight (unit: g) by the unit equivalent of active hydrogen (g / eq) for each compound is obtained, and the sum thereof is contained in the amine curing agent of Equation 1 above. The total equivalent active hydrogen equivalent can be obtained.

The active hydrogen contained in the amine curing agent means a hydrogen atom contained in the amino group (-NH ₂ ) present in the amine curing agent, and the active hydrogen can form a cured structure through reaction with the curable functional group of the thermosetting resin. have.

In addition, in Equation 1, the total curable functional group equivalent contained in the thermosetting resin means a value obtained by dividing the total weight (unit: g) of the thermosetting resin by the unit equivalent (g / eq) of the curable functional group of the thermosetting resin. do.

When the thermosetting resin is a mixture of two or more kinds, the value obtained by dividing the weight (unit: g) by the unit equivalent (g / eq) of the curable functional group for each compound is obtained, and the sum thereof is contained in the thermosetting resin of Equation 1 above. The total curable functional group equivalent can be obtained.

The curable functional group contained in the thermosetting resin means a functional group that forms a cured structure through the reaction with the active hydrogen of the amine curing agent, and the type of the curable functional group may also vary according to the thermosetting resin type.

For example, when using an epoxy resin as the thermosetting resin, the curable functional group contained in the epoxy resin may be an epoxy group, when using a bismaleimide resin as the thermosetting resin, curable contained in the bismaleimide resin The functional group can be a maleimide group.

That is, when the thermosetting resin composition satisfies the equivalent ratio calculated by Equation 1 above 1.4, it means that the curable functional group contained in all the thermosetting resins contains a sufficient level of the amine curing agent to cause a curing reaction. do. Therefore, when the equivalent ratio calculated by Equation 1 in the thermosetting resin composition is reduced to less than 1.4, it is difficult for the thermosetting resin to be uniformly cured to a more sufficient level under the influence of the filler charged with a high content, resulting in the reliability of the final product. There is a disadvantage that this can be reduced, and mechanical properties can also be reduced.

The amine compound may be a sulfone group; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an alkylamine group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; and an aromatic amine compound including at least one functional group selected from the group consisting of 2 to 5 amine groups. have.

More specifically, the amine compound may include one or more compounds selected from the group consisting of the following Chemical Formulas 1 to 3.

[Formula 1]

In Formula 1, A is a sulfone group, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms, and X ₁ to X ₈ are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms. , An aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, R _1, R ₁ ′ _, R ₂ and R ₂ ′ each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, An aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms, n may be an integer of 1 to 10.

The alkylene group having 1 to 10 carbon atoms, the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently selected from the group consisting of nitro, cyano and halogen groups It may be substituted with the above functional groups.

[Formula 2]

In Chemical Formula 2, Y ₁ to Y ₈ are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R _3, R ₃ ′ _, R ₄ and R ₄ ′ each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. , m is an integer of 1 to 10, wherein the alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms are each independently selected from the group consisting of nitro group, cyano group and halogen group It may be substituted with one or more functional groups.

[Formula 3]

In Chemical Formula 3, Z ₁ to Z ₄ are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. R _5, R ₅ ′ _, R ₆ and R ₆ ′ each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms. The alkyl group having 1 to 6 carbon atoms, the aryl group having 6 to 15 carbon atoms, and the heteroaryl group having 2 to 20 carbon atoms may be independently substituted with one or more functional groups selected from the group consisting of nitro, cyano and halogen groups. .

The alkyl group is a monovalent functional group derived from alkane, and is, for example, linear, branched or cyclic, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, Hexyl and the like. At least one hydrogen atom included in the alkyl group may be substituted with each substituent.

The alkylene group is a divalent functional group derived from an alkane, and is, for example, a linear, branched or cyclic group, such as a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, tert-butylene group, pentylene group, hexylene group and the like. One or more hydrogen atoms contained in the alkylene group may be substituted with the same substituents as in the case of the alkyl group, respectively.

The aryl group is a monovalent functional group derived from arene, and may be, for example, monocyclic or polycyclic. Specifically, the monocyclic aryl group may be a phenyl group, biphenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. At least one hydrogen atom of such an aryl group may be each substituted with the same substituent as in the alkyl group.

The heteroaryl group is a heterocyclic group including O, N or S as a hetero atom, and the number of carbon atoms is not particularly limited, but may be 2 to 30 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group and dibenzofuran And the like, but are not limited thereto. At least one hydrogen atom of such a heteroaryl group may be each substituted with the same substituent as in the alkyl group.

The term "substituted" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent may be substituted, and when two or more are substituted, two or more The substituents may be the same or different from one another.

More specifically, Chemical Formula 1 may include a compound represented by Chemical Formula 1-1 below.

[Formula 1-1]

In Chemical Formula 1-1, A, X ₁ to X ₈ , R _1, R ₁ ′ _, R ₂ and R ₂ ′, and the content of n include the above-described information in Chemical Formula 1.

Specific examples of the formula 1-1 is 4,4'-diaminodiphenyl sulfone (A in formula 1-1 is a sulfone group, X ₁ to X _8, R _1, R ₁ ' _, R ₂ and R ₂ ' are each independently Hydrogen atom, n is 1), bis (4-aminophenyl) methanone (In Formula 1-1, A is a carbonyl group, X ₁ , X _2, R _1, R ₁ ' _, R ₂ and R ₂ ' are respectively. Independently hydrogen atom, n is 1), 4,4 '-(perfluoropropane-2,2-diyl) dianiline (A in formula 1-1 is perfluoropropane-2,2-diyl, X ₁ to X _8, R _1, R ₁ ′ _, R ₂ and R ₂ ′ each independently represent a hydrogen atom, n is 1), 4,4 '-(2,2,2-trifluoroethane-1,1-diyl) dianiline ( In Formula 1-1, A is 2,2,2-trifluoroethane-1,1-diyl, X ₁ to X _8, R _1, R ₁ ′ _, R ₂ and R ₂ ′ are each independently a hydrogen atom, and n is 1).

In addition, Chemical Formula 2 may include a compound represented by Chemical Formula 2-1.

[Formula 2-1]

In Chemical Formula 2-1, the contents of Y ₁ to Y ₈ , R _3, R ₃ ′ _, R ₄ and R ₄ ′, m include the above-mentioned contents in Chemical Formula 2.

Specific examples of Chemical Formula 2-1 include 2,2 ', 3,3', 5,5 ', 6,6'-octafluorobiphenyl-4,4'-diamine (Y ₁ to Y ₈ in Chemical Formula 2-1 is halogen. Fluorine groups _, R _3, R ₃ ' _, R ₄ and R ₄ ' are each independently a hydrogen atom, m is 1), 2,2'-bis (trifluoromethyl) biphenyl-4,4'-diamine ( Y ₂ and Y ₇ are each trifluoromethyl group, and Y ₁ , Y ₃ , Y ₄ , Y ₅ , Y ₆ , Y ₈ are hydrogen atoms _, R _3, R ₃ ' _, R ₄ and R ₄ ' are each independently And a hydrogen atom, m is 1).

In addition, Chemical Formula 3 may include a compound represented by Chemical Formula 3-1.

[Formula 3-1]

In Formula 3-1, the contents of Z ₁ to Z ₄ , R _5, R ₅ ′ _, R ₆ and R ₆ ′ include the above-mentioned details in Formula 3 above.

Specific examples of the formula 3-1 include 2,3,5,6-tetrafluorobenzene-1,4-diamine (wherein Z ₁ to Z ₄ in the formula 3-1 is a fluorine group _, R _5, R ₅ ' _, R ₆ And R ₆ ′ are each independently a hydrogen atom.

The thermosetting resin composition may include an amine compound, a thermosetting resin, a thermoplastic resin, and an inorganic filler.

Although the content of the components is not particularly limited, the above-described components may be included in consideration of the physical properties of the final product manufactured from the thermosetting resin composition, and the content ratio between these components is as described below.

The thermosetting resin may include an epoxy resin. As the epoxy resin, those commonly used in thermosetting resin compositions for semiconductor packages can be used without limitation, and the type thereof is not limited, and bisphenol A type epoxy resins, phenol novolac epoxy resins, phenyl aralkyl epoxy resins, and tetra It may be at least one selected from the group consisting of a phenyl ethane epoxy resin, a naphthalene epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene epoxy resin, and a mixture of a dicyclopentadiene epoxy resin and a naphthalene epoxy resin.

Specifically, the epoxy resin is a bisphenol-type epoxy resin represented by the formula (5), a novolak-type epoxy resin represented by the formula (6), a phenyl aralkyl-based epoxy resin represented by the formula (7), tetraphenyl represented by the formula (8) 1 selected from the group consisting of an ethane type epoxy resin, a naphthalene type epoxy resin represented by the following Chemical Formulas 9 and 10, a biphenyl type epoxy resin represented by the following Chemical Formula 11, and a dicyclopentadiene type epoxy resin represented by the following Chemical Formula 12: More than one species can be used.

[Formula 5]

In Chemical Formula 5,

또는

이고, R is

or

ego,

n is 0 or an integer from 1 to 50.

More specifically, the epoxy resin of Formula 5 may be a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol M type epoxy resin, or a bisphenol S type epoxy resin, respectively, according to the type of R.

[Formula 6]

In Chemical Formula 6,

R is H or CH ₃ ,

n is 0 or an integer from 1 to 50.

More specifically, the novolak-type epoxy resin of Formula 6 may be a phenol novolak-type epoxy resin or cresol novolak-type epoxy resin, respectively, depending on the type of R.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Chemical Formula 11,

n is 0 or an integer from 1 to 50.

[Formula 12]

In Formula 12, n is 0 or an integer of 1 to 50.

On the other hand, the thermosetting resin may further comprise at least one resin selected from the group consisting of bismaleimide resin, cyanate ester resin and bismaleimide-triazine resin.

Usually, the bismaleimide resin can be used without limitation, which is used in a thermosetting resin composition for a semiconductor package, and the kind thereof is not limited. As a preferable example, the bismaleimide resin is a diphenylmethane bismaleimide resin represented by the following formula (13), a phenylene type bismaleimide resin represented by the following formula (14), and a bisphenol A diphenyl represented by the following formula (15). It may be at least one selected from the group consisting of an ether bismaleimide resin, and a bismaleimide resin composed of an oligomer of a diphenylmethane bismaleimide represented by the following formula (16) and a phenylmethane type maleimide resin.

[Formula 13]

In Chemical Formula 13,

R ₁ and R ₂ are each independently H, CH ₃ or C ₂ H ₅ .

[Formula 14]

[Formula 15]

[Formula 16]

In Chemical Formula 16,

n is 0 or an integer from 1 to 50.

In addition, cyanate ester resin may be cited as a specific example of the cyanate-based resin, and generally used in thermosetting resin compositions for semiconductor packages may be used without limitation, and the kind thereof is not limited.

As a preferable example, the cyanate ester resin is a novolac cyanate resin represented by the following formula (17), a dicyclopentadiene type cyanate resin represented by the following formula (18), and a bisphenol type cyanate resin represented by the following formula (19). And some triazineized prepolymers thereof, and these may be used alone or in combination of two or more thereof.

[Formula 17]

In Chemical Formula 17,

n is 0 or an integer from 1 to 50.

[Formula 18]

In Chemical Formula 18,

n is 0 or an integer from 1 to 50.

[Formula 19]

In Chemical Formula 19,

또는

이다.R is

or

to be.

More specifically, the cyanate resin of Formula 19 may be bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F type cyanate resin, or bisphenol M type cyanate resin, respectively, according to the type of R. .

The bismaleimide-triazine resin may be cited as the bismaleimide resin, and the bismaleimide-triazine resin may be used without limitation in the thermosetting resin composition for a semiconductor package. Kind is not limited.

On the other hand, the thermoplastic resin has the effect of increasing the toughness (Toughness) after the curing of the prepreg, and serves to reduce the warpage of the semiconductor package by lowering the coefficient of thermal expansion and elastic modulus. Specific examples of the thermoplastic resin include (meth) acrylate-based polymers.

Examples of the (meth) acrylate-based polymer are not particularly limited, and for example, an acrylic ester copolymer including a repeating unit derived from a (meth) acrylate monomer and a repeating unit derived from (meth) acrylonitrile; Or it may be an acrylic ester copolymer containing a repeating unit derived from butadiene. For example, the (meth) acrylate-based polymer is a monomer such as butyl acrylate, ethyl acrylate, acrylonitrile, methyl methacrylate, glycidyl methacrylate in the range of 1 to 40% by weight, respectively ( Relative to the total weight of the entire monomer).

The (meth) acrylate-based polymer may have a weight average molecular weight of 500,000 to 1,000,000. If the weight average molecular weight of the (meth) acrylate-based polymer is too small, after curing, the effect of increasing the toughness (Toughnes) of the thermosetting resin composite for metal foil laminate or decrease in thermal expansion rate and elastic modulus may be technically disadvantageous. In addition, when the weight average molecular weight of the (meth) acrylate-based polymer is too large, it is possible to reduce the flowability of the prepreg.

The thermoplastic resin may determine the content used in consideration of the use and properties of the final product, for example, the thermosetting resin composition for a semiconductor package includes 10 to 200 parts by weight of the thermoplastic resin relative to 100 parts by weight of the thermosetting resin. can do.

Meanwhile, the thermosetting resin composition may include the amine compound described above, and may further include an additional curing agent other than the amine compound.

More specifically, the thermosetting resin composition is selected from the group consisting of a second amine compound different from the amine compound, an acid anhydride resin, a bismaleimide resin, a cyanate resin, a phenol novolak resin and a benzoxazine resin. It may further comprise one or more curing agents.

The thermosetting resin composition may include an inorganic filler.

The inorganic filler may be used without limitation in the thermosetting resin composition for the conventional semiconductor package, specific examples are silica, aluminum trihydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate , Zinc stannate, alumina, clay, kaolin, talc, calcined kaolin, calcined talc, mica, short glass fiber, glass fine powder and hollow glass, and may be one or more selected from the group consisting of these.

The thermosetting resin composition may include 30 to 300 parts by weight, or 30 to 200 parts by weight, or 50 to 150 parts by weight of the inorganic filler relative to a total of 100 parts by weight of the thermosetting resin, the thermoplastic resin, and the amine compound. If the content of the inorganic filler is too small, the coefficient of thermal expansion increases, so that the warpage phenomenon in the reflow process is intensified, and the rigidity of the printed circuit board is reduced.

In addition, when the surface-treated filler is used, a packing density may be increased by using a small size of the nano particle size and a large size of the micro particle size to increase the filling rate.

The inorganic filler may include two or more inorganic fillers having different average particle diameters. Specifically, at least one of the two or more inorganic fillers may be an inorganic filler having an average particle diameter of 0.1 μm to 100 μm, and the other one may be an inorganic filler having an average particle diameter of 1 nm to 90 nm.

The content of the inorganic filler having an average particle diameter of 1 nm to 90 nm may be 1 part by weight to 30 parts by weight based on 100 parts by weight of the inorganic filler having an average particle diameter of 0.1 μm to 100 μm.

The inorganic filler may use silica surface-treated with a silane coupling agent from the viewpoint of improving moisture resistance and dispersibility.

As the method for surface treatment of the inorganic filler, a method of dry or wet treatment of silica particles using a silane coupling agent as a surface treatment agent may be used. For example, the silica may be surface treated by a wet method using 0.01 to 1 part by weight of the silane coupling agent based on 100 parts by weight of the silica particles.

Specifically, as the silane coupling agent, such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane Aminosilane coupling agent, epoxy silane coupling agent such as 3-glycidoxypropyltrimethoxysilane, vinyl silane coupling agent such as 3-methacryloxypropyl trimethoxysilane, N-2- (N-vinylbenzylaminoethyl Cation silane coupling agent and phenyl silane coupling agent such as) -3-aminopropyltrimethoxysilane hydrochloride, and the silane coupling agent may be used alone, or at least two silane coupling agents may be combined as necessary. Can be used.

More specifically, the silane compound may include aromatic amino silane or (meth) acrylsilane, and the inorganic filler having an average particle diameter of 0.1 μm to 100 μm may use silica treated with aromatic amino silane. As the inorganic filler having an average particle diameter of 1 nm to 90 nm, silica treated with (meth) acryl silane can be used. Specific examples of the aromatic amino silane-treated silica may include SC2050MTO (Admantechs), and specific examples of the (meth) acrylsilane-treated silica may include AC4130Y (Nissan chemical). The (meth) acryl was used to mean both acryl or methacryl.

In the prepreg manufacturing process, the thermosetting resin composition may be used as a solution by adding a solvent as necessary. The solvent is not particularly limited as long as it shows good solubility in the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, nitrile, and the like can be used. Or you may use the mixed solvent which used 2 or more types together. In addition, the content of the solvent is not particularly limited as long as it can impregnate the resin composition in the glass fiber during prepreg production.

In addition, the thermosetting resin composition may further include various high molecular compounds such as other thermosetting resins, thermoplastic resins, and oligomers and elastomers thereof, and other flame retardant compounds or additives, so long as the properties inherent in the resin composition are not impaired. These are not particularly limited as long as they are selected from those commonly used.

For example, additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, pigments, dyes, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, brightening agents, and the like. It is also possible.

The thermosetting resin composite for a metal foil laminate means that the thermosetting resin composition for a semiconductor package is impregnated into a fiber substrate in a cured state.

Although the kind of the fiber base material is not particularly limited, polyamide-based resin fibers, such as glass fiber base material, polyamide resin fiber, aromatic polyamide resin fiber, polyester resin fiber, aromatic polyester resin fiber, all aromatic polyester Synthetic fiber base, kraft paper, cotton linter paper, linter and kraft pulp composed of woven or non-woven fabric mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, polybenzoxazole fibers, and fluororesin fibers Paper substrates based on honcho paper and the like may be used, and glass fiber substrates are preferably used. The glass fiber substrate can improve the strength of the prepreg, lower the absorption rate, and reduce the coefficient of thermal expansion.

The glass fiber substrate may be selected from glass substrates used for various printed circuit board materials. Examples thereof include, but are not limited to, glass fibers such as E glass, D glass, S glass, T glass, NE glass and L glass, Q glass. If necessary, the glass-based material may be selected according to the intended use or performance. Glass-based forms are typically woven, nonwoven, roving, chopped strand mats or surfacing mats. Although the thickness of the glass substrate is not particularly limited, about 0.01 to 0.3 mm or the like can be used. Of these materials, glass fiber materials are more preferred in terms of strength and water absorption properties.

In addition, the method for preparing the prepreg is not particularly limited, and may be prepared by a method well known in the art. For example, the method of manufacturing the prepreg may be used by an impregnation method, a coating method using various coaters, a spray injection method, or the like.

In the case of the impregnation method, after preparing the varnish, the prepreg may be prepared by impregnating the fiber substrate with the varnish.

That is, although the manufacturing conditions, etc. of the said prepreg are not specifically limited, It is preferable to use it in the varnish state which added the solvent to the said thermosetting resin composition for semiconductor packages. The solvent for the resin varnish is not particularly limited as long as it can be mixed with the resin component and has good solubility. Specific examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide and dimethylacetamide, methylcello Aliphatic alcohols such as solve and butyl cellosolve.

In the preparation of the prepreg, the solvent used is preferably volatilized by 80% by weight or more. For this reason, there is no restriction | limiting also in a manufacturing method, drying conditions, etc., The temperature at the time of drying is about 80 degreeC-200 degreeC, and time does not have a restriction | limiting in particular in balance with the gelation time of a varnish. The varnish impregnation amount is preferably such that the resin solid content of the varnish is about 30 to 80% by weight relative to the total amount of the resin solid content of the varnish and the base material.

In addition, according to another embodiment of the invention, the above-mentioned thermosetting resin composite for metal foil laminate having a sheet shape; And a metal foil formed on at least one surface of the thermosetting resin composite for the metal foil laminate.

The metal foil is copper foil; Aluminum foil; A composite foil having a three-layer structure including nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy as an intermediate layer, and including copper layers having different thicknesses on both surfaces thereof; Or the composite foil of the two-layered structure which combined aluminum and copper foil.

According to a preferred example, the metal foil may be copper foil or aluminum foil, and a material having a thickness of about 2 to 200 μm may be used, but the thickness thereof is preferably about 2 to 35 μm. Preferably, copper foil is used as said metal foil. In addition, as the metal foil, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, or lead-tin alloy is used as an intermediate layer, and on both sides thereof, a copper layer of 0.5 to 15 µm and a thickness of 10 to 300 µm. You may use the composite foil of the 3-layered structure which provided the copper layer, or the 2-layered composite foil which combined aluminum and copper foil.

The metal laminated plate containing the thermosetting resin composite for metal foil laminated plates thus manufactured can be used for manufacture of single-sided, double-sided, or multilayer printed circuit boards. The metal foil laminate may be circuit processed to manufacture single-sided or double-sided or multilayer printed circuit boards, and the circuit processing may be performed by a general single-sided, double-sided or multilayer printed circuit board manufacturing process.

According to the present invention, it has excellent flowability in a prepreg stage or a semi-cured state, and can realize low glass transition temperature and modulus, low thermal expansion coefficient, and minimize warpage, and thus, thermosetting property of a metal foil laminate plate for a semiconductor package. A metal foil laminate comprising a resin composite and the thermosetting resin composite for the metal foil laminate may be provided.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

<Examples and Comparative Examples: Thermosetting Resin Compositions for Semiconductor Packages, Prepregs, Thermosetting Resin Composites for Metal Foil Laminates, and Copper Foil Laminates>

(1) Preparation of thermosetting resin composition for semiconductor package

According to the composition of Table 1 and Table 2, each component was added to methyl ethyl ketone according to the solid content of 40% and mixed, and then stirred at room temperature at 400 rpm for one day at room temperature for resin compositions for semiconductor packages of Examples and Comparative Examples (resin Varnish) was prepared. Specifically, the specific composition of the resin composition prepared in Example is as shown in Table 1 below, and the specific composition of the resin composition prepared in Comparative Example is as shown in Table 2 below.

(2) Preparation of prepreg, thermosetting resin composite for metal foil laminate and copper foil laminate

The resin composition (resin varnish) prepared for the semiconductor package was impregnated into glass fiber having a thickness of 13 μm (T-glass # 1010, manufactured by Nittobo Co., Ltd.), followed by hot air drying at a temperature of 170 ° C. for 2 to 5 minutes to obtain 18 μm. Prepregs were prepared.

After laminating the two prepregs prepared above, copper foil (thickness 12 μm, manufactured by Mitsui) was placed on both sides thereof, and laminated, and cured for 100 minutes under conditions of 220 ° C. and 35 kg / cm 2 to prepare a copper foil laminate. It was.

<Experimental Example: Measurement of physical properties of the thermosetting resin composition for semiconductor packages, prepregs, thermosetting resin composites for metal foil laminates and copper foil laminates obtained in Examples and Comparative Examples>

Thermosetting resin composition for semiconductor packages, prepregs, obtained in Examples and Comparative Examples, The physical properties of the thermosetting resin composite and the copper foil laminate for a metal foil laminate were measured by the following method, and the results are shown in Table 3.

1.Coefficient of Thermal Expansion (CTE)

After etching and removing the copper foil layer of the copper foil laminated board obtained by the said Example and the comparative example, the test piece was produced in MD direction, and 30 degreeC to 260 degreeC using TMA (TA Instruments, Q400), and the temperature increase rate 10 degreeC / After measurement under min conditions, the measured value in the range of 50 ° C to 150 ° C was recorded as the coefficient of thermal expansion.

At this time, the resultant obtained by etching the copper foil layer of the copper foil laminated sheet is called "the thermosetting resin composite for metal foil laminated sheets", which is formed by curing the prepreg obtained by hot air drying the thermosetting resin composition as described above.

2. Glass transition temperature (Tg)

After etching and removing the copper foil layer of the copper foil laminated board obtained by the said Example and the comparative example, the test piece (thermosetting resin composite for metal foil laminated boards) was produced in MD direction, and it was 5 degreeC in tension mode using DMA (TA Instruments, Q800). The peak temperature of tan delta was measured as the glass transition temperature by measuring from 25 ° C. to 300 ° C. under an elevated temperature condition of / min.

3. Storage Modulus Measurement

After etching and removing the copper foil layer of the copper foil laminated board obtained by the said Example and the comparative example, the test piece (thermosetting resin composite for metal foil laminated boards) was produced in MD direction, and it was 5 degreeC in tension mode using DMA (TA Instruments, Q800). The storage modulus was measured from 25 ° C. to 300 ° C. under an elevated temperature condition per minute.

4. Filling of circuit pattern

The prepreg obtained by the said Example and the comparative example was located on both surfaces of a circuit pattern (pattern height 7um, 50% of residual ratio), and copper foil (12 micrometers in thickness, the Mitsui company make) was placed on it, and 220 degreeC and 35 After pressing for 100 minutes under the condition of kg / cm 2, the copper foils on both sides were etched to evaluate the circuit pattern fillability under the following criteria.

○: no void

Ｘ: Void occurs

5. Tensile Elongation Measurement

15 sheets of the prepreg obtained in the above Examples and Comparative Examples were laminated so as to match the MD and TD directions of the glass fibers, and pressed for 100 minutes under conditions of 220 ° C. and 35 kg / cm 2, followed by IPC-TM-650 ( According to 2.4.18.3), tensile elongation in the MD direction was measured using a Universal Testing Machine (Instron 3365).

6. Warpage of semiconductor package (Warpage measurement)

In the copper foil laminated sheet obtained by the said Example and the comparative example, a part of copper foil was processed through the normal etching method, and the printed wiring board was manufactured (thickness 90um). A semiconductor package (14.5 mm x 14.5 mm x thickness 390 um) was manufactured by mounting a semiconductor chip (11.5 mm x 11.5 mm x thickness 80 um) on the manufactured printed wiring board. For the semiconductor package, the warpage was measured on the basis of the Shadow Moire measurement theory using a warpage measuring device (AKROMETRIX Co., Ltd. THERMOIRE PS100). The warpage was determined by measuring the semiconductor package from 30 ° C. to 260 ° C., and then cooled to 30 ° C. by the difference between the maximum value and the minimum value of the warpage. The warpage of the semiconductor package was evaluated based on the following criteria.

○: The difference between the maximum value and the minimum value of the warpage is 170 μm or less

Ｘ: The difference between the maximum and minimum value of deflection is 170um or more

7. Calculation of Thermal Stress Factor

Based on the obtained thermal expansion coefficient and storage modulus, multiply the coefficient of thermal expansion and storage modulus at each temperature in units of 1 ° C. from 30 ° C. to 260 ° C., and then add them together to measure the thermal stress factor of the following general formula (1). (Calculated).

[Formula 1]

Thermal Stress Factor (Unit: MPa)

= ∫ [Storage Modulus * Thermal expansion coefficient] dT

Composition of thermosetting resin composition for semiconductor packages and physical properties of thermosetting resin composites for metal foil laminates of Examples (unit: g) Example 1 Example 2 Example 3 Example 4 Epoxy resin XD-1000
(Epoxy equivalent 253 g / eq) 0 0 14 0 NC-3000H
(Epoxy equivalent 290 g / eq) 46.1 39.48 33.5 12 HP-6000 (epoxy equivalent 250 g / eq) 24 Bismaleimide BMI-2300
(Maleimide equivalent 179 g / eq) 4.3 3.72 4.3 3.72 Diamine compounds DDS
(Active hydrogen equivalent 62g / eq) 19.6 16.8 18.2 10.14 TFB
(Active hydrogen equivalent 80 g / eq) 10.14 DDM (active hydrogen equivalent 49.5 g / eq) Thermoplastic resin Acrylic rubber B (KG-3015P, Mw 80 only) 30 30 Acrylic rubber C (KG-3113, Mw 60 only) 40 40 Inorganic filler SC2050MTO 70 90 108 135 AC4130Y 0 10 12 15 Equivalence Ratio (Diamine / Epoxy) 1.73 1.73 1.51 1.84 Tg ℃ 212 209 221 197 CTE ppm / ℃ 9.1 8.5 8.1 7.8 Circuit Pattern Fillability ○ ○ ○ ○ Storage modulus
(Storage Modulus) 30 ℃ Gpa 13.1 14.5 15.1 15.4 180 ℃ Gpa 9.7 11.2 11.6 11.8 260 ℃ Gpa 6.4 6.6 6.8 6.4 Tensile elongation
(Elongation) % 4.1 3.9 3.8 3.6 TSF Mpa 17.3 20.4 20.4 20.2 Warpage um ○ ○ ○ ○

Composition of thermosetting resin composition for semiconductor package of Comparative Example and physical properties confirmation of thermosetting resin composite for metal foil laminate (unit: g) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Epoxy
Suzy XD-1000
(Epoxy equivalent 253 g / eq) 14.0 0 0 NC-3000H
(Epoxy equivalent 290 g / eq) 65.8 65.8 65.8 HP-6000 (epoxy equivalent 250 g / eq) 28.0 Bismaleimide BMI-2300
(Maleimide equivalent 179 g / eq) 6.2 16.8 6.2 6.2 Hardener DDS
(Active hydrogen equivalent 62g / eq) 11.2 28 28 TFB
(Active hydrogen equivalent 80 g / eq) DDM (active hydrogen equivalent 49.5 g / eq) 28 Thermoplastic resin Acrylic rubber B (KG-3015P, Mw 80 only) 30 Acrylic rubber C (KG-3113, Mw 60 only) Inorganic filler SC2050MTO 260 135 260 135 AC4130Y 0 15 0 15 Equivalence Ratio (Diamine / Epoxy) 2.16 0.69 1.73 1.73 Tg ℃ 195 289 213 215 CTE ppm / ℃ 9.8 7.8 9.6 11.6 Circuit Pattern Fillability X ○ ○ ○ Storage modulus
(Storage Modulus) 30 ℃ Gpa 21.7 16.1 21.3 18.3 180 ℃ Gpa 18.2 15 19.2 16.6 260 ℃ Gpa 7.9 13.1 8.1 7 Tensile elongation
(Elongation) % 2.4 3.1 2.6 3 TSF Mpa 40.3 28.5 39.6 41.2 Warpage um Inability to manufacture board due to poor moldability X X X

* DDS: 4,4'-diaminodiphenyl sulfone * TFB: 2,2'-bis (trifluoromethyl) benzidine; 2,2'-Bis (trifluoromethyl) -4,4'-biphenyldiamine

* DDM: 4,4'-diaminodiphenyl methane

* XD-1000: epoxy resin (Nippon kayaku)

* NC-3000H: epoxy resin (Nippon kayaku)

* HP-6000: Epoxy Resin (DIC Corporation)

* BMI-2300: Bismaleimide Resin (DAIWA KASEI Co., Ltd.)

* Acrylic rubber B (Mw 800,000): PARACRON KG-3015P (Negami chemical industrial Co., LTD)

* Acrylic rubber C (Mw 600,000): PARACRON KG-3113 (Negami chemical industrial Co., LTD)

* Equivalence Ratio: calculated by Equation 1 below

[Equation 1]

Equivalent compound ratio of amine compound to thermosetting resin

= (Total active hydrogen equivalent of DDS + total active hydrogen equivalent of TFB + total active hydrogen equivalent of DDM) / {(total epoxy equivalent of XD-1000 + total epoxy equivalent of NC-3000H + total epoxy equivalent of HP-6000) + (Total maleimide equivalent of BMI-2300)}

In Equation 1, the total active hydrogen equivalent weight of the DDS is a value obtained by dividing the total weight (g) of the DDS by the unit equivalent weight of the active hydrogen of the DDS (62 g / eq),

The total active hydrogen equivalent of TFB is the total weight of TFB in g divided by the unit equivalent of TFB (80 g / eq),

The total active hydrogen equivalent of DDM is the total weight of DDM divided by the unit equivalent of active hydrogen of DDM (49.5 g / eq),

The total epoxy equivalent of the XD-1000 is the total weight (g) of the XD-1000 divided by the epoxy unit equivalent (253 g / eq) of the XD-1000,

The total epoxy equivalent of NC-3000H is the total weight (g) of NC-3000H divided by the epoxy unit equivalent (290 g / eq) of NC-3000H.

The total epoxy equivalent of HP-6000 is the total weight of HP-6000 divided by the epoxy equivalent of HP-6000 (250 g / eq).

The total maleimide equivalent of BMI-2300 is the total weight (g) of BMI-2300 divided by the male equivalent of BMI-2300 (179 g / eq).

As shown in Table 1, the thermosetting resin composite for a metal foil laminate formed from a prepreg containing an amine compound having an electron withdrawing group (EWG) as in the embodiment has a glass transition temperature of 230 ° C. or less, and 10 ppm. It was confirmed that it has excellent circuit pattern fillability while having a low coefficient of thermal expansion of / ° C or lower.

That is, the thermosetting resin of 290 parts by weight or less relative to 100 parts by weight of the amine compound having an electron withdrawing group (EWG) as in the embodiment, and the equivalent ratio of the amine compound equivalent ratio based on the thermosetting resin equivalent satisfies 1.4 or more When the addition amount of the inorganic additive includes 150 parts by weight of the inorganic additive in a 50 weight ratio relative to the total 100 parts by weight of the thermosetting resin, the thermoplastic resin and the amine compound, the thermal properties bonded to the semiconductor packaging, excellent low thermal expansion properties, flowability and mechanical It was confirmed that the physical properties can be secured.

On the other hand, it is confirmed that the thermal stress factor for each of the thermosetting resin composites for metal foil laminates obtained in the examples is 21 Mpa or less, and the semiconductor package manufactured using the thermosetting resin composites for metal foil laminates having such thermal stress factors is relatively As a result, only low levels of warpage were found.

On the contrary, the thermal stress factor of each of the thermosetting resin composites for metal foil laminates obtained in Comparative Examples is greater than 25 Mpa, and the semiconductor package manufactured using the thermosetting resin composites for metal foil laminates having such a high thermal stress factor is relatively. It was confirmed that high warpage occurred.

Claims (14)

A thermosetting resin composite for a metal foil laminate, wherein the thermal stress factor of the following general formula 1 is 25 Mpa or less:
[Formula 1]
Thermal Stress Factor
= ∫ [Storage Modulus * Thermal expansion coefficient] dT
In the general formula 1,
The thermal stress factor, storage modulus and coefficient of thermal expansion are values defined or measured in the range of 30 ° C. to 260 ° C., respectively.
The method of claim 1,
The thermosetting resin composite for metal foil laminated plates whose thermal stress factor of the said General formula (1) which the said thermosetting resin composite for metal foil laminated plates has is 10-25 Mpa.
The method of claim 1,
The thermosetting resin composite for metal foil laminated sheets in which the said thermosetting resin composite for metal foil laminated sheets contains a thermosetting resin composition and a fiber base material.
The method of claim 3,
The thermosetting resin composition,
Sulfone groups; Carbonyl group; Halogen group; An alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; An aryl group having 6 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; A heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; And an amine compound including at least one functional group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group;
Thermosetting resin,
Thermoplastic resin,
A thermosetting resin composite for a metal foil laminate comprising an inorganic filler.
The method of claim 3,
The said thermosetting resin composition has a glass transition temperature of 230 degrees C or less, The thermosetting resin composite for metal foil laminated sheets.
The method of claim 4, wherein
The thermosetting resin composition, the thermosetting resin composite for a metal foil laminate comprising a thermosetting resin 400 parts by weight or less relative to 100 parts by weight of the amine compound.
The method of claim 4, wherein
The thermosetting resin composition is a thermosetting resin composite for a metal foil laminate, the equivalent ratio calculated by Equation 1 below 1.4 or more:
[Equation 1]
Equivalence ratio = total active hydrogen equivalents contained in said amine compound / total curable functional group equivalents contained in said thermosetting resin.
The method of claim 4, wherein
The amine compound is a thermosetting resin composite for a metal foil laminate comprising an aromatic amine compound containing 2 to 5 amine groups.
The method of claim 4, wherein
The thermosetting resin composition includes 50 parts by weight to 150 parts by weight of the inorganic filler based on 100 parts by weight of the total of the thermosetting resin, the thermoplastic resin and the amine compound.
The method of claim 4, wherein
The inorganic filler may include two or more inorganic fillers having different average particle diameters,
At least one of the two or more inorganic fillers is an inorganic filler having an average particle diameter of 0.1 μm to 100 μm, and the other one is an inorganic filler having an average particle diameter of 1 nm to 90 nm.
The method of claim 1,
The thermosetting resin composite for metal foil laminated plates whose storage elastic modulus in 30 degreeC and 180 degreeC of the said thermosetting resin composite for metal foil laminated plates is 16 Gpa or less, respectively.
The method of claim 11,
The thermosetting resin composite for metal foil laminated sheets whose storage elastic modulus at 260 degreeC of the said thermosetting resin composite for metal foil laminated sheets is 8 Gpa or less.
The method of claim 1,
The thermosetting resin composite for metal foil laminated sheets whose thermal expansion coefficient of the said thermosetting resin composite for metal foil laminated sheets is 5-12 ppm / degreeC.
The thermosetting resin composite for metal foil laminated plates of Claim 1 which has a sheet shape; And a metal foil formed on at least one surface of the thermosetting resin composite for the metal foil laminate.