WO2019199033A1 - Thermosetting resin composite for metal clad laminate and metal clad laminate - Google Patents

Abstract

The present invention relates to a thermosetting resin composite for a metal clad laminate and a metal clad laminate and, more specifically, 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

 [Explanation of invention]

 [Name of invention]

 Thermosetting resin composite and metal foil laminate for metal foil laminate

 Technical Field

 Cross Citation with Related Application (s)

 The present application is the Korean Patent Application No. 10-2018-0041697 dated April 10, 2018, Korea Patent Application No. 10-2018-0071076 dated June 20, 2018, Korea Patent Application No. 10-2019 dated March 28, 2019 -0036079, and the benefit of priority based on Korean Patent Application No. 10-2019-0036078 filed March 28, 2019, all the contents disclosed in the documents of the relevant Korean patent applications are incorporated as part of this specification.

 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, modulus, low thermal expansion rate, and whip The present invention relates to a thermosetting resin composite for a metal foil laminate and a metal foil laminate including the same.

 [Technique to become background of invention]

Copper clad laminate used in the conventional printed circuit board is a prepreg by impregnating the substrate of the glass fiber (Gl ass Fabr ic) in the varnish of the thermosetting resin and then semi-cured, it is heated together with the copper foil It is prepared by pressing. The prepreg is used again to construct a circuit pattern on the copper foil laminate and to build up thereon. Recently, as the performance, thickness, and light weight of 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 decreases, and the warpage problem of the semiconductor package occurs due to the difference in thermal expansion coefficient between the chip and the printed circuit board. This warpage phenomenon is a phenomenon in which the printed circuit board does not become rolled back through a high temperature process such as reflow. Deepen.

 Accordingly, researches on lowering the thermal expansion coefficient of a substrate have been conducted to improve the warpage phenomenon. For example, a technique of filling a prepreg with a high content of a filler has been proposed, but simply a high content of a filler in the prepreg is proposed. There was a limit to decrease the flow of prepreg when only filling with. [Content of invention]

 Problem to be solved

 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.

 [Measures of problem]

 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.

 [General formula 1]

 Thermal Stress Factor

= J ^" [Storage Modulus * Thermal Expansion Coefficient] dT

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

 Moreover, 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 invention, there is provided a thermosetting resin composite for a metal foil laminate having a thermal stress factor of 25 Mpa or less.

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

 The present inventors continue to study the prepreg and the thermosetting resin composite for metal foil laminate and metal foil laminate formed by curing it, the thermal stress factor defined by the general formula 1 in the temperature range of 30 ° C to 260 C Experiments confirmed that the thermosetting resin composite for a metal foil laminate having a value of 25 Mpa or less, or 10 to 25 Mpa, or 12 to 21 Mpa can prevent warpage.

More specifically, the thermal stress factor (Thermal Stress? & 01) 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 to 2601: and then adds 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 of the product of the coefficient of thermal expansion and the storage modulus at each temperature is related to the strain (stress or stress) of the t-curable resin composite for the metal foil laminate, and accordingly, in units of TC from 30 ^° C to 260 ^° C. The thermal stress factor of the general formula 1, which is a value obtained by multiplying the coefficient of thermal expansion and the storage modulus at each temperature and adding them together, represents the total strain (stress or stress) from 30 ^° C to 260 ° C. Since printed wiring boards made of a thermosetting resin composite for laminated boards exhibit strain (stress or stress) applied to a semiconductor package. 2019/199033 1 »（： 1 ^ 1 {2019/004223

The warp of the semiconductor package 3印3 _§6) is directly or indirectly factor showing.

수 있으며， 이에 따라 휨As 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 at high temperature the prepreg obtained by hot air drying the thermosetting resin composition as described above. The thermosetting resin composite for metal foil laminates has a thermal stress factor of 25 1 切 3 or less, or 10 to 10, in the temperature range of 30 ° to 260 ° ⁽ :

Can bend accordingly

(¾ 1 for 6) Minimize the phenomenon.

조건을 만족하지 않는 경우, 이를 이용하여 제조된 반도체 패키지는 상대적으로 높은 휨이 발생한다는 점이 확인되었다. 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

When the condition was not satisfied, it was confirmed that the semiconductor package manufactured by using the same produced relatively high warpage.

수 있고, 상기 금속박 적층판용 열경화성 수지 복합체의 180^ 에서의 저장 탄성율은 7 Gpa내지

있다. On the other hand, the storage elastic modulus at 30 ° 0 and 180 ° ⁽ : of the thermosetting resin composite for metal foil laminates may be 16 ~ å1 or less, respectively, specifically the storage elastic modulus at 30 ^ of the thermosetting resin composite for metal foil laminates is 12

And the storage modulus at 180 ^ of the thermosetting resin composite for the metal foil laminate is 7 Gpa to

have.

이하의 낮은 저장 탄성율을 갖는데， 이에 따라 동일 열팽창계수에서 상대적으로 낮은 열응력인자를 가질 수 있으므로 30^ 및 180° (:와 같이 낮은 온도 범위에서 반도체패키지의 휨이 상대적으로 낮은특징을 가질 수 있다. In the relatively low temperature range, such as 30 ^ and 180 of the thermosetting resin composite for the metal foil laminate

It has a low storage modulus of less than below, and thus may have a relatively low thermal stress factor at the same coefficient of thermal expansion, so that the warpage of the semiconductor package may have a relatively low characteristic at a low temperature range such as 30 ^ and 180 ° (:). .

In addition, 260 ° ⁽ⁱⁿ the thermosetting resin composite material for the metal foil-clad laminate: on

have. The thermosetting resin composite for the metal foil laminate is described above at 260 °. Thus in having a storage modulus, and thus can have a relatively low thermal stress factor at the same coefficient of thermal expansion it may have a warpage of the semiconductor package characterized by relatively low at 260 C ^O.

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

 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 mM / ° C, or 10 µm / ° 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, the thermal stress factor of the general formula 1 is 25 Mpa or less, the semiconductor package manufactured by using the thermosetting resin composite for the metal foil laminate 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 which is substituted or unsubstituted with a nitro group, cyano group or halogen group; An aryl group having 6 to 20 carbon atoms or unsubstituted or substituted with a nitro, cyano 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 unsubstituted or substituted 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 ) May contain inorganic fillers.

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

The thermosetting resin composition may contain the above-mentioned amine compound including the strong electron withdrawing group It exhibits a relatively low reactivity as included, 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, and induces the thermosetting resin to be uniformly curable to a sufficient level without the influence of the filler charged in a high content. to, and can improve the reliability of the final product to be produced, it can increase mechanical properties such as toughness (toughness) also has a glass transition temperature of 230 ° ^(: can be reduced to less than a.

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

 However, even when an excessive amount of a specific amine curing agent having reduced reactivity, including the electron withdrawing group (別 ¾) as described above, is added, an increase in the curing rate of the thermosetting resin is suppressed due to a decrease in the reactivity of the curing agent. It is possible to exhibit high flowability even during long-term storage in the resin composition for semiconductor packages or in the prepreg state obtained therefrom, thereby having 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 thermosetting resin mixture content is also 400 parts by weight or less, or 150 parts by weight to 400 parts by weight, or 180 parts by weight of 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 may be reduced, Mechanical properties such as toughness can also be reduced.

 On the other hand, the thermosetting resin composition may satisfy the 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]

 Equivalence 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 equivalents contained in the amine curing agent is the total amount of the amine curing agent The weight (unit: g) means the unit weight of the active hydrogen of the amine curing agent (g / eq).

 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 refers to a hydrogen atom contained in the amino group (-N¾) present in the amine curing agent, and the active hydrogen may form a cured structure through reaction with the curable functional group of the thermosetting resin.

 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 reaction with 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 epoxy, 2019/199033 1 »（： 1 ^ 1 {2019/004223

When the bismaleimide resin is used as the thermosetting resin, the curable functional group contained in the bismaleimide resin may be a maleimide group.

 That is, the thermosetting resin composition satisfies that the equivalent ratio calculated by Equation (1) is equal to or greater than 1.4, wherein the amine curing agent of a sufficient level is contained so that the curable functional groups contained in all the thermosetting resins can cause a curing reaction. Means. Therefore, when the equivalent ratio calculated by Equation 1 in the thermosetting resin composition is reduced to less than 1.4, it is difficult to uniformly cure the thermosetting resin to a more sufficient level under the influence of the filler charged in a high content, the final product The reliability of can be reduced, mechanical properties also have the disadvantage that can 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 alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a nitro group, cyano group, or halogen group; an aromatic amine compound containing 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]

상기 화학식 1에서， 뇨는 술폰기, 카보닐기， 또는 탄소수 1 내지 10의 알킬렌기이며, ¾ 내지 ¾는 각각 독립적으로 니트로기， 시아노기， 수소원자, 할로겐기, 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기, 또는 2019/199033 1»（：1^1{2019/004223

In Formula 1, urine is a sulfone group, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms, and ¾ to ¾ are each independently a nitro group, cyano group, hydrogen atom, halogen group, alkyl group having 1 to 6 carbon atoms, and carbon number. Aryl groups of 6 to 15, or 2019/199033 1 »（： 1 ^ 1 {2019/004223

독립적으로 수소원자， 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기, 또는 탄소수 2 내지 20의 헤테로아릴기이며， II은 1 내지 10의 정수일 수 있다. A heteroaryl group having 2 to 20 carbon atoms,

Independently a hydrogen atom, a halogen group, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms, or a heteroaryl group of 2 to 20 carbon atoms, II 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 group, cyano group and halogen group It may be substituted with the above functional groups.

 [Formula 2]

및 요₄ '는 각각 독립적으로 수소원자， 할로겐기, 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기 , 또는 탄소수 2 내지 20의 헤테로아릴기이며， 01은 1 내지 10의 정수이고， 상기 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기， 및 탄소수 2 내지 20의 헤테로아릴기는 각각 독립적으로 니트로기， 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 작용기로 치환될 수 있다. In Formula 2, to are each independently a nitro group, a cyano group, a hydrogen atom, a halogen group, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms, or a heteroaryl group of 2 to 20 carbon atoms,

And 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, 01 is an integer of 1 to 10, and 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 at least one functional group selected from the group consisting of nitro group, cyano group and halogen group.

 [Formula 3]

In Chemical Formula 3, 1 to ¾ are each independently a nitro group, 2019/199033 1 »（： 1 ^ 1 {2019/004223

및 ¾ '는 각각 독립적으로 수소원자， 할로겐기， 탄소수 1 내지 6의 알킬기， 탄소수 6 내지 15의 아릴기, 또는 탄소수 2 내지 20의 헤테로아릴기이며, 상기 탄소수 1 내지 6의 알킬기 , 탄소수 6 내지 15의 아릴기， 및 탄소수 2 내지 20의 헤테로아릴기는 각각 독립적으로 니트로기, 시아노기 및 할로겐기로 이루어진 군에서 선택된 1종 이상의 작용기로 치환될 수 있다. 상기 알킬기는, 알케인（ 1¾116）으로부터 유래한 1가의 작용기로, 예를 들어, 직쇄형， 분지형 또는 고리형으로서， 메틸, 에틸， 프로필， 이소부틸，

아卜부틸， 펜틸, 핵실 등이 될 수 있다. 상기 알킬기에 포함되어 있는 하나 이상의 수소 원자는 각각 치환기로 치환가능하다. 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,

And ¾ 'are each independently a hydrogen atom, a halogen group, an alkyl group of 1 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms, or a heteroaryl group of 2 to 20 carbon atoms, the alkyl group of 1 to 6 carbon atoms, 6 to 6 carbon atoms The aryl group of 15 and the heteroaryl group having 2 to 20 carbon atoms may each be independently substituted with one or more functional groups selected from the group consisting of nitro groups, cyano groups, and halogen groups. The alkyl group is a monovalent functional group derived from alkane (1¾116), and is, for example, linear, branched or cyclic, methyl, ethyl, propyl, isobutyl,

Acebutyl, pentyl, nuclear chamber and the like. At least one hydrogen atom included in the alkyl group may be substituted with each substituent.

라 부틸텐기, 펜틸텐기, 핵실렌기 등이 될 수 있다. 상기 알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 각각 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다. 상기 아릴기는 아렌 ）으로부터 유래한 1가의 작용기로, 예를 들어, 단환식 또는 다환식일 수 있다. 구체적으로， 단환식 아릴기로는 페닐기, 바⁰ᅵ페닐기， 터페닐기， 스틸베닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 다환식 아릴기로는 나프틸기, 안트릴기， 페난트릴기， 파이레닐기， 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 돨 수 있으나， 이에 한정되는 것은 아니다. 이러한 아릴기 중 하나 이상의 수소 원자는 각각 상기 알킬기의 경우와 마찬가지의 치환기로 치환가능하다. The alkylten group is a divalent functional group derived from alkane (1¾1½), and is, for example, linear, branched or cyclic, methylene group, ethylene group, propylten group, isobutyltene group,

It may be a la butylten group, a pentylten group, a nuclear silane 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, a bar ⁰ phenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto. Examples of the polycyclic aryl group include naphthyl group, anthryl group, phenanthryl group, pyrenyl group, perrylenyl group, chrysenyl group, fluorenyl group, and the like, but are 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 containing 0, N or 3 as a hetero atom, and the carbon number is not particularly limited, but may be 2 to 30 carbon atoms. Examples of heterocyclic groups 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 ， 02019/199033 1 »（： 1 ^ 1 {2019/004223

Dibenzothiophene group, benzofuranyl group, dibenzofuran group and the like, but are not limited thereto. At least one hydrogen atom of such a heteroaryl group may be each substituted with a substituent as in the alkyl group.

 The term "substituted" means that another functional group is bonded to a hydrogen atom in the compound, and the position to be substituted is not limited to a position where a hydrogen atom is substituted, that is, a position where a substituent may be substituted. The substituents may be the same or different from each other.

 More specifically; Formula 1 may include a compound represented by the following Formula 1-1.

 [Formula 1-1]

_{, ,} II에 대한 내용은상기 화학식 1에서 상술한 내용을 포함한다.

_{, And} about II, including the above information, in formula (I).

 Specific examples of the formula 1-1. 4,4 '-（1 11 ^ 110 （131161¾ ^ 1

IV_, ¾ 및 ¾'는 각각 독립적으로 수소원자이며， 은 1 이다.）, 4,4’-（2,2,2-|；1 11101061:1131½- （화학식 1-1에서 X는 2,2,2- 11101，061:113116-1,1- 71,

, ¾ 및 ¾’는 각각 독립적으로 수소원자이며, II은 1 이다.） 등을 들 수 있다. IV is each independently a hydrogen atom, II is 1.), 4,4'- Near 11101'01) 1 'Macro 1½-2,2- （1 1 1 ½ (wherein 1 is 1) 2, 2- （1171, X _! To X

IV _, ¾, and ¾ 'are each independently a hydrogen atom, and is 1.), 4,4'-(2,2,2- |; 1 11101061: 1131½- (wherein X is 2,2 in Formula 1-1) , 2- 11101,061: 113116-1,1- 71,

, ¾ and ¾ 'are each independently a hydrogen atom, and II is 1).

In addition, Chemical Formula 2 may include a compound represented by Chemical Formula 2-1. 2019/199033 1 1/10 公 019/004223

[Formula 2-1]

!11에 대한 내용은 상기 화학식 2에서 상술한 내용을 포함한다.

The information about! 11 includes the above-described information in Chemical Formula 2.

 Specific examples of Chemical Formula 2-1 include 2,2 ', 3,3', 5,5 ', 6,6'-

¾ 및 ¾’는 각각 독립적으로 수소원자이며， 은 1 이다.）, 2,2’- 3（ 1 01'011161上3，1）1）^116]¾1-4,4¹- 3111 ½ （ 2 및 ₇은 각각 트리플루오로메틸기이며 ,

및 ¾’는 각각 독립적으로 수소원자이며， m은 1 이다.） 등을 들 수 있다. ◦ Large 1110101 1） 1161171-4,4 ^| -(1 11 ^ 116 (In formula 2-1 to ¾ is halogen, fluorine group _, ¾ _,

¾ and ¾ 'are each independently a hydrogen atom, is 1), 2,2'- 3 (1 01'011161上3,1) 1) ^ 116] ¾1-4,4 1 -. 3111 ½ (2 And ₇ are each trifluoromethyl group,

And ¾ 'are each independently a hydrogen atom, m is 1).

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

 [Formula 3-1]

대한 내용은 상기 화학식 3에서 상술한 내용을 포함한다.

Information on the above includes the above-described information in Chemical Formula 3.

Specific examples of the formula (3_1) is 2,3,5,6a 61; £ 111 is "056 _{] 1} 26 _{] 1} 6-1,4- ½ (In formula 3-1, 1 to ¾ is a halogen fluorine group _, ¾ _, ¾ ' _, ¾, and ¾' 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. 2019/199033 1 »（： 1/10 公 019/004223

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 used in the thermosetting resin composition for a semiconductor package can be used without limitation, and the type thereof is not limited, and bisphenol show type epoxy resin, phenol novolac epoxy resin, phenyl aralkyl epoxy resin, tetra It may be at least one selected from the group consisting of phenyl ethane epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, and a mixture of dicyclopentadiene epoxy resin and 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 Formulas 9 and 10, a biphenyl type epoxy resin represented by Formula 11, and a dicyclopentadiene type epoxy resin represented by Formula 12: More than one species can be used.

 [Formula 5]

2019/199033 1»（그1^1{2019/004223

2019/199033 1 »（1 ^ 1 {2019/004223

II is 0 or an integer from 1 to 50.

More specifically, the epoxy resin of Formula 5 may be a bisphenol show type epoxy resin, a bisphenol I ⁷ type epoxy resin, a bisphenol type epoxy resin, or a bisphenol type epoxy resin, respectively, according to the type of urine.

 [Formula 6]

 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 I?

 [Formula 7]

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2019/199033 1 »（1 ^ 1 {2019/004223

[Formula 9]

상기 화학식 11에서,

In Chemical Formula 11,

 II is 0 or an integer from 1 to 50.

 [Formula 12]

In Formula 12, II is 0 or an integer of 1 to 5 ◦. On the other hand, the thermosetting ^'resins are bismaleimide resins, cyanate ester resins and bismaleimide-can be further comprising at least one resin selected from the group consisting of a triazine resin.

The bismaleimide resin is usually a thermosetting resin for a semiconductor package 2019/199033 1 »（： 1 ^ 1 {2019/004223

Anything used in the composition can be used without limitation, and the kind thereof is not limited. As a preferred 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 show diphenyl ether represented by the following formula (15). It may be at least one selected from the group consisting of a bismaleimide resin and a bismaleimide resin composed of an oligomer of diphenylmethane bismaleimide and phenylmethane type maleimide resin represented by the following formula (16).

 [Formula 13]

 In Chemical Formula 13,

 ¾ and ¾ are each independently (: ¾ or ¾¾).

 [Formula 14]

[Formula 16] 2019/199033 1 ^» （1 ^ 112019/004223

 In Chemical Formula 16,

 II is 0 or an integer from 1 to 50.

 In addition, specific examples of the cyanate-based resins include cyanate ester resins, and those commonly used in thermosetting resin compositions for semiconductor packages may be used without limitation, and the type 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,

 II is 0 or an integer from 1 to 50.

 [Formula 1 到

상기 화학식 18에서,

In Chemical Formula 18,

 Is 0 or an integer from 1 to 50.

 [Formula 19]

 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 urine. .

 The bismaleimide-triazine resin may be exemplified 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 curing of the prepreg, and may serve to reduce the warpage of the semiconductor package by lowering the coefficient of thermal expansion and elastic modulus. As a specific example of the said thermoplastic resin, a (meth) acrylate type polymer is mentioned.

Examples of the (meth) acrylate-based polymer are not particularly limited, and for example, an acrylic ester containing a repeating unit derived from a (meth) acrylate monomer and a repeating unit derived from a (meth) acrylonitrile. 2019/199033 1 »（： 1 ^ 1 {2019/004223

Copolymers; 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 ( 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, it may be technically disadvantageous after curing because the effect is decreased in increasing the toughness of the thermosetting resin composite for the metal foil laminate or decreasing the thermal expansion and elastic modulus. In addition, when the weight average molecular weight of the (meth) acrylate-based polymer is too large, the flowability of the prepreg can be reduced.

 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, an acid anhydride resin, a bismaleimide resin, a cyanate resin, a phenol novolak resin and a benzoxazine resin different from the amine compound. It may further comprise one or more curing agents. The thermosetting resin composition may include an inorganic filler.

The inorganic filler can be used in the thermosetting resin composition for the semiconductor package usually without limitation, and specific examples include 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 is increased, so that warpage intensifies during the reflow process, and the rigidity of the printed circuit board is reduced. In addition, when the surface-treated filler is used, the 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 packing density.

 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 m to 100 _, and the other one may be an inorganic filler having an average particle diameter of 1 nm to 90.

 The inorganic filler having an average particle diameter of 1 nm to 90 ran 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 m to 100 ran.

 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 neutralizing agent, a method of dry or wet treatment of silica particles using a silane cudling 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, the silane coupling agent may include amino such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-2-aminoethyl) -3 aminopropyltrimethoxysilane. Silane coupling agent, epoxy silane coupling agent such as 3-glycidoxypropyltrimethoxysilane, vinyl silane coupling agent such as 3-methacryloxypropyl trimethoxysilane, N-2- (N- \ ¥ 0 2019/199033 1 ＞ （: 1 '/ 100019/004223

Vinyl benzylaminoethyl) -3 cationic silane coupling agent such as 3-aminopropyltrimethoxysilane hydrochloride and phenyl silane coupling agent, and the silane coupling agent may be used alone, or at least two silanes as necessary. Coupling agents can be used in combination.

 More specifically, the silane compound is an aromatic amino silane or

(Meth) acrylsilane may be included, and as the inorganic filler having an average particle diameter of 0.1 _ to 100 ！!, silica having an aromatic amino silane treated may be used, and the average particle diameter of 11 to 90 11 As the inorganic filler, silica treated with (meth) acryl silane can be used. Specific examples of the aromatic amino silane-treated silica include 205 (1 ^' 0 (111 6 (± 3)), and the specific example of the (meth) acryl silane-treated silica is shown in Show0413 (g). Can be mentioned. The said (meth) acryl was used by the meaning containing all 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 additive solvent is not particularly limited as long as it shows good solubility in the resin component, and alcohol, ether, ketone, amide, aromatic hydrocarbon, ester, and nitrile may 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 the resin composition may be impregnated into the glass fiber during prepreg manufacture.

 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, 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, the additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, pigments, dyes, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, and brightening agents. To use It is 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.

 The fiber base is not particularly limited in kind, but may be a polyamide resin fiber such as a glass fiber base, a polyamide resin fiber, an aromatic polyamide resin fiber, a polyester resin fiber, an aromatic polyester resin fiber, a wholly aromatic polyester, etc. Synthetic fiber base, kraft paper, cotton linter paper, linter and kraft pulp composed of woven or nonwoven fabrics mainly composed of polyester resin fibers such as resin fibers, polyimide resin fibers, polybenzoxazole fibers, and fluorine resin 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, and Q glass. If desired, the glass-based material may be selected depending on the intended use or performance. Glass-based forms are typically woven, nonwoven, roving, chopped strand mats or surfacing mats. The thickness of the glass base material is not particularly limited, and about 0.01 to 0.3 mm may 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 an impregnation method, a coating method using various coaters, a spray injection method, or the like.

In the case of the impregnation method, after the varnish is manufactured, the fiber substrate is varnished 2019/199033 1 »（： 1 ^ 1 {2019/004223

Prepreg can be prepared by impregnation.

 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 cyclonuxanone, aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide and dimethylacetamide, methylcello Solv, aliphatic alcohols such as butyl cellosolve.

내지 200 ^°0 , 시간은 바니시의 겔화 시간과의 균형으로 특별히 제한은 없다. 또한, 바니시의 함침량은 바니시의 수지 고형분과 기재의 총량에 대하여 바니시의 수지 고형분이 약 30 내지 80중량%가 되도록 하는 것이 바람직하다. 또한, 발명의 다른 구현예에 따르면， 시트 형상을 갖는 상술한 금속박 적층판용 열경화성 수지 복합체; 및 상기 금속박 적층판용 열경화성 수지 복합체의 적어도 일면에 형성된 금속박;을 포함하는 금속박 적층판이 제공될 수 있다. In addition, when the prepreg is prepared, it is preferable that the solvent used is volatilized by 80% by weight or more. For this reason, there is no restriction | limiting in manufacturing method, drying conditions, etc., The temperature at the time of drying is about 80

To 200 ^° 0, the time is not particularly limited in balance with the gelation time of the varnish. The varnish impregnation amount is preferably such that the resin solid content of the varnish is about 30 to 80% by weight based on 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 a 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 embodiment, the metal foil may be a copper foil or an aluminum foil, and a metal having a thickness of about 2 to 200 — may be used, but the thickness thereof is preferably about 2 to 35. Preferably, copper foil is used as said metal foil. Further, as the metal foil, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, or the like may be used as an intermediate layer. \ ¥ 0 2019/199033

It is also possible to use a three-layered composite foil or a two-layered composite foil in which aluminum and copper foil are provided on both surfaces thereof with a copper layer of 0.5 to 15! And a copper layer of 10 to 300 _.

 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 processed to fabricate a single-sided or double-sided or multilayer printed circuit board, and the circuit processing may be performed by a general single-sided, double-sided or multilayer printed circuit board manufacturing process.

【Effects of the Invention】

 According to the present invention, a thermosetting resin 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 and modulus, low thermal expansion rate, and minimize warp large size seedling phenomenon. A metal foil laminate comprising a composite and the thermosetting resin composite for the metal foil laminate may be provided.

 [Specific contents for carrying out invention]

 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 Composition for Semiconductor Package, Prepreg, Thermosetting Resin Composite and Copper Foil Laminating Plate>

 (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 a rate of 400 days for 1 day to prepare a resin composition for a semiconductor package of Example and Comparative Example (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 prepregs, thermosetting resin composites for metal foil laminates and copper foil laminates After impregnating the resin composition (resin varnish) for the semiconductor package prepared in 13_ glass fiber (T-gl ass # 1010, manufactured by Ni ttobo Co., Ltd.), hot-air dried at a temperature of 170 ^° C for 2-5 minutes. A prepreg of 18 // m was prepared. After the two prepregs prepared above were laminated, copper foil (thickness 12 sun), manufactured by Mi tsui) was placed on both sides thereof, and laminated, and cured for 100 minutes under conditions of 220 ^° C. and 35 kg / cuf. Laminates were prepared.

<Experimental example: Measurement of physical properties of the thermosetting resin composition for semiconductor packages, the prepreg, the thermosetting resin composite for metal foil laminated sheets, and the copper foil laminated sheets obtained by the Example and the comparative example>

 The physical properties of the thermosetting resin composition for a semiconductor package, the prepreg, the thermosetting resin composite for a metal foil laminated sheet, and the copper foil laminated sheet obtained by the said Example and the comparative example were measured by the following method, and the result is 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 it heated up at 30 degrees (: to 260 degrees (:) up to 30 degrees using TMA (TA Instruments, Q400). After measuring at a rate of 10 ° C / min, 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 sheet obtained by the said Example and the comparative example, the test piece (thermosetting resin composite for metal foil laminated sheets) was produced in MD direction, and it was 5 degrees in tension mode using DMA (TA Instruments, Q800). The peak temperature of tan del ta was measured as the glass transition temperature by measuring from 25 ° C. to 300 ° C. under an elevated temperature condition of C / min. 3. Storage Modulus

 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 degree (;;) in tension mode using DMATA Instruments, Q800). Storage modulus was measured from 25 ° C to 300 ° C at a temperature rise of / min.

4. Filling of circuit pattern

The prepregs obtained in the above examples and comparative examples are placed on both sides of the circuit pattern (pattern height 7 m, residual ratio 50%), and copper foil (thickness 12 _/ zm,

Mitsui Co., Ltd.) was placed, pressed for 100 minutes under conditions of 220 ° C. and 35 kg / cm ² , and then the copper foils on both sides were etched, and the circuit pattern fillability was evaluated under the following criteria.

 O: No void

 X: Void occurrence

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 / oif, followed by IPC-TM-650 According to (2.4.18.3), Universal Testing

Tensile elongation in the MD direction was measured using a MachineClnstron 3365).

6. Measurement of warpage of semiconductor package)

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 90 *). A semiconductor package (14.5mm x 14.5mm x 390um) was manufactured by mounting a semiconductor chip (11.5mm x 11.5mm x thickness 80um) 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 (Therm0ire PS100 by AKR0METRIX). Warpage measures the semiconductor package from 30 ° C. to 260 ° C. and thereafter When cooled to 30 ° C, the difference between the maximum value and the minimum value of the warpage was obtained, and the warpage of the semiconductor package was evaluated based on the following criteria.

 O ： The difference between the maximum value and the minimum value of the warpage is 170um or less

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

7. Calculation of Thermal Stress Factor

 Based on the obtained thermal expansion coefficient and storage modulus at 30 ° C

After multiplying the coefficient of thermal expansion and the storage modulus at each temperature in units of 1 ° C. up to 260 ° C., all were combined to measure (calculate) the Thermal Stress Factor of the following general formula (1).

 [Formula 1]

 Thermal Stress Factor (Unit: MPa)

_. = J [Storage Modulus * Thermal expansion coefficient] dT

 [Table 1]

 Composition of thermosetting resin composition for semiconductor packages and physical properties of thermosetting resin composites for metal foil laminates of Examples (per unit)

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Table 2

 Properties of Thermosetting Resin Compositions and Compositions for Semiconductor Packages of Comparative Examples and Thermosetting Resin Composites for Metal Foil Laminates (Unit: for)

* DDS: 4,4'-diaminodiphenyl sulfone

* 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)

 * BM1-2300 ： Bismaleimide Resin (DAIWA KAVI)

 * Acrylic rubber B (Mw 800,000): PARACR0N KG_3015P (Negami chemical industrial Co., LTD)

 * Acrylic rubber C (Mw 600,000): PARACR0N KG-3113 (Negami chemical industrial Co., LTD)

 * Equivalence Ratio: Calculated Through Equation 1

 [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 + ¨ epoxy equivalent of NC-3000H + total epoxy equivalent of HP-6000) + (Total maleimide equivalent of BMI-2300)} In the above formula, the total active hydrogen equivalent of DDS is the total weight in g divided by the unit equivalent of active hydrogen in DDS (62 g / eq),

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

 The total active hydrogen equivalent of DDM is the total weight of DDM divided by the unit equivalent 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 maleimide 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 attracting (Electron Withdrawing Group, CTG) as in Example has a glass transition temperature of 230 ° C or less, It was confirmed that the circuit pattern fillability was excellent while having a low coefficient of thermal expansion of 10 ppm / ° C or less.

 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 draw (EWG) as in the embodiment, and the equivalent ratio of the equivalent amine compound equivalent ratio based on the thermosetting resin equivalent satisfies 1.4 or more In the case where the amount of the inorganic additive is added in an amount of 150 parts by weight in an amount of 50 parts by weight based on 100 parts by weight of the total amount 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 It was confirmed that mechanical 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 the comparative examples is greater than 25 Mpa, and the semiconductor package manufactured by using the thermosetting resin composites for metal foil laminates having such a high thermal stress factor is relatively high. It was confirmed that high whip occurred.

Claims

[Claim 1] The thermosetting resin composite for metal foil laminates having a thermal stress factor of 25 Mpa or less according to the following general formula (1):  [Formula 1]  Thermal Stress Factor = J ^' [Storage modulus (St or age 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. [Claim 2]  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 thermosetting resin composite for metal foil laminated plates has is 10-25 Mpa. [Claim 3]  According to claim 11,  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. [Claim 4]  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 substituted or unsubstituted with nitro, cyano or halogen groups 2019/199033 1 »（： 1 ^ 1 {2019/004223 An amine compound containing at least one functional group selected from the group consisting of alkylene groups having 1 to 20 carbon atoms, and  Thermosetting resin,  With thermoplastic resin ，  A thermosetting resin composite for a metal foil laminate comprising an inorganic filler. [Claim 5]  The method of claim 3,  The said thermosetting resin composition has a glass transition temperature of 230 ^ or less, The thermosetting resin composite for metal foil laminated sheets. [Claim 6]  The method of claim 4,  The thermosetting resin composition comprises less than 400 parts by weight of the thermosetting resin relative to 100 parts by weight of the amine compound, thermosetting resin composite for metal foil laminate. [Claim 7]  The method of claim 4,  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. [Claim 8]  The method of claim 4, The amine compound is a thermosetting resin composite for a metal foil laminate comprising an aromatic amine compound containing 2 to 5 amine groups. 2019/199033 1 »（： 1 ^ 1 {2019/004223 [Claim 9]  The method of claim 4, wherein  The thermosetting resin composition comprises 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. [Claim 10]  The method of claim 4,  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 0.01 to 100 kPa !, and the other is an inorganic filler having an average particle diameter of 1 to 90. The thermosetting resin composite for metal foil laminate. [Claim 11]  According to claim 1 The storage elastic modulus at 30 degrees [and 180 degrees (of the said thermosetting resin composite for metal foil laminated sheets

Thermosetting resin composites for metal foil laminates, as follows. [Claim 12]  The method of claim 11,  The thermosetting resin composite for metal foil laminated plates whose storage elastic modulus at 260 degrees (:) of the said thermosetting resin composite for metal foil laminated pipes is 8 Gpa or less.  The method of claim 1, The thermal expansion coefficient of the said thermosetting resin composite for metal foil laminated sheets is 5 thru | or

Thermosetting Resin Composites for Metal Foil Laminates. [Claim 14] 2019/199033 1 »（： 1/10 公 019/004223 The thermosetting resin composite for metal foil laminated sheets 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.