WO2023063277A1

WO2023063277A1 - Resin composition, laminate, semiconductor chip having resin composition layer, substrate for mounting semiconductor chip having resin composition layer, and semiconductor device

Info

Publication number: WO2023063277A1
Application number: PCT/JP2022/037755
Authority: WO
Inventors: 孝幸亀井; 勝利猪原; 源希杉山; 健太郎高野; 剛木田
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2021-10-15
Filing date: 2022-10-11
Publication date: 2023-04-20
Also published as: TW202323344A

Abstract

Provided are a resin composition, a laminate, a semiconductor chip having a resin composition layer, a substrate for mounting a semiconductor chip having a resin composition layer, and a semiconductor device which achieve superior chip adhesiveness and low void formation. A resin composition according to the present invention includes an aminotriazine novolac resin (A) and at least one compound (B) selected from the group consisting of maleimide compounds (BA) and citraconimide compounds (BB), and contains 15-60 parts by mass of the aminotriazine novolac resin (A) per a total 100 parts by mass of the aminotriazine novolac resin (A) and the compound (B).

Description

Resin composition, laminate, semiconductor chip with resin composition layer, substrate for mounting semiconductor chip with resin composition layer, and semiconductor device

The present invention relates to a resin composition, a laminate, a semiconductor chip with a resin composition layer, a substrate for mounting a semiconductor chip with a resin composition layer, and a semiconductor device. Specifically, the present invention relates to a resin composition useful as an underfill material.

In recent years, semiconductor chips (hereinafter sometimes abbreviated as "chips") have been replaced with semiconductor chip mounting substrates (hereinafter sometimes abbreviated as "substrates") along with miniaturization and higher performance of semiconductor devices. As a mounting method, flip-chip mounting has attracted attention. In flip-chip mounting, after bonding a chip and a substrate, the gap between the chip and the substrate is filled with an underfill material, which is then hardened. There is also a method of filling a chip or a substrate with an underfill material (also referred to as a pre-applied underfill material) and then bonding the chip, the underfill material, and the substrate.

In flip-chip mounting, one of the important characteristics required for the underfill material is to maintain insulation reliability. For this purpose, in the process of manufacturing a semiconductor device, voids (bubbles) are not generated between the underfill material and the chip and substrate, and peeling of the cured underfill material from the chip and substrate is suppressed. There is a need.

Patent Document 1 describes an underfill material that uses a radically polymerizable monomer as the main resin. This patent document 1 describes the addition of a silane coupling agent for the purpose of improving the adhesion to the chip.

Japanese Patent Publication No. 2015-503220

However, since radically polymerizable monomers generally cure quickly, the reaction sites of the silane coupling agent cure before forming a sufficient number of bonds with the silanol groups on the chip surface. Therefore, with the underfill material described in Patent Document 1, sufficient adhesion and adhesiveness cannot be obtained between the resin composition and substrates such as chips and printed wiring boards, and voids tend to occur as a result. In addition, since the resin composition cures before being embedded in the unevenness existing on the surfaces of the chip and the substrate, the underfill material described in Patent Document 1 cannot provide a sufficient anchor effect useful for adhesiveness. There is also

The present invention has been made in view of such problems, and includes a resin composition, a laminate, a semiconductor chip with a resin composition layer, and a semiconductor chip mounting with a resin composition layer, which are excellent in low void property and chip adhesiveness. It is an object of the present invention to provide a substrate for a semiconductor device and a semiconductor device.

As a result of intensive studies aimed at solving the above problems of the prior art, the present inventors have found that a specific resin composition can solve the above problems, and have completed the present invention.

That is, the present invention includes the following contents.
[1] containing an aminotriazine novolac resin (A) and one or more compounds (B) selected from the group consisting of a maleimide compound (BA) and a citraconimide compound (BB), wherein the aminotriazine novolac resin ( A resin composition, wherein the content of A) is 15 to 60 parts by mass with respect to a total of 100 parts by mass of the aminotriazine novolac resin (A) and the compound (B).

[2] The aminotriazine novolac resin (A) contains one or more selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2) [1] The resin composition according to .

(In formula (1), R ₁ each independently represents a hydrogen atom, a methyl group, or an ethyl group; l, m, and n each independently represent an integer of 0 to 10; (l + m + n) indicates an integer from 1 to 20.)

(In formula (2), each R ₂ independently represents a hydrogen atom, a methyl group, or an ethyl group; o, p, q, r, and s each independently represents an integer of 0 to 10; , (o+p+q+r+s) represents an integer from 1 to 20).

[3] The compound (B) comprises a compound (B1) and a compound (B2), and the compound (B1) is a maleimide compound (BA- 1) and one or more selected from the group consisting of a citraconimide compound (BB-1) having a weight average molecular weight of 3,000 or more and 9,500 or less, and the compound (B2) has a weight average molecular weight of 300 or more. One or more selected from the group consisting of a maleimide compound (BA-2) having a weight average molecular weight of less than 3,000 and a citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000, and each weight average molecular weight The resin composition according to [1] or [2], which is a standard polystyrene-equivalent value determined by GPC (gel permeation chromatography).

[4] The content of the compound (B1) is 45 to 90 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2), and the content of the compound (B2) is 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2).

[5] The resin composition according to any one of [1] to [4], further comprising a flux activator (C).

[6] The resin composition according to [5], wherein the flux activator (C) contains a rosin-based resin.

[7] The resin composition according to any one of [1] to [6], further comprising an inorganic filler (D).

[8] The inorganic filler (D) contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, [7 ] The resin composition as described in .

[9] The resin composition according to [7] or [8], wherein the inorganic filler (D) has an average particle size of 3 μm or less.

[10] The content of the inorganic filler (D) is 20 to 500 parts by mass with respect to a total of 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B) [7] The resin composition according to any one of to [9].

[11] The resin composition according to any one of [1] to [10], further comprising a curing catalyst (E).

[12] The resin composition according to [11], wherein the curing catalyst (E) contains one or more selected from the group consisting of organic peroxides and imidazole compounds.

[13] The aminotriazine novolak resin (A) contains one or more selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2),

(In formula (2), each R ₂ independently represents a hydrogen atom, a methyl group, or an ethyl group; o, p, q, r, and s each independently represents an integer of 0 to 10; , (o + p + q + r + s) represents an integer from 1 to 20.)

The compound (B) comprises a compound (B1) and a compound (B2), wherein the compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less, and It is one or more selected from the group consisting of citraconimide compounds (BB-1) having a weight average molecular weight of 3,000 or more and 9,500 or less, and the compound (B2) has a weight average molecular weight of 300 or more and 3,000. less than maleimide compound (BA-2) and a citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000, and each weight average molecular weight is determined by GPC (Gel permeation chromatography) is a value in terms of standard polystyrene obtained by the method, and the content of the compound (B1) is, with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2), 45 to 90 parts by mass, the content of the compound (B2) is 10 to 55 parts by mass with respect to the total 100 parts by mass of the compound (B1) and the compound (B2), and an inorganic filler (D), wherein the inorganic filler (D) contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide. , the average particle size of the inorganic filler (D) is 3 μm or less, and the content of the inorganic filler (D) is 100 mass in total of the aminotriazine novolac resin (A) and the compound (B). The resin composition according to [1], which is 20 to 500 parts by mass per part.

[14] The resin composition according to [13], further comprising a flux activator (C).

[15] The resin composition according to [14], wherein the flux activator (C) contains a rosin-based resin.

[16] The resin composition according to any one of [13] to [15], further comprising a curing catalyst (E).

[17] The resin composition according to [16], wherein the curing catalyst (E) contains one or more selected from the group consisting of organic peroxides and imidazole compounds.

[18] The resin composition according to any one of [1] to [17], which is used as an underfill material.

[19] A laminate comprising a supporting substrate and a layer containing the resin composition according to any one of [1] to [17] laminated on the supporting substrate.

[20] The laminate according to [19], wherein the layer containing the resin composition has a thickness of 5 to 500 μm.

[21] A semiconductor chip with a resin composition layer, comprising a semiconductor chip and a layer formed using the resin composition according to any one of [1] to [17], which is laminated on the semiconductor chip. .

[22] A resin comprising a substrate for mounting a semiconductor chip and a layer formed using the resin composition according to any one of [1] to [17], which is laminated on the substrate for mounting a semiconductor chip A substrate for mounting a semiconductor chip with a composition layer.

A semiconductor device comprising the semiconductor chip with a resin composition layer according to [23] and [21].

A semiconductor device comprising the substrate for mounting a semiconductor chip with a resin composition layer according to [24] and [22].

A semiconductor device comprising a semiconductor chip with a resin composition layer according to [25] and [21] and/or a substrate for mounting a semiconductor chip with a resin composition layer according to [22].

According to the present invention, it is possible to provide a resin composition, a laminate, a semiconductor chip with a resin composition layer, a substrate for mounting a semiconductor chip with a resin composition layer, and a semiconductor device, which are excellent in low void property and chip adhesiveness. can.

A mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described below. In addition, the following embodiment is an example for explaining the present invention, and the present invention is not limited only to this embodiment.

In the present embodiment, "(meth)acryloxy" means both "acryloxy" and its corresponding "methacryloxy", and "(meth)acrylonitrile" means "acrylonitrile" and its corresponding "methacrylonitrile". and "(meth)acrylic" means both "acrylic" and the corresponding "methacrylic".

Further, in the present embodiment, unless otherwise specified, the term "resin solid content" or "resin solid content in the resin composition" refers to the inorganic filler (D), curing catalyst (E), Silane coupling agents, wetting and dispersing agents, various additives, and components excluding solvents (organic solvents). It means that the total of components excluding curing catalyst (E), silane coupling agent, wetting and dispersing agent, various additives, and solvent (organic solvent) is 100 parts by mass.

[Resin composition]
The resin composition of the present embodiment comprises an aminotriazine novolac resin (A) (hereinafter also simply referred to as "resin (A)"), a maleimide compound (BA) (hereinafter also simply referred to as "compound (BA)") and one or more compounds (B) (hereinafter simply referred to as "compound (B)") selected from the group consisting of citraconimide compounds (BB) (hereinafter also simply referred to as "compound (BB)"); Including, the content of aminotriazine novolac resin (A) is 15 to 60 parts by mass with respect to a total of 100 parts by mass of aminotriazine novolak resin (A) and compound (B). Since it is configured in this way, the resin composition of the present embodiment is excellent in low void property and chip adhesion. Since the resin composition of the present embodiment has such properties, it is suitably used as an underfill material for flip chip mounting.

The resin composition of the present embodiment may further contain one or more selected from the group consisting of flux activators (C), inorganic fillers (D), and curing catalysts (E).

Although it is not clear why a resin composition having excellent low void properties and chip adhesiveness can be obtained in the present embodiment, the present inventors presume as follows.
Generally, a resin composition containing a maleimide compound and/or a citraconimide compound as a main component does not provide sufficient chip adhesiveness, and voids or voids generated by heat during semiconductor chip mounting or thermal curing (during post-curing). , it is difficult to suppress peeling from the chip and substrate after curing.

Here, since the aminotriazine novolak resin (A) has a triazine skeleton, it can react favorably with maleimide groups and/or citraconimide groups. Therefore, the resin (A) can suitably control the rate of the radical polymerization reaction of the compound (B), and the resin composition containing the resin (A) and the compound (B) can be applied to the unevenness existing on the surfaces of the chip and the substrate. It can be hardened while following. Therefore, the resin composition can have an excellent anchoring effect to the semiconductor chip and the substrate, and can exhibit excellent chip adhesiveness with excellent low void property to the semiconductor chip and the substrate. Further, since the resin (A) has a novolak skeleton bonded to the triazine skeleton, it can contain many hydroxy groups and amino groups even after curing. Therefore, even after curing, good chemical bonding occurs between these groups and the silanol groups on the chip surface, and in addition to the above-mentioned anchoring effect, the resulting chemical bond provides even better chip adhesion. have. Such an effect is not sufficient for a novolac resin having no triazine skeleton from the viewpoint of practical use.

For the reasons described above, the resin composition containing the resin (A) and the compound (B) has excellent chip adhesiveness, and the use of such a resin composition facilitates the mounting of semiconductor chips and heat resistance. Voids that are likely to occur due to heat during curing (during post-curing) can be suitably suppressed. It is also speculated that peeling of the cured product from the chip and substrate can be effectively suppressed even after the semiconductor chip is mounted and after post-curing.

And it is speculated that such an effect can be obtained by using the resin (A) in a specific amount with respect to the compound (B). That is, in the resin composition, the content of the resin (A) is 15 parts by mass or more with respect to the total of 100 parts by mass of the resin (A) and the compound (B), so that the effect of the resin (A) That is, it is speculated that the reactivity between the resin (A) and the compound (B), the control of the polymerization rate of the compound (B), and the anchor effect can be suitably obtained, and sufficient chip adhesiveness can be obtained. . In addition, when the content of the resin (A) is 60 parts by mass or less with respect to the total of 100 parts by mass of the resin (A) and the compound (B), the curing of the compound (B) does not become too fast. , the followability to the chip and the substrate is improved, and it is speculated that sufficient chip adhesion and anchoring effect can be obtained. However, the reason is not limited to this.

[Aminotriazine novolak resin (A)]
The resin composition of the present embodiment contains an aminotriazine novolac resin (A) from the viewpoint of obtaining excellent reactivity with the compound (B) and obtaining a resin composition having low void properties and excellent chip adhesiveness. . As the aminotriazine novolak resin (A), any phenol-formaldehyde resin (phenol resin) having a triazine ring in the molecule may be used, and known resins can also be used. Such an aminotriazine novolac resin (A) can be produced by a known method, for example, by modifying a phenolic resin with a nitrogen compound such as melamine. The aminotriazine novolak resin (A) can be used singly or in an appropriate mixture of two or more.

In the resin composition of the present embodiment, the content of aminotriazine novolac resin (A) is 15 to 60 parts by mass with respect to a total of 100 parts by mass of aminotriazine novolac resin (A) and compound (B). From the viewpoint of obtaining excellent reactivity with the compound (B) and obtaining more excellent low void properties and chip adhesion, the content of the resin (A) is the same as that of the aminotriazine novolac resin (A) and the compound (B). It is preferably 16 to 50 parts by mass, more preferably 17 to 45 parts by mass, and even more preferably 20 to 40 parts by mass with respect to the total 100 parts by mass.

In the resin composition of the present embodiment, the content of the aminotriazine novolak resin (A) is preferably 12 to 48 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. From the viewpoint of obtaining excellent reactivity with the compound (B) and obtaining more excellent low void property and chip adhesiveness, the content of the resin (A) is 100 parts by mass of the resin solid content in the resin composition. On the other hand, it is more preferably 16 to 40 parts by mass, still more preferably 21 to 35 parts by mass, and even more preferably 24 to 32 parts by mass.

As the aminotriazine novolak resin (A), excellent reactivity with the compound (B) is obtained, and there is a tendency to obtain even more excellent low void properties and chip adhesion. 9,500 is preferable, and 500 to 5,000 is more preferable. In addition, in this specification, a weight average molecular weight is a value of standard polystyrene conversion calculated|required by GPC (gel permeation chromatography) method.

The nitrogen content of the aminotriazine novolac resin (A) is set to that of the aminotriazine novolac resin from the viewpoint of obtaining excellent reactivity with the compound (B) and further excellent low void property and chip adhesion. It is preferably 10 to 25% by mass in 100% by mass, and more preferably 15 to 20% by mass because it provides even better low void property and even better chip adhesion. .

The aminotriazine novolac resin (A) has a hydroxyl group equivalent weight of 80 to 200 g/ eq. is preferably 100 to 180 g/eq. It is more preferable that the content is 130 to 170 g/eq. is more preferable. In the present embodiment, the hydroxy group equivalent means mg of potassium hydroxide required to acetylate the hydroxy groups contained in 1 g of the aminotriazine novolak resin. Specifically, it is measured according to JIS K 0070.

As the aminotriazine novolak resin (A), the compound (B) exhibits even better reactivity, and tends to yield even better low void properties and chip adhesion. It preferably contains one or more selected from the group consisting of the compound represented by the following formula (2) and the compound represented by the following formula (2).

In formula (1), each R ₁ independently represents a hydrogen atom, a methyl group, or an ethyl group. Each R ₁ is preferably a hydrogen atom or a methyl group, because better reactivity with compound (B) can be obtained, and even better low void properties and chip adhesion can be obtained. l, m, and n each independently represent an integer of 0 to 10; l, m, and n are each independently an integer of 1 to 6, since better reactivity with the compound (B) is obtained, and even better low void property and chip adhesion are obtained. is preferred. (l+m+n) represents an integer of 1-20. (l+m+n) is preferably an integer of 3 to 18 because better reactivity with compound (B) can be obtained, and even better low void property and chip adhesion can be obtained. The compounds represented by the formula (1) are, for example, compounds in which the number of R ₁ groups and the number thereof are different, compounds in which the numbers of l, m, and n are different, and compounds in which the number of (l + m + n) is It may be a mixture containing different compounds and the like.

In formula (2), each R ₂ independently represents a hydrogen atom, a methyl group, or an ethyl group. It is preferable that each R ₂ is independently a hydrogen atom or a methyl group, since more excellent reactivity with the compound (B) can be obtained, and even more excellent low void property and chip adhesiveness can be obtained. . o, p, q, r, and s each independently represent an integer of 0 to 10; o, p, q, r, and s are each independently from 1 to 4, because better reactivity with the compound (B) can be obtained, and even better low void properties and chip adhesion can be obtained. is preferably an integer of (o+p+q+r+s) represents an integer of 1-20. (o + p + q + r + s) is preferably an integer of 5 to 20 because better reactivity with compound (B) can be obtained, and even better low void property and chip adhesion can be obtained. The compounds represented by the formula (2) include, for example, compounds in which the number of R ₂ groups and the number thereof are different in the formula (2), compounds in which the numbers of o, p, q, r, and s are different, (o + p + q + r + s ) may be a mixture containing compounds having different numbers of .

Since the compound (B) exhibits even better reactivity and even better low-void property and chip adhesion, the aminotriazine novolac resin (A) is represented by the formula (1) It is more preferable to be a mixture of the compound represented by and the compound represented by formula (2). As such a mixture, even better reactivity with the compound (B) can be obtained, and even better low void properties and chip adhesion can be obtained. The mass ratio of the compound represented by (2) (compound represented by formula (1) (parts by mass): compound represented by formula (2) (parts by mass)) is 50:50 to 90:10. and more preferably 60:40 to 85:15.

As the aminotriazine novolak resin (A), a commercially available product may be used. ), LA-7054 (trade name), and LA-7751 (trade name).

[Compound (B)]
The resin composition of the present embodiment is one or more selected from the group consisting of a maleimide compound (BA) and a citraconimide compound (BB) from the viewpoint of obtaining a resin composition excellent in low void properties and chip adhesion. contains the compound (B) of Compound (B) is not particularly limited as long as it contains one or more selected from the group consisting of a maleimide group and a citraconimide group in the molecule. The compound (B) preferably does not show reactivity with the flux activator (C) described below. Compound (B) can be used individually by 1 type or in mixture of 2 or more types.

As the compound (B) according to the present embodiment, a maleimide compound is used because it tends to provide better reactivity with the aminotriazine novolac resin (A) and to provide better low void properties and chip adhesion. (BA) is preferably included. In addition, the maleimide compound (BA) is less likely to react with the flux activator during storage or heat treatment than the epoxy compound, and the deactivation of the flux activator is less likely to occur.

The compound (B) includes a compound (B1) and a compound (B2), wherein the compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less and a weight average One or more selected from the group consisting of citraconimide compounds (BB-1) having a molecular weight of 3,000 or more and 9,500 or less, and the compound (B2) is a maleimide having a weight average molecular weight of 300 or more and less than 3,000. It is preferably one or more selected from the group consisting of compound (BA-2) and citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000.

By containing the compounds (B1) and (B2) as the compound (B), the resin composition of the present embodiment is even more excellent in low void properties and chip adhesion. The reason for this is not clear, but the inventors presume as follows.
That is, since the resin composition contains the compound (B1) having a relatively high molecular weight, the stress generated during cure shrinkage during semiconductor chip mounting or thermal curing (during post-curing) is alleviated. Therefore, the effect of improving adhesiveness by using the resin (A) is further promoted. The resin composition also contains a compound (B2) having a relatively low molecular weight. Therefore, the cross-linking density can be improved during semiconductor chip mounting or thermal curing (post-curing). In addition, it is speculated that stress relaxation due to inclusion of the resin (A) and the compound (B1) can further promote the developed adhesiveness. However, the reason is not limited to this.

The compound (B1) preferably contains a maleimide compound (BA-1) because it tends to provide even better low void properties and chip adhesion.

The compound (B2) preferably contains a maleimide compound (BA-2) because it tends to provide even better low void properties and chip adhesion.

The weight average molecular weight of the maleimide compound (BA-1) is preferably 3,200 or more and 8,000 or less because it tends to provide even better low void properties and chip adhesion. , 3,300 or more and 6,000 or less.

Since the citraconimide compound (BB-1) tends to have even better low void properties and chip adhesiveness, the weight average molecular weight is 3,200 or more and 8,000 or less. It is preferably 3,300 or more and 6,000 or less.

The weight average molecular weight of the maleimide compound (BA-2) is preferably 350 or more and 2,800 or less, since it tends to provide even more excellent low void properties and chip adhesion. It is more preferable that it is more than 2,500 and less than 2,500.

As the citraconimide compound (BB-2), the weight average molecular weight thereof is preferably 350 or more and 2,800 or less, since it tends to obtain even more excellent low void properties and chip adhesiveness. It is more preferably 400 or more and 2,500 or less.

(Maleimide compound (BA))
The maleimide compound (BA) is not particularly limited as long as it is a resin or compound having one or more maleimide groups in the molecule. The maleimide compound (BA) can be used singly or in combination of two or more.

Examples of such maleimide compounds (BA) include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4 -maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m- Phenylenebismaleimide, p-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4 -methyl-1,3-phenylenebismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3- Bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, polyphenylmethane maleimide, novolac-type maleimide compound, biphenylaralkyl-type maleimide compound, 2,2-bis(4-(4-maleimide) phenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,3-phenylenedimaleimide, N , N′-1,4-phenylenedimaleimide, N-phenylmaleimide, a maleimide compound represented by the following formula (3), a structural unit represented by the following formula (4) and a maleimide group at both ends of the molecular chain a bismaleimide compound containing, a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6), and a maleimide compound represented by the following formula (7). The compound (B) is in the form of a prepolymer obtained by polymerizing a maleimide compound, a prepolymer obtained by polymerizing a maleimide compound with another compound such as an amine compound, or the like, and the resin composition according to the present embodiment. can also be contained in

In formula (3), ⁿ³ represents an integer of 1-30.

In formula (4), R ¹¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. R ¹² represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. Each R ¹³ independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkenyl group having 2 to 16 carbon atoms. ⁿ⁵ represents an integer of 1-10.
Details of the structural unit represented by formula (4) will be described later.

In formula (5), each R ₈ independently represents a hydrogen atom, a methyl group, or an ethyl group. Each _R9 independently represents a hydrogen atom or a methyl group.

In formula (6), each R ¹⁰ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. ⁿ⁴ represents an integer of 1-10. R ¹⁰ is preferably a hydrogen atom.

In formula (7), each R ¹⁰ independently represents a hydrogen atom or a methyl group, and n ² represents an integer of 1 or more, preferably an integer of 1-10.

Next, the structure of the bismaleimide compound containing the structural unit represented by formula (4) and maleimide groups at both ends of the molecular chain will be described.
The bismaleimide compound may have a plurality of structural units represented by formula (4), in which case R ¹¹ , R ¹² and R in the plurality of structural units represented by formula (4) ¹³ may be the same or different. In the bismaleimide compound, at least one of R ¹¹ , R ¹² , and R ¹³ in the structural unit represented by formula (4) and the number of structural units represented by formula (4) in the bismaleimide compound is It may be a mixture of different compounds.
In the structural unit represented by formula (4), R ¹¹ represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. . R ¹¹ is a linear or branched alkylene because the resin composition has a suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be controlled favorably. is preferably a group, more preferably a linear alkylene group.

The number of carbon atoms in the alkylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
Examples of linear or branched alkylene groups include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. group, dodecylene group, undecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, neopentylene group, dimethylbutylene group, methylhexylene group, ethylhexylene group, dimethylhexylene group, trimethylhexylene group, methylheptylene group, dimethylheptylene group, trimethylheptylene group, tetramethylheptylene group, ethylheptylene group, methyloctylene group, methylnonylene group, methyldecylene group, methyldodecylene group, methylundecylene group, methyltridecylene group, methyltetradecylene group , and methylpentadecylene groups.

The number of carbon atoms in the alkenylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
Linear or branched alkenylene groups include, for example, vinylene group, 1-methylvinylene group, arylene group, propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2 -pentenylene group, isopentylene group, cyclopentenylene group, cyclohexenylene group, dicyclopentadienylene group, and the like.

In the structural unit represented by formula (4), R ¹² represents a linear or branched alkylene group having 1 to 16 carbon atoms or a linear or branched alkenylene group having 2 to 16 carbon atoms. . R ¹² is a linear or branched alkylene because the resin composition has a suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be suitably controlled. is preferably a group, more preferably a linear alkylene group.

The number of carbon atoms in the alkylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
As the linear or branched alkylene group, the above R ¹¹ can be referred to.

The number of carbon atoms in the alkenylene group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
As the linear or branched alkenylene group, the above R ¹¹ can be referred to.

In the structural unit represented by formula (4), R ¹¹ and R ¹² may be the same or different, but from the viewpoint of easier synthesis of the bismaleimide compound, they are preferably the same. preferable.

In the structural unit represented by formula (4), each R ¹³ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or a linear or branched alkyl group having 2 to 16 carbon atoms. It represents a branched alkenyl group. Each of R ¹³ is independently a hydrogen atom or a carbon A linear or branched alkyl group having a number of 1 to 16 is preferable, and among R ¹³ , 1 to 5 groups (R ¹³ ) are linear or branched alkyl groups having 1 to 16 carbon atoms. and the remaining groups (R ¹³ ) are more preferably hydrogen atoms, and among R ¹³ , 1 to 3 groups (R ¹³ ) are linear or branched groups having 1 to 16 carbon atoms. More preferably, it is an alkyl group and the remaining groups (R ¹³ ) are hydrogen atoms.

The number of carbon atoms in the alkyl group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
Linear or branched alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 1-ethylpropyl group, n-butyl group, 2-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-pentyl group, tert-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl groups.

The number of carbon atoms in the alkenyl group is 2 to 14 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred, and 4 to 12 is more preferred.
Linear or branched alkenyl groups include, for example, vinyl group, allyl group, 4-pentenyl group, isopropenyl group, isopentenyl group, 2-heptenyl group, 2-octenyl group, and 2-nonenyl group. be done.

In the structural unit represented by formula (4), n ⁵ represents an integer of 1-10.

A bismaleimide compound has maleimide groups at both ends of its molecular chain. Both ends mean both ends in the molecular chain of the bismaleimide compound. , at the chain end of R ¹¹ , at the chain end at the N atom of the maleimide ring, or at both ends. The bismaleimide compound may have maleimide groups other than both ends of the molecular chain.
The maleimide group is represented by formula (8) and the N atom is bonded to the molecular chain of the bismaleimide compound. In addition, the maleimide groups bonded to the bismaleimide compound may all be the same or different, but the maleimide groups at both ends of the molecular chain are preferably the same.

In formula (8), each R ₁₁ independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Both R ₁₁ are preferably hydrogen atoms from the viewpoint that they can more preferably react with the resin (A).
The number of carbon atoms in the alkyl group is preferably from 1 to 3, more preferably from 1 to 2, from the viewpoint of more preferably reacting with the resin (A).
As the linear or branched alkyl group, the above R ¹³ can be referred to.

Examples of such bismaleimide compounds include maleimide compounds represented by formula (9). These can be used singly or in combination of two or more compounds having different repeating numbers of a in formula (9).

In formula (9), a represents an integer of 1-10. a is an integer of 1 to 6 because the resin composition has a more suitable viscosity when the resin composition layer is mounted on the chip, and the increase in melt viscosity during mounting can be more suitably controlled. is preferred. The maleimide compound represented by formula (9) may be a mixture of compounds in which a is different.

The maleimide compound (BA) has excellent reactivity with the resin (A), is excellent in low void property and chip adhesion, and is excellent in solvent solubility. 2,2′-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N , N′-1,3-phenylenedimaleimide, N,N′-1,4-phenylenedimaleimide, N-phenylmaleimide, the maleimide compound represented by the above formula (3), the above formula (4) A bismaleimide compound containing a structural unit and a maleimide group at both ends of the molecular chain, a maleimide compound represented by the above formula (5), a maleimide compound represented by the above formula (6), and a maleimide compound represented by the above formula (7) It is preferable to contain one or more selected from the group consisting of maleimide compounds represented by 2,2'-bis(4-(4-maleimidophenoxy)phenyl)propane, represented by the above formula (3) A maleimide compound, a bismaleimide compound containing maleimide groups at both ends of a structural unit represented by the above formula (4) and a maleimide group represented by the above formula (5), a maleimide compound represented by the above formula (6) and maleimide compounds represented by the above formula (7). Furthermore, the maleimide compound (BA) tends to provide better reactivity with the resin (A) and to provide better low void properties, chip adhesion, and solvent solubility. 3) a maleimide compound represented by formula (4) above, a bismaleimide compound containing maleimide groups at both ends of the structural unit represented by formula (4) above, a maleimide compound represented by formula (5) above, and the above It is even more preferable to contain one or more selected from the group consisting of maleimide compounds represented by formula (6).

Since the maleimide compound (BA-1) tends to exhibit even better reactivity with the resin (A), and even better low void properties, chip adhesion, and solvent solubility, One or more selected from the group consisting of a maleimide compound represented by the above formula (3) and a bismaleimide compound containing a maleimide group at both ends of a structural unit represented by the above formula (4) and a molecular chain. is preferred.

Since the maleimide compound (BA-2) tends to exhibit even better reactivity with the resin (A), and even better low void properties, chip adhesion, and solvent solubility, It is preferably one or more selected from the group consisting of the maleimide compound represented by the above formula (5) and the maleimide compound represented by the above formula (6).

As the maleimide compound (BA), a commercially available product may be used. (trade name). As the maleimide compound represented by formula (3), for example, BMI-1000P (trade name, n ³ in formula (3) = 14 (average value), weight average molecular weight: 3 , 700), K-I Kasei Co., Ltd. BMI-650P (trade name, n ³ = 9 (average value) in formula (3)), K-I Kasei Co., Ltd. BMI-250P (trade name, n ³ =3 to 8 (average value) in formula (3)), CUA-4 (trade name, n ³ =1 in formula (3)) manufactured by K.I Kasei Co., Ltd., and the like. As the bismaleimide compound containing maleimide groups at both ends of the structural unit represented by the formula (4) and the molecular chain, MIZ-001 manufactured by Nippon Kayaku Co., Ltd. (trade name, represented by the formula (9) Weight-average molecular weight: 3,900), which contains a maleimide compound and a in formula (9) is a mixture of 1 to 6 (integers). Examples of the maleimide compound represented by formula (5) include BMI-70 (trade name; bis(3-ethyl-5-methyl-4-maleimidophenyl)methane manufactured by K.I. Kasei Co., Ltd., weight average molecular weight : 550). Examples of the maleimide compound represented by formula (6) include MIR-3000-70MT (trade name, manufactured by Nippon Kayaku Co., Ltd., where all R ¹⁰ in formula (6) are hydrogen atoms, n ⁴ is 1 ~10 mixture, weight average molecular weight: 1,050). Examples of the maleimide compound represented by formula (7) include BMI-2300 (trade name) manufactured by Daiwa Kasei Kogyo Co., Ltd.

(Citraconimide compound (BB))
Examples of the citraconimide compound (BB) include, but are not limited to, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 4,4-diphenylmethanebiscitraconimide, 2,2- bis[4-(4-citraconimidophenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidophenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidophenyl)methane, bis (3,5-diethyl-4-citraconimidophenyl)methane, 1,3-xylylenebis(citraconimide), N-[3-bis(trimethylsilyl)amino-1-propyl]citraconimide, N-[3-bis( triethylsilyl)amino-1-propyl]citraconimide, N-[3-bis(triphenylsilyl)amino-1-propyl]citraconimide, N,N'-(m-phenylenedimethylene)dicitraconimide, and N -[3-(methylidenesuccinimidemethyl)benzyl]citraconimide, a citraconimide compound represented by the following formula (10), a structural unit represented by the above formula (4) and a citraconimide group at both ends of the molecular chain A biscitraconimide compound containing, a citraconimide compound represented by the following formula (11), and a citraconimide compound represented by the following formula (12). As for the biscitraconimide compound, the above bismaleimide compound can be referred to. The details of the structural unit represented by the formula (4) are as described above, and the _{citraconimide} group is represented by the formula ( 8) can be referred to. The citraconimide compound (BB) can be used singly or in combination of two or more.

The citraconimide compound (BB) is among the above-mentioned from the viewpoint of obtaining a resin composition having excellent solvent solubility, excellent low void property and chip adhesion, and excellent reactivity with the resin (A). , a citraconimide compound represented by the following formula (10), a biscitraconimide compound containing a structural unit represented by the above formula (4) and a citraconimide group at both ends of the molecular chain, represented by the following formula (11) and one or more selected from the group consisting of a citraconimide compound represented by the following formula (12).

Since the citraconimide compound (BB-1) tends to have better reactivity with the resin (A) and better low void properties, chip adhesion, and solvent solubility. , a citraconimide compound represented by the following formula (10) and a biscitraconimide compound containing a citraconimide group at both ends of a structural unit represented by the above formula (4) and a molecular chain 1 selected from the group consisting of Seeds or more are preferred.

In formula (10), ⁿ⁶ represents an integer of 1-30.

Since the citraconimide compound (BB-2) tends to have better reactivity with the resin (A) and better low void properties, chip adhesion, and solvent solubility. , a citraconimide compound represented by the following formula (11) and a citraconimide compound represented by the following formula (12).

In formula (11), each R ₈ independently represents a hydrogen atom, a methyl group, or an ethyl group. Each _R9 independently represents a hydrogen atom or a methyl group.

In formula (12), each R ¹⁰ independently represents a hydrogen atom or a methyl group, and n ⁴ represents an integer of 1 or more, preferably an integer of 1-10. R ¹⁰ is preferably a hydrogen atom.

In the resin composition of the present embodiment, the content of the compound (B) is not particularly limited. It is preferably 40 to 85 parts by mass, more preferably 50 to 84 parts by mass, still more preferably 55 to 83 parts by mass, and 60 to 80 parts by mass, relative to the total 100 parts by mass of B). is even more preferable.

In the resin composition of the present embodiment, the content of the compound (B) is not particularly limited. parts, preferably 32 to 68 parts by mass, more preferably 40 to 65 parts by mass, even more preferably 43 to 60 parts by mass, more preferably 45 to 59 parts by mass More preferred.

When the compound (B) contains the compound (B1) and the compound (B2), even better reactivity with the resin (A) can be obtained, and even better low void properties, chip adhesion, and solvent solubility can be obtained. The content of compound (B1) is preferably 45 to 90 parts by mass with respect to a total of 100 parts by mass of compound (B1) and compound (B2). It is more preferably 85 parts by mass, and even more preferably 45 to 78 parts by mass. The content of compound (B2) is preferably 10 to 55 parts by mass, more preferably 15 to 55 parts by mass, with respect to 100 parts by mass in total of compound (B1) and compound (B2). More preferably, it is 22 to 55 parts by mass.

When the compound (B) contains the compound (B1) and the compound (B2), the content of the compound (B1) tends to provide even better low void property and chip adhesion, so the resin It is preferably 27 to 63 parts by mass, more preferably 32 to 57 parts by mass, even more preferably 32 to 49 parts by mass, with respect to 100 parts by mass of the resin solid content in the composition. More preferably, it is up to 45 parts by mass.

When the compound (B) contains the compound (B1) and the compound (B2), the content of the compound (B2) tends to provide even better low void property and chip adhesion, so the resin It is preferably 5 to 41 parts by mass, more preferably 8 to 33 parts by mass, even more preferably 11 to 28 parts by mass, with respect to 100 parts by mass of the resin solid content in the composition. More preferably, it is up to 24 parts by mass.

When the compound (B1) is included as the compound (B), the content of the resin (A) is 22 to 56 parts by mass with respect to the total 100 parts by mass of the resin (A) and the compound (B1). is preferable, 28 to 50 parts by mass is more preferable, and 35 to 45 parts by mass is even more preferable. The content of the compound (B1) is preferably 44 to 78 parts by mass, more preferably 50 to 72 parts by mass, with respect to the total of 100 parts by mass of the resin (A) and the compound (B1). , 55 to 65 parts by mass. When the compound (B1) is included as the compound (B) and the relationship between the content of the resin (A) and the compound (B1) is within the above range, even more excellent low void property and chip adhesion tend to be obtained. be. The reason for this is not clear, but the inventors presume as follows.

That is, as described above, the resin (A) produces good chemical bonds between the hydroxy groups and amino groups and the silanol groups on the chip surface even after curing, and exhibits an anchoring effect. and chip adhesion. By using the compound (B1), the stress generated during curing shrinkage during semiconductor chip mounting or thermal curing (during post-curing) is alleviated. Therefore, by using the resin (A) together with the compound (B1), the chemical bonding between the resin (A) and the chip and the effect of improving the adhesiveness due to the anchor effect can be preferably obtained. Further, this effect can be further promoted by setting the amount ratio of the resin (A) and the compound (B1) within the above range, since more suitable stress relaxation can be obtained in the cured product. I'm assuming it can. However, the reason is not limited to this.

When the compound (B2) is included as the compound (B), the content of the resin (A) is 25 to 84 parts by mass with respect to the total 100 parts by mass of the resin (A) and the compound (B2). is preferred, 50 to 75 parts by mass is more preferred, and 52 to 70 parts by weight is even more preferred. The content of the compound (B2) is preferably 16 to 75 parts by mass, more preferably 25 to 50 parts by mass, with respect to the total of 100 parts by mass of the resin (A) and the compound (B2). , 30 to 48 parts by mass. When the compound (B2) is included as the compound (B) and the relationship between the content of the resin (A) and the compound (B2) is within the above range, even more excellent low void property and chip adhesion tend to be obtained. be. The reason for this is not clear, but the inventors presume as follows.

That is, as described above, the resin (A) produces good chemical bonds between the hydroxy groups and amino groups and the silanol groups on the chip surface even after curing, and exhibits an anchoring effect. and chip adhesion. The compound (B2) can improve the crosslink density during semiconductor chip mounting or thermal curing (post-curing). When the amount ratio between the resin (A) and the compound (B2) is within the above range, the chemical bonding between the resin (A) and the chip and the anchor effect are not inhibited in the cured product. can suitably improve the crosslink density of. Therefore, it is speculated that the cured product obtained from the resin composition becomes stronger and exhibits even more excellent low void properties and chip adhesion. However, the reason is not limited to this.

When the maleimide compound (BA-1) and the maleimide compound (BA-2) are included as the compound (B), there is a tendency to obtain even better low void properties and chip adhesion. Therefore, the maleimide compound (BA -1) content is preferably 45 to 90 parts by mass, preferably 45 to 85 parts by mass, with respect to the total 100 parts by mass of compound (BA-1) and compound (BA-2). is more preferable, and 45 to 78 parts by mass is even more preferable. In addition, the content of the maleimide compound (BA-2) is preferably 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (BA-1) and the compound (BA-2). It is more preferably 55 parts by mass, and even more preferably 22 to 55 parts by mass.

When the compound (B) contains the citraconimide compound (BB-1) and the citraconimide compound (BB-2), a more excellent reactivity with the resin (A) can be obtained, and an even more excellent low void property can be obtained. , chip adhesiveness, and solvent solubility tend to be obtained, the content of the citraconimide compound (BB-1) is a total of 100 parts by mass of the compound (BB-1) and the compound (BB-2). The amount is preferably 45 to 90 parts by mass, more preferably 45 to 85 parts by mass, and even more preferably 45 to 78 parts by mass. Further, the content of the citraconimide compound (BB-2) is preferably 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (BB-1) and the compound (BB-2). It is more preferably 55 parts by mass, and even more preferably 22 to 55 parts by mass.

In the resin composition of the present embodiment, the content of the resin (A) and the compound (B) is set to 100 parts by mass of the resin solid content in the resin composition in order to obtain more excellent low void properties and chip adhesion. is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, and may be 80 parts by mass or more. The upper limit of the content of the resin (A) and the compound (B) may be 100 parts by mass or less, or 95 parts by mass or less with respect to 100 parts by mass of the resin solid content in the resin composition. good.

[Flux activator (C)]
The resin composition of the present embodiment preferably further contains a flux activator (C) from the viewpoint of exhibiting flux activity in flip-chip mounting. The flux activator (C) is not particularly limited as long as it is an organic compound having one or more acidic sites in its molecule. As the acidic site, for example, a phosphoric acid group, a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group are preferable. A phenolic hydroxyl group or a carboxyl group is more preferable from the viewpoint of more effectively preventing the migration and corrosion of metals such as copper. The flux activator (C) can be used singly or in an appropriate mixture of two or more.

Although the flux activator (C) is not particularly limited, it preferably has an acid dissociation constant pKa of 3.8 or more and 15.0 or less from the viewpoint of sufficiently removing the oxide film at the junction, and the storage stability of the varnish is improved. It is more preferably 4.0 or more and 14.0 or less from the viewpoint of compatibility between the storage stability and flux activity of a laminate (underfill material with a supporting substrate) provided with a layer of a resin composition.

The weight average molecular weight or molecular weight of the flux activator (C) is not particularly limited. From the viewpoint of preventing volatilization of (C), the weight average molecular weight or molecular weight is preferably 200 or more, more preferably 250 or more. From the viewpoint of having motility as a flux activator and obtaining sufficient flux activity, the weight average molecular weight or molecular weight of the flux activator (C) is preferably 8000 or less, more preferably 1000 or less. , 600 or less.

Examples of the flux activator (C) include, but are not limited to, abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, parastric acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, hydrogenation Rosin resins such as rosin esters and rosin-modified maleic acid resins; N,N'-bis(salicylidene)-1,2-propanediamine, N,N'-bis(salicylidene)-1,3-propanediamine, etc. diamine series; phenolphthalin. Among these, the flux activator (C) preferably contains a rosin-based resin. These flux activators (C) are preferable from the viewpoints of solubility in solvents, storage stability of varnishes, and excellent storage stability and flux activity of laminates having a layer containing a resin composition.

Among them, from the viewpoint of preventing deactivation by the compound (B), the flux activator (C) is dehydroabietic acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, hydrogenated rosin ester, rosin-modified maleic acid resin. , N,N'-bis(salicylidene)-1,2-propanediamine, and N,N'-bis(salicylidene)-1,3-propanediamine are more preferred. In addition, since these flux activators have relatively low reactivity, they hardly react with the resin (A) and the compound (B), and sufficient flux activity necessary for removing the oxide film is maintained. It is more preferable from the viewpoint of Further, the flux activator (C) is more preferably a hydrogenated rosin ester in terms of obtaining even better flux activity.

A commercially available product can be used as the flux activator (C). Examples of rosin-based resins include Pine Crystal (registered trademark, hereinafter the same) series KR-85 (trade name, hereinafter the same), KR-612, KR-614, KE-100, KE-311, PE-590, KE-359, KE-604, KR-120, KR-140, KR-614, D-6011, and KR-50M; Marquid No. 32 (manufactured by Arakawa Chemical Industries, Ltd.) and the like.

In the resin composition of the present embodiment, the content of the flux activator (C) is not particularly limited, but from the viewpoint of ensuring insulation reliability and sufficient flux activity during mounting, It is preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, relative to 100 parts by mass of compound (B).

In the resin composition of the present embodiment, the content of the flux activator (C) is not particularly limited, but from the viewpoint of ensuring insulation reliability and sufficient flux activity during mounting, the resin solid content in the resin composition is 100 It is preferably 4 to 56 parts by mass, more preferably 8 to 44 parts by mass, still more preferably 12 to 36 parts by mass, and even more preferably 15 to 31 parts by mass. .

[Inorganic filler (D)]
The resin composition of the present embodiment preferably further contains an inorganic filler (D) in order to improve flame resistance, improve thermal conductivity, and reduce the coefficient of thermal expansion. By using the inorganic filler (D), the flame resistance and thermal conductivity of a cured product such as a film formed using the resin composition of the present embodiment can be improved, and the coefficient of thermal expansion can be reduced. can. Furthermore, the minimum melt viscosity of the resin composition can be suitably controlled. The minimum melt viscosity of the resin composition is preferably 200 Pa·s or more and 30,000 Pa·s or less because it is suitable for use as an underfill material.

The average particle size of the inorganic filler (D) is not particularly limited. From a corresponding viewpoint, it is preferably 3 μm or less, more preferably 1 μm or less, and may be 0.1 μm or less. Although the lower limit of the average particle size is not particularly limited, it is, for example, 10 nm. In addition, in this embodiment, the "average particle size" of the inorganic filler (D) shall mean the median size of the inorganic filler (D). Here, the median diameter is the volume of particles on the larger particle size side and the volume of particles on the smaller particle size side when the particle size distribution of powder is divided into two based on a certain particle size. means a particle size such that each accounts for 50% of the total powder. The average particle size (median size) of the inorganic filler (D) is measured by a wet laser diffraction/scattering method.

Examples of the inorganic filler (D) include, but are not limited to, silica such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum compounds such as boehmite, aluminum hydroxide, alumina, and aluminum nitride; magnesium oxide; Calcium compounds such as calcium carbonate and calcium sulfate; Molybdenum compounds such as molybdenum oxide and zinc molybdate; Boron nitride; Barium sulfate; Talc such as natural talc and calcined talc; glass such as short fiber glass, spherical glass, and fine powder glass (eg, E glass, T glass, D glass); Further, when it is desired to impart electrical conductivity or anisotropic electrical conductivity to the resin composition of the present embodiment, metal particles such as gold, silver, nickel, copper, tin alloys, and palladium can be used as the inorganic filler (D). may be used.

Among these, from the viewpoint of improving the flame resistance of the resin composition and reducing the coefficient of thermal expansion, the inorganic filler (D) includes silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, more preferably at least one selected from the group consisting of silica, alumina, and boron nitride, with silica being even more preferred.

These inorganic fillers (D) can be used singly or in an appropriate mixture of two or more.

The inorganic filler (D) may be surface-treated with a silane coupling agent. The silane coupling agent used for surface treatment of the inorganic filler (D) is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances. For example, vinylsilane-based silane coupling agents such as vinyltrimethoxysilane and γ-(meth)acryloxypropyltrimethoxysilane; phenylaminosilane-based silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane; trimethoxysilane; phenylsilane-based silane coupling agents such as phenylsilane; and imidazolesilane-based silane coupling agents. These silane coupling agents can be used singly or in admixture of two or more.

As the silane coupling agent, one or more selected from the group consisting of vinylsilane-based silane coupling agents and phenylsilane-based silane coupling agents because they tend to provide better low void properties and chip adhesion. is preferred, and a vinylsilane-based silane coupling agent is preferred.

Examples of silica or silica surface-treated with a silane coupling agent include SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Corporation; 0.3 μmSX manufactured by Admatechs Co., Ltd. -CM1 (trade name), 0.3 μm SX-EM1 (trade name), 0.3 μm SV-EM1 (trade name), SC1050-MLQ (trade name), SC2050-MNU (trade name), SC2050-MTX (trade name) , 2.2 μm SC6103-SQ (trade name), SE2053-SQ (trade name), Y50SZ-AM1 (trade name), YA050C-MJE (trade name), YA050C-MJM (trade name), YA050C-MJF (trade name) , and YA050C-MJA (trade name).

In the resin composition of the present embodiment, the content of the inorganic filler (D) is not particularly limited, but from the viewpoint of ensuring insulation reliability and sufficient flux activity during mounting, the aminotriazine novolac resin (A) and It is preferably 20 to 500 parts by mass, more preferably 50 to 400 parts by mass, even more preferably 70 to 300 parts by mass, based on 100 parts by mass of compound (B). The upper limit of the content of the inorganic filler (D) may be 250 parts by mass.

In the resin composition of the present embodiment, the content of the inorganic filler (D) is not particularly limited, but from the viewpoint of ensuring insulation reliability and sufficient flux activity during mounting, the resin solid content in the resin composition It is preferably 15 to 500 parts by mass, more preferably 40 to 400 parts by mass, even more preferably 55 to 300 parts by mass, based on 100 parts by mass. The upper limit of the content of the inorganic filler (D) may be 250 parts by mass.

[Curing catalyst (E)]
The resin composition of the present embodiment preferably further contains a curing catalyst (E). By including the curing catalyst (E) in the resin composition, the reaction rate between the resin (A) and the compound (B) and the polymerization rate of the compound (B) can be controlled more appropriately, and moderate moldability can be achieved. There is a tendency to obtain a resin composition having The curing catalyst (E) is not particularly limited as long as it is a compound capable of promoting the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B). Curing catalyst (E) can be used individually by 1 type or in mixture of 2 or more types.

The curing catalyst (E) of the present embodiment is not particularly limited, but includes, for example, organic peroxides, imidazole compounds, azo compounds, tertiary amines such as triethylamine and tributylamine, and derivatives thereof. Among these, from the viewpoint of obtaining a good reaction rate and polymerization rate and obtaining a good curing rate, the curing catalyst (E) is one or more selected from the group consisting of organic peroxides and imidazole compounds. It preferably contains both an organic peroxide and an imidazole compound, more preferably.

In the present embodiment, the content of the curing catalyst (E) is not particularly limited, but from the viewpoint of obtaining a good curing speed, it is , preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass.

In the present embodiment, the content of the curing catalyst (E) is not particularly limited. It is preferably 0.04 to 6.5 parts by mass, more preferably 0.04 to 6.5 parts by mass.

(organic peroxide)
The organic peroxide according to the present embodiment is a compound that releases an active substance (radical) that can promote the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B) by heat. Any known organic peroxide can be used without any particular limitation. An organic peroxide can be used individually by 1 type or in mixture of 2 or more types.

In the present embodiment, the 10-hour half-life temperature of the organic peroxide is not particularly limited, but is preferably 100°C or higher, and more preferably 110°C or higher from the viewpoint of productivity. It is preferable that the organic peroxide satisfies the 10-hour half-life temperature in the above range, since it is possible to increase the temperature of the solvent removal step during production.

Examples of organic peroxides include dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5 - Ketone peroxides of bis(tert-butylperoxy)hexyne-3, benzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide; 1,1-di(t-butylperoxy)cyclohexane , and peroxyketals of 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane; tert-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide Peroxides and hydroperoxides of t-butyl hydroperoxide; di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t- Butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, α,α'-di(t-butylperoxy)diisopropyl dialkyl peroxide of benzene and di-t-butyl peroxide; dibenzoyl peroxide and diacyl peroxide of di(4-methylbenzoyl) peroxide; di-n-propylperoxydicarbonate and diisopropylperoxydicarbonate Peroxydicarbonates of carbonates; 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, and t-butylperoxy-2-ethyl Peroxyester of hexanonate and the like can be mentioned. Dicumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5- one or more selected from the group consisting of dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, α,α'-di(t-butylperoxy)diisopropylbenzene, and tert-butyl hydroperoxide is preferred.

In the resin composition of the present embodiment, the content of the organic peroxide is not particularly limited, but the aminotriazine novolak resin (A) and the compound (B) are combined in order to obtain a better reaction rate and curing rate. It is preferable to contain 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass with respect to the total 100 parts by mass.

In the resin composition of the present embodiment, the content of the organic peroxide is not particularly limited. On the other hand, it preferably contains 0.04 to 8 parts by mass, more preferably 0.04 to 6.5 parts by mass.

(Imidazole compound)
The imidazole compound is not particularly limited as long as it can promote the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B), and known imidazole compounds can be used. An imidazole compound can be used individually by 1 type or in mixture of 2 or more types.

Examples of imidazole compounds include 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 2,4,5-triphenylimidazole. Among them, 2-ethyl-4-methylimidazole is preferred because it is easier to control the reaction speed and curing speed.

In the resin composition of the present embodiment, the content of the imidazole compound is not particularly limited. It is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, based on 100 parts by mass in total.

In the resin composition of the present embodiment, the content of the imidazole compound is not particularly limited. 0.04 to 8 parts by mass, more preferably 0.04 to 6.5 parts by mass.

(azo compound)
The azo compound is not particularly limited as long as it can promote the reaction between the resin (A) and the compound (B) and the polymerization reaction of the compound (B), and known azo compounds can be used. Azo compounds can be used singly or in combination of two or more.
Examples of azo compounds include 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4- dimethylvaleronitrile) and the like.

In the resin composition of the present embodiment, the content of the azo compound is not particularly limited. It is preferably contained in an amount of 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, based on 100 parts by mass.

In the resin composition of the present embodiment, the content of the azo compound is not particularly limited, but from the viewpoint of obtaining a better reaction rate and curing rate, it is , preferably 0.04 to 8 parts by mass, more preferably 0.04 to 6.5 parts by mass.

[Other ingredients]
The resin composition of the present embodiment includes, as other components, aminotriazine novolak resin (A), compound (B), flux activator (C), inorganic filler (D), and components other than curing catalyst (E). may contain one or more.

Examples of other components include, but are not limited to, flexibility-imparting components. The flexibility imparting component is not particularly limited as long as it is a component capable of imparting flexibility to the layer containing the resin composition. Such components include, for example, aminotriazine novolak resin (A), compound (B), flux activator (C), inorganic filler (D), and curing catalyst (E) other than polyimide, polyamideimide, Polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), (meth)acrylonitrile butadiene rubber (NBR), polyurethane, polypropylene, (meth)acrylic oligomer, (meth)acrylic polymer, and thermoplastic polymer compounds such as silicone resins. These flexibility-imparting components can be used singly or in admixture of two or more.

When using a flexibility imparting component, its content is not particularly limited, but usually 0.05 to 20 parts by mass with respect to 100 parts by mass of aminotriazine novolak resin (A) and compound (B). is.

When using a flexibility-imparting component, the content is not particularly limited, but is usually 0.04 to 16 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

The resin composition of the present embodiment includes other components such as the aminotriazine novolak resin (A) and the compound (B), which improve the adhesiveness at the interface between the resin component and the inorganic filler (D), and the moisture absorption and heat resistance. A silane coupling agent can also be included for the purpose of improvement. Silane coupling agents include, for example, vinyltrimethoxysilane and γ-(meth)acryloxypropyltrimethoxysilane, and other vinylsilane-based silane coupling agents; N-phenyl-3-aminopropyltrimethoxysilane, and other phenylaminosilane-based silane coupling agents. silane coupling agents; phenylsilane-based silane coupling agents such as trimethoxyphenylsilane; and imidazolesilane-based silane coupling agents. These silane coupling agents can be used singly or in admixture of two or more.

When a silane coupling agent is used, its content is not particularly limited, but from the viewpoint of further improving moisture absorption and heat resistance and further reducing the amount of volatilization during flip chip mounting, aminotriazine novolak resin (A) and It is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of compound (B).

When using a silane coupling agent, its content is not particularly limited, but from the viewpoint of further improving moisture absorption and heat resistance and further reducing the amount of volatilization during flip chip mounting, the resin solid content in the resin composition It is preferably 0.04 to 16 parts by mass with respect to 100 parts by mass.

The resin composition of the present embodiment may contain, as other components, a wetting and dispersing agent for the purpose of further improving the manufacturability of the laminate and further improving the dispersibility of the filler. The wetting and dispersing agent is not particularly limited as long as it is a wetting and dispersing agent generally used for paints and the like. For example, BYK-Chemie Japan Co., Ltd. DISPERBYK (registered trademark) -110 (trade name), -111 (trade name), -180 (trade name), -161 (trade name), BYK-W996 ( (trade name), W9010 (trade name), and W903 (trade name). These wetting and dispersing agents can be used singly or in admixture of two or more.
When a wetting and dispersing agent is used, its content is not particularly limited, but from the viewpoint of further improving the manufacturability of the laminate, it is 0.1 to 5 parts by mass with respect to 100 parts by mass of the inorganic filler (D). It is preferably 0.5 to 3 parts by mass, more preferably 0.5 to 3 parts by mass. When two or more wetting and dispersing agents are used in combination, the total amount thereof preferably satisfies the above ratio.

As other components, the resin composition of the present embodiment may contain various additives for various purposes as long as the desired properties are not impaired. Additives include, for example, ultraviolet absorbers, antioxidants, dyes, pigments, thickeners, lubricants, defoamers, leveling agents, brighteners, flame retardants, and ion trapping agents. These additives can be used singly or in admixture of two or more.

In the resin composition of the present embodiment, the content of other additives is not particularly limited, but is usually 0.01 for each of the total 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B). ~10 parts by mass.

In the resin composition of the present embodiment, the content of other additives is not particularly limited, but is usually 0.008 to 8 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. .

[Use of resin composition]
The resin composition of this embodiment is excellent in low void property and chip adhesion. When the resin composition of the present embodiment is used as an underfill material used in the form of a laminate, preferably as a pre-applied underfill material, it is excellent in low void properties and chip adhesion, and in addition, bonding properties and insulation Excellent reliability. Since the resin composition of the present embodiment has various excellent characteristics, it is more useful as an underfill material, and further useful as a pre-applied underfill material. In addition, a laminated body is mentioned later.

Since the resin composition of the present embodiment is suitable as an underfill material and more suitable as a pre-applied underfill material, a sheet obtained using the resin composition and a layer containing the resin composition (simply (also referred to as a "resin composition layer") is preferably in a semi-cured state (B stage). Details of the sheet and the resin composition layer will be described later. Since the sheet and the resin composition layer are in a semi-cured state, even more excellent low void properties and chip adhesion can be obtained. In the present embodiment, the semi-cured state (B stage) means that each component contained in the sheet or resin composition layer has not actively started to react (cured), but the sheet or resin composition layer is dried. It refers to a state in which the solvent is volatilized by heating to the extent that the adhesive is no longer present, and includes a state in which the solvent is volatilized without curing without heating. In this embodiment, the minimum melt viscosity in a semi-cured state (B stage) is usually 50,000 Pa·s or less. The lower limit of the lowest melt viscosity is, for example, 10 Pa·s or more. The minimum melt viscosity in the semi-cured state (B stage) is preferably 200 Pa·s or more and 30,000 Pa·s or less because it is suitable for use as an underfill material. In addition, in this specification, melt viscosity is measured by the following method. That is, using a laminator, a resin piece having a thickness of about 0.4 to 0.6 mm is obtained by laminating a resin composition layer on a support substrate or the like, and this resin piece is used as a sample, and a rheometer (thermofisher Melt viscosity is measured by HAAKE MARS60 (trade name) manufactured by Scientific. For the measurement, a disposable parallel plate with a plate diameter of 8 mm is used, and the temperature is increased from 40° C. to 300° C. under the conditions of a heating rate of 10° C./min, a frequency of 10.0 rad/s, and a strain of 0.1%. , to measure the melt viscosity of the resin pieces. The lowest melt viscosity means the lowest viscosity in the range from 40°C to 300°C.

[Method for producing resin composition]
The production method of the resin composition of the present embodiment is not particularly limited as long as the resin composition having the composition described above can be obtained. The resin composition comprises, for example, an aminotriazine novolak resin (A), a compound (B), optionally a flux activator (C), an inorganic filler (D), a curing catalyst (E), It can be prepared by appropriately mixing other components. If necessary, these components may be dissolved or dispersed in an organic solvent to form a varnish. A varnish can be suitably used when producing a laminated body. The varnish is usually prepared by adding 10 to 900 parts by mass of an organic solvent to 100 parts by mass of the components excluding the organic solvent in the resin composition and performing known treatments (stirring, mixing, kneading, etc.). Obtainable. As for a specific manufacturing method, the method for manufacturing a laminate and Examples described later can be referred to.

The organic solvent is not particularly limited as long as it can suitably dissolve or disperse each component in the resin composition of the present embodiment and does not impair the effects of the resin composition of the present embodiment. Examples of organic solvents include alcohols such as methanol, ethanol, and propanol; ketones such as acetone, methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK"), and methyl isobutyl ketone; dimethylacetamide, and dimethylformamide. amides such as; aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used singly or in admixture of two or more.

[Resin sheet]
A resin sheet contains the resin composition of this embodiment. Specifically, the resin sheet has a supporting substrate and a resin layer disposed on one side or both sides of the supporting substrate, and the resin layer contains the resin composition of the present embodiment. This resin sheet is also called a laminated resin sheet. The resin layer of the resin sheet is preferably formed by coating an uncured (A-stage) resin composition on a supporting substrate and then semi-curing (B-stage) the resin composition. As a method for producing such a resin sheet, a method for producing a composite of a B-stage resin layer and a supporting substrate is generally preferred. Specifically, the resin composition in an uncured state (A stage) is in the form of a varnish, and the varnish is applied to a supporting substrate such as a copper foil using a known method such as a bar coater. ° C. in a dryer for 1 to 60 minutes for semi-curing (to B-stage) to produce a resin sheet.
In addition, in this embodiment, the uncured state (A stage) refers to a state in which the resin composition is not substantially cured and is not gelled. The resin composition before being applied to the supporting substrate of the resin sheet is, for example, a mixture of constituent components of the resin composition (which may or may not contain a solvent), or the mixture dissolved or dispersed in a solvent. It is in the form of varnish and is in an uncured state (A stage).

The supporting substrate is not particularly limited, but for example, organic films such as polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylenetetrafluoroethylene copolymer film, and polyimide film; release films coated with a release agent on the surface; conductor foils such as copper foil and aluminum foil; and plate-shaped ones such as glass plates, SUS plates, and FRP.

The coating method is not particularly limited, but includes, for example, a method in which a solution obtained by dissolving the resin composition in a solvent is applied onto the supporting substrate using a bar coater, die coater, doctor blade, baker applicator, or the like.

Among resin sheets, a single-layer resin sheet is obtained by molding a resin composition into a sheet. The method for producing the single-layer resin sheet is not particularly limited and can be carried out according to a conventional method. For example, in the method for producing a resin sheet, a method of applying a solution in which a resin composition is dissolved in a solvent onto a supporting substrate and drying it, and then peeling or etching the supporting substrate from the resin sheet can be mentioned. In addition, a single-layer resin sheet without using a supporting substrate can be formed by forming a sheet by, for example, supplying a solution in which a resin composition is dissolved in a solvent into a mold having a sheet-like cavity and drying it. You can also get

In the preparation of the resin sheet or single-layer resin sheet, the drying conditions for removing the solvent are not particularly limited. 1 to 90 minutes at a temperature of 20 to 170° C. is preferred because it progresses.

The thickness of the resin layer of the resin sheet or single-layer resin sheet can be adjusted by adjusting the concentration of the solution of the resin composition and the thickness of the coating, and is not particularly limited. 0.1 to 500 .mu.m is preferred because it tends to remain.

A resin sheet or a single-layer resin sheet can be used, for example, as a material for forming wiring circuits on semiconductor wafers and semiconductor chip mounting substrates.

[Laminate]

By applying the resin composition of the present embodiment onto a supporting substrate, it is possible to obtain a laminate having a layer containing the resin composition, which is excellent in low void properties and chip adhesion. The laminate of the present embodiment includes a supporting base material and a layer containing the resin composition of the present embodiment laminated on the supporting base material. Such a laminate is obtained by attaching the resin composition of the present embodiment to a supporting substrate. A polymer film can be used as the supporting substrate, although not particularly limited. Examples of polymer film materials include polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polybutene, polybutadiene, ethylene-propylene copolymer, polymethylpentene, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol. vinyl-based resins such as copolymers; polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyurethane-based resins; polyimide-based resins; Examples of supporting substrates include films containing these resins and the like, and release films obtained by applying a release agent to the surface of these films. Among these, films containing one or more resins selected from the group consisting of polyester-based resins, polyimide-based resins, and polyamide-based resins, and release films obtained by applying a release agent to the surface of these films. More preferably, it is a film containing polyethylene terephthalate, which is a type of polyester resin, or a release film obtained by applying a release agent to the surface of a film containing polyethylene terephthalate.

The thickness of the supporting substrate is not particularly limited. From the viewpoint of better transportability, it is preferably 10 to 100 μm. The lower limit of the thickness of the supporting substrate is more preferably 10 μm or more, still more preferably 20 μm or more, further preferably 25 μm or more, from the viewpoint of ensuring a higher yield in manufacturing the laminate. is even more preferred. The upper limit of the thickness of the supporting base material is 80 μm or less in view of the fact that the supporting base material does not exist as a component of the semiconductor device in the end and is peeled off in the middle of the process and the manufacturing cost of the laminate. and more preferably 50 μm or less.

A method for forming a layer (resin composition layer) containing the resin composition of the present embodiment on a supporting substrate to produce the laminate of the present embodiment is not particularly limited. As such a production method, for example, a varnish obtained by dissolving or dispersing the resin composition of the present embodiment in an organic solvent is applied to the surface of the supporting substrate, heated and / or dried under reduced pressure, and the solvent is removed to solidify the resin composition of the present embodiment to form a resin composition layer. The drying conditions are not particularly limited, but the content ratio of the organic solvent to the resin composition layer is usually 10 parts by mass or less, preferably 5 parts by mass or less with respect to the total mass (100 parts by mass) of the resin composition layer. Dry to dry. The conditions for achieving such drying also vary depending on the type and amount of organic solvent in the varnish. For example, in the case of a varnish containing 10 to 200 parts by mass of methyl ethyl ketone with respect to a total of 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B), 2.5% under heating conditions of 90 to 160°C under 1 atmosphere. Drying for ~15 minutes is a guideline. The thickness of the resin composition layer in the laminate of the present embodiment is not particularly limited, but when the resin composition layer is dried, the viewpoint of better removal of relatively low molecular weight volatile matter and the function as a laminate is preferably in the range of 5 to 500 μm, and more preferably in the range of 10 to 100 μm, from the viewpoint of achieving the above effectively and reliably. As used herein, the thickness can be measured using, for example, a micrometer. After manufacturing the laminate of the present embodiment, a protective film may be separately laminated on the surface of the laminate opposite to the surface having the support substrate for the purpose of storage or the like.

[Semiconductor chip with resin composition layer and substrate for mounting semiconductor chip with resin composition layer]
A semiconductor chip with a resin composition layer of the present embodiment includes a semiconductor chip and a layer formed using the resin composition of the present embodiment laminated on the semiconductor chip. A semiconductor chip mounting substrate with a resin composition layer of the present embodiment includes a semiconductor chip mounting substrate and a layer formed using the resin composition of the present embodiment laminated on the semiconductor chip mounting substrate. .
A semiconductor chip with a resin composition layer of the present embodiment includes a semiconductor chip and a layer containing the resin composition of the present embodiment laminated on the semiconductor chip. A semiconductor chip mounting substrate with a resin composition layer of the present embodiment includes a semiconductor chip mounting substrate and a layer containing the resin composition of the present embodiment laminated on the semiconductor chip mounting substrate.

The method for producing a semiconductor chip with a resin composition layer of the present embodiment is not particularly limited. A semiconductor chip with a resin composition layer can be obtained by bonding together so that the resin composition layers of the body face each other, peeling off the support base material in the laminate, and then singulating with a dicing saw or the like. . The method for producing the semiconductor chip mounting substrate with the resin composition layer of the present embodiment is not particularly limited. It can be obtained by bonding the composition layers so that they face each other, and peeling off the supporting substrate in the laminate.

A method for bonding the laminate of the present embodiment to a semiconductor wafer or a substrate for mounting a semiconductor chip is not particularly limited, but a vacuum pressure laminator can be preferably used. In this case, it is preferable to apply pressure to the laminate of the present embodiment via an elastic body such as rubber to bond them together. The lamination conditions are not particularly limited as long as they are conditions commonly used in the industry, but for example, a temperature of 50 to 140° C., a contact pressure in the range of 1 to 11 kgf/cm ² , and an atmospheric pressure reduction of 20 hPa or less. done below. After the lamination step, the bonded laminate may be smoothed by hot pressing with a metal plate. The lamination step and the smoothing step can be performed continuously by a commercially available vacuum pressure laminator. In any case, the laminate attached to a semiconductor wafer or a substrate for mounting a semiconductor-mounted chip is subjected to removal of the support base material before flip-chip mounting of the chip. Thus, a semiconductor chip with a resin composition layer is obtained, which includes a semiconductor chip and a layer formed using the resin composition laminated on the semiconductor chip. Also, a semiconductor chip mounting substrate with a resin composition layer, which includes a semiconductor chip mounting substrate and a layer formed using a resin composition laminated on the semiconductor chip mounting substrate, is obtained. The layer formed using the resin composition is usually a partially cured layer, but may be a completely cured layer.

[Semiconductor device]
The semiconductor device of the present embodiment includes the semiconductor chip with the resin composition layer of the present embodiment and/or the substrate for mounting the semiconductor chip with the resin composition layer of the present embodiment. The method for manufacturing the semiconductor device of the present embodiment is not particularly limited, but for example, a method of mounting the semiconductor chip with the resin composition layer of the present embodiment on a substrate for mounting a semiconductor chip can be mentioned. A semiconductor chip may be mounted on the substrate for mounting a semiconductor chip with a resin composition layer of the present embodiment. In the method of mounting a semiconductor chip with a resin composition layer on a semiconductor chip mounting substrate and the method of mounting a semiconductor chip on a semiconductor chip mounting substrate with a resin composition layer, a flip chip bonder compatible with the thermocompression bonding method is preferably used. can be used. In addition, in the present embodiment, the case of flip-chip mounting a semiconductor chip on a substrate for mounting a semiconductor chip is described for convenience, but the object to which the resin composition of the present embodiment is applied while flip-chip mounting a semiconductor chip is can be a substrate other than a substrate for mounting a semiconductor chip. For example, the resin composition of the present embodiment is used to connect semiconductor chips via a junction between a semiconductor wafer and a semiconductor chip when mounting a semiconductor chip on a semiconductor wafer, or through TSV (Through Silicon Via). It is also possible to use it for the junction between each semiconductor chip of a chip stack, and the effect of this embodiment can be obtained in either case.

Hereinafter, the present embodiment will be described more specifically using examples and comparative examples. This embodiment is not limited at all by the following examples.

[Preparation of resin composition and laminate]
(Example 1)
As the aminotriazine novolak resin (A), Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation, weight average molecular weight: 1,500, nitrogen content: 19% by mass, hydroxy group equivalent: 146 g/eq. , Non-volatile content: 60% by mass) 66.7 parts by mass (40 parts by mass in terms of non-volatile content), and a maleimide compound represented by formula (3) as compound (B) (BMI-1000P (trade name), Kay Ai Kasei Co., Ltd., in formula (3), n ³ = 14 (average value), weight average molecular weight: 3,700) 50 parts by mass, and bis(3-ethyl-5-methyl-4 as compound (B) - Maleimidophenyl) methane (BMI-70 (trade name), K-I Kasei Co., Ltd., molecular weight: 550) 10 parts by mass, and hydrogenated rosin ester (Pine Crystal (registered trademark) KR) as a flux activator (C) -140 (trade name), Arakawa Chemical Industries, Ltd., acid dissociation constant pKa: 4.7, weight average molecular weight: 521) 25 parts by mass, slurry silica (YA050C-MJE (trade name) as an inorganic filler (D) ), Admatechs Co., Ltd., methacrylic surface-treated silica, solid content 50% by mass, dispersion medium: MEK, average particle size: 50 nm) 250 parts by mass (125 parts by mass in terms of nonvolatile matter), and as a curing catalyst (E) 1.12 mass of α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation, 10-hour half-life temperature: 119.20° C.), which is an organic peroxide Part, 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.), which is an imidazole compound as a curing catalyst (E), is mixed, and a high-speed stirring device is used in a hot water bath at 60 ° C. and stirred for 40 minutes, and then MEK was added to obtain a varnish with a solid content concentration of 60% by mass. This varnish was applied to a 38 μm thick polyethylene terephthalate film (TR1-38 (trade name, support base material), Unitika Ltd.) coated with a release agent on the surface, and dried at 100° C. under 1 atmosphere for 5 minutes. After heating and drying for 1 minute, a laminate having a resin composition layer with a thickness of 30 μm was obtained.

Incidentally, LA-1356 (trade name, manufactured by DIC), which is an aminotriazine novolak resin (A), is a compound represented by the formula (1) (a mixture of compounds represented by the formula (1), in which is a compound in which R ₁ is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l + m + n) is an integer of 3 to 18 group) and a compound represented by formula (2) (a mixture of compounds represented by formula (2), in which each R ₂ is independently a hydrogen atom or a methyl group and o, p, q, r, and s are each independently an integer of 1 to 4, and (o + p + q + r + s) is an integer of 5 to 20. , in the mixture, the mass ratio of the compound (mixture) represented by formula (1) to the compound (mixture) represented by formula (2) (formula (1): formula (2)) is 65 (parts by mass ): 35 (parts by mass).

(Example 2)
The compounding amount of Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as the aminotriazine novolac resin (A) was changed from 66.7 parts by mass (40 parts by mass in terms of nonvolatile matter) to 83.3 parts by mass. (50 parts by mass in terms of non-volatile content), and the compounding amount of the maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by the formula (3) as the compound (B) was changed to 50. A varnish was prepared in the same manner as in Example 1, except that the amount was changed from parts by mass to 40 parts by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 3)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) 33.3 parts by mass (20 parts by mass in terms of non-volatile content) as aminotriazine novolak resin (A) and a bismaleimide compound as compound (B) (MIZ-001 (trade name), Nippon Kayaku Co., Ltd., containing a maleimide compound represented by formula (9), where a is a mixture of 1 to 6 (integers), weight average Molecular weight: 3,900) 70 parts by mass, and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name) as compound (B), K-I Kasei Co., Ltd., molecular weight : 550) 10 parts by mass, a hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) 25 parts by mass as a flux activator (C), and an inorganic filler ( Slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) as D) 250 parts by mass (125 parts by mass in terms of non-volatile content), and an organic peroxide α, α' as a curing catalyst (E) -Di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole) which is an imidazole compound as a curing catalyst (E) 2E4MZ and 1 part by mass of Shikoku Kasei Kogyo Co., Ltd. are mixed, stirred in a hot water bath at 60 ° C. using a high-speed stirrer for 40 minutes, and then MEK is added to make the solid content concentration 60 mass. % varnish. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 4)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) 33.3 parts by mass (20 parts by mass in terms of nonvolatile matter) as aminotriazine novolac resin (A), and compound (B) of formula (3 ) represented by a maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) 35 parts by mass, and a bismaleimide compound (MIZ-001 (trade name), Nippon Kayaku ( Co., Ltd.) and 10 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K-I Kasei Co., Ltd.) as the compound (B). , 25 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C), and slurry silica (YA050C -MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of non-volatile matter), and α,α'-di(t-butylper), which is an organic peroxide as a curing catalyst (E) Oxy) diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) which is an imidazole compound as a curing catalyst (E) )) and 1 part by mass were mixed, stirred for 40 minutes using a high-speed stirrer in a hot water bath at 60°C, and then MEK was added to obtain a varnish with a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 5)
The compounding amount of Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as the aminotriazine novolac resin (A) was changed from 66.7 parts by mass (40 parts by mass in terms of nonvolatile matter) to 41.7 parts by mass. (25 parts by mass in terms of non-volatile content), and the compounding amount of the maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by the formula (3) as the compound (B) was changed to 50. A varnish was prepared in the same manner as in Example 1, except that parts by mass were changed to 65 parts by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 6)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as aminotriazine novolak resin (A) 56.7 parts by mass (34 parts by mass in terms of nonvolatile matter), and compound (B) of formula (3 ) and 51 parts by mass of a maleimide compound (BMI-1000P (trade name), K.I. Kasei Co., Ltd.) represented by ), and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane as compound (B). (BMI-70 (trade name), K-I Kasei Co., Ltd.) 15 parts by mass, and a hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical) as a flux activator (C). Kogyo Co., Ltd.) 25 parts by mass, slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of nonvolatile content) as an inorganic filler (D), and a curing catalyst (E) is an organic peroxide α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, curing catalyst (E) 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.), which is an imidazole compound, is mixed and stirred for 40 minutes in a hot water bath at 60 ° C. using a high-speed stirrer, After that, MEK was added to obtain a varnish having a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 7)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as aminotriazine novolak resin (A) 56.7 parts by mass (34 parts by mass in terms of nonvolatile matter), and compound (B) of formula (3 ) and 51 parts by mass of a maleimide compound (BMI-1000P (trade name), K.I Kasei Co., Ltd.) represented by the formula (B) and a maleimide compound represented by the formula (6) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd., non-volatile content 70% by mass, weight average molecular weight: 1,050) 21.4 parts by mass (15 parts by mass in terms of non-volatile content), and water as a flux activator (C) Added rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) 25 parts by mass, slurry silica (YA050C-MJE (trade name), Co., Ltd.) as an inorganic filler (D) ) Admatechs) 250 parts by mass (125 parts by mass in terms of non-volatile content), and α,α'-di(t-butylperoxy) diisopropylbenzene (Perbutyl (registered trademark)) which is an organic peroxide as a curing catalyst (E) ) P, NOF Co., Ltd.) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) 1 part by mass, which is an imidazole compound as a curing catalyst (E). Then, the mixture was stirred in a hot water bath at 60° C. for 40 minutes using a high-speed stirrer, and then MEK was added to obtain a varnish having a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 8)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as aminotriazine novolak resin (A) 50.0 parts by mass (30 parts by mass in terms of non-volatile matter), and compound (B) of formula (3 ) 45 parts by mass of a maleimide compound (BMI-1000P (trade name), K.I. Kasei Co., Ltd.) represented by ), and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane as compound (B). (BMI-70 (trade name), K-I Kasei Co., Ltd.) 25 parts by mass, and a hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical) as a flux activator (C) Kogyo Co., Ltd.) 25 parts by mass, slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of nonvolatile content) as an inorganic filler (D), and a curing catalyst (E) is an organic peroxide α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, curing catalyst (E) 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.), which is an imidazole compound, is mixed and stirred for 40 minutes in a hot water bath at 60 ° C. using a high-speed stirrer, After that, MEK was added to obtain a varnish having a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 9)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) 25 parts by mass (15 parts by mass in terms of non-volatile matter) as aminotriazine novolac resin (A), and compound (B) represented by formula (3) 40 parts by mass of the represented maleimide compound (BMI-1000P (trade name), K.I Kasei Co., Ltd.) and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI) as compound (B) -70 (trade name), K-I Kasei Co., Ltd.) 31 parts by mass, and a maleimide compound represented by formula (6) as compound (B) (MIR-3000-70MT (trade name), Nippon Kayaku ( Co., Ltd.) 20 parts by mass (14 parts by mass in terms of non-volatile content), and a hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C). 25 parts by mass, slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of non-volatile content) as an inorganic filler (D), and an organic curing catalyst (E) 1.12 parts by mass of α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation), which is a peroxide, and an imidazole compound as a curing catalyst (E) 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) was mixed, stirred in a hot water bath at 60°C for 40 minutes using a high-speed stirrer, and then MEK was added. By doing so, a varnish having a solid content concentration of 60% by mass was obtained. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Example 10)
Phenolite (registered trademark) LA-3018-50P (trade name, DIC Corporation) as aminotriazine novolac resin (A), weight average molecular weight: 1,400, nitrogen content: 18% by mass, hydroxy group equivalent: 151 g/ eq., non-volatile content 50% by mass) 80 parts by mass (40 parts by mass in terms of solid content), and a maleimide compound represented by formula (3) as compound (B) (BMI-1000P (trade name), K.I. Kasei Co., Ltd.) 50 parts by mass, and 10 parts by mass of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K-I Kasei Co., Ltd.) as compound (B) part, hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C) 25 parts by mass, and slurry silica as an inorganic filler (D) (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of non-volatile matter), and an organic peroxide α,α'-di(t- Butylperoxy) diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo) which is an imidazole compound as a curing catalyst (E) Co., Ltd.) and 1 part by mass are mixed, stirred for 40 minutes using a high-speed stirrer in a hot water bath at 60 ° C., and then MEK is added to obtain a varnish with a solid content concentration of 60% by mass. rice field. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

Incidentally, LA-3018-50P (trade name, manufactured by DIC), which is an aminotriazine novolak resin (A), is a compound represented by formula (1) (a mixture of compounds represented by formula (1), In the mixture, R ₁ is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l + m + n) is an integer of 3 to 18. a compound group) and a compound represented by formula (2) (a mixture of compounds represented by formula (2), in which each R ₂ is independently a hydrogen atom or a methyl group, wherein o, p, q, r, and s are each independently an integer of 1 to 4, and (o+p+q+r+s) is an integer of 5 to 20) and is.

(Example 11)
As the aminotriazine novolac resin (A), Phenolite (registered trademark) LA-7054 (trade name, DIC Corporation, weight average molecular weight: 2,400, nitrogen content: 12% by mass, hydroxy group equivalent: 125 g/eq. , Non-volatile content: 60% by mass) 66.7 parts by mass (40 parts by mass in terms of non-volatile content), and a maleimide compound represented by formula (3) as compound (B) (BMI-1000P (trade name), Kay Ai Kasei Co., Ltd.) 50 parts by mass, and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 (trade name), K-I Kasei Co., Ltd.) 10 as the compound (B) Parts by mass, 25 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C), and slurry as an inorganic filler (D) Silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of non-volatile matter), and α,α'-di(t), which is an organic peroxide as a curing catalyst (E) -Butylperoxy) diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei) which is an imidazole compound as a curing catalyst (E) Kogyo Co., Ltd.) 1 part by mass, and stirred for 40 minutes using a high-speed stirrer in a hot water bath at 60 ° C., and then MEK is added to obtain a varnish with a solid content concentration of 60% by mass. Obtained. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

Incidentally, LA-7054 (trade name, manufactured by DIC), which is an aminotriazine novolak resin (A), is a compound represented by the formula (1) (a mixture of compounds represented by the formula (1), in which is a compound in which R ₁ is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l + m + n) is an integer of 3 to 18 group) and a compound represented by formula (2) (a mixture of compounds represented by formula (2), in which each R ₂ is independently a hydrogen atom or a methyl group and o, p, q, r, and s are each independently an integer of 1 to 4, and (o + p + q + r + s) is an integer of 5 to 20. .

(Example 12)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as the aminotriazine novolak resin (A) is 66.7 parts by mass (40 parts by mass in terms of non-volatile matter) to 25 parts by mass (in terms of non-volatile matter 15 parts by mass), and the maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by the formula (3) as the compound (B) was changed from 50 parts by mass to 75 parts by mass. A varnish was prepared in the same manner as in Example 1, except that Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative example 1)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as an aminotriazine novolak resin (A) was added from 66.7 parts by mass (40 parts by mass in terms of nonvolatile matter) to 16.7 parts by mass (nonvolatile matter 10 parts by mass in terms of conversion), and 50 to 80 parts by mass of a maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by the formula (3) as the compound (B). A varnish was prepared in the same manner as in Example 1, except that it was changed to Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative example 2)
Cresol novolak resin (Phenolite (registered trademark) KA-1163 (trade name), DIC Corporation, weight average molecular weight: 2,100, nitrogen content: 0% by mass, hydroxy group equivalent: 118 g/eq.) 40 mass part, 50 parts by mass of a maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by formula (3) as compound (B), and bis(3-ethyl -5-Methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K-I Kasei Co., Ltd.) 10 parts by mass, and a hydrogenated rosin ester (Pine Crystal (registered trademark) as a flux activator (C) ) KR-140 (trade name), Arakawa Chemical Industries Co., Ltd.) 25 parts by mass, and slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (non-volatile 125 parts by mass in terms of minutes), and an organic peroxide α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) as a curing catalyst (E). 1.12 parts by mass and 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.), which is an imidazole compound as a curing catalyst (E), were mixed and mixed in a hot water bath at 60 ° C. The mixture was stirred for 40 minutes using a high-speed stirrer, and then MEK was added to obtain a varnish having a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative Example 3)
Phenol novolak resin (Phenolite (registered trademark) TD-2090-60M (trade name), DIC Corporation, weight average molecular weight: 8,500, nitrogen content: 0% by mass, hydroxy group equivalent: 105 g/eq.) 66.7 parts by mass of MEK solution (60% by mass of non-volatile content) (40 parts by mass in terms of non-volatile content), and a maleimide compound represented by formula (3) as compound (B) (BMI-1000P (trade name), silica Ai Kasei Co., Ltd.) 50 parts by mass, and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 (trade name), K-I Kasei Co., Ltd.) as the compound (B) 10 parts by mass, 25 parts by mass of a hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C), and an inorganic filler (D) Slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of non-volatile matter) and an organic peroxide α,α'-di( t-butylperoxy) diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku) which is an imidazole compound as a curing catalyst (E) Kasei Kogyo Co., Ltd.) 1 part by mass, and stirred in a hot water bath at 60 ° C. for 40 minutes using a high-speed stirrer, and then MEK is added to obtain a varnish with a solid content of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative Example 4)
Bisphenol A type novolac resin (Phenolite (registered trademark) LF-4871 (trade name), DIC Corporation, weight average molecular weight: 5,500, nitrogen content: 0% by mass, hydroxy group equivalent: 118 g/eq.) 66.7 parts by mass of MEK solution (60% by mass of non-volatile content) (40 parts by mass in terms of non-volatile content), and a maleimide compound represented by formula (3) as compound (B) (BMI-1000P (trade name), silica Ai Kasei Co., Ltd.) 50 parts by mass, and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (BMI-70 (trade name), K-I Kasei Co., Ltd.) as the compound (B) 10 parts by mass, 25 parts by mass of a hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C), and an inorganic filler (D) Slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass (125 parts by mass in terms of non-volatile matter) and an organic peroxide α,α'-di( t-butylperoxy) diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl-4-methylimidazole (2E4MZ, Shikoku) which is an imidazole compound as a curing catalyst (E) Kasei Kogyo Co., Ltd.) 1 part by mass, and stirred in a hot water bath at 60 ° C. for 40 minutes using a high-speed stirrer, and then MEK is added to obtain a varnish with a solid content of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative Example 5)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) 16.7 parts by mass (10 parts by mass in terms of nonvolatile matter) as aminotriazine novolac resin (A), and compound (B) of formula (3 ) and 40 parts by mass of a maleimide compound (BMI-1000P (trade name), K.I. Kasei Co., Ltd.) represented by ), and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane as compound (B). (BMI-70 (trade name), K-I Kasei Co., Ltd.) 35 parts by mass) and a maleimide compound represented by formula (6) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd.) ) 21 parts by mass (15 parts by mass in terms of non-volatile content), and 25 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C). part, 250 parts by mass of slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) as an inorganic filler (D) (125 parts by mass in terms of non-volatile content), and an organic peroxide as a curing catalyst (E) 2- Mix 1 part by mass of ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Co., Ltd.), stir in a hot water bath at 60 ° C. for 40 minutes using a high-speed stirrer, and then add MEK. to obtain a varnish having a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative Example 6)
Phenolite (registered trademark) LA-1356 (trade name, DIC Corporation) as aminotriazine novolac resin (A) 8.3 parts by mass (5 parts by mass in terms of nonvolatile matter), and compound (B) of formula (3 ) and 40 parts by mass of a maleimide compound (BMI-1000P (trade name), K.I. Kasei Co., Ltd.) represented by ), and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane as compound (B). (BMI-70 (trade name), K-I Kasei Co., Ltd.) 38 parts by mass, and a maleimide compound represented by formula (6) (MIR-3000-70MT (trade name), Nippon Kayaku Co., Ltd.) 24 parts by mass (17 parts by mass in terms of non-volatile content), and 25 parts by mass of hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 (trade name), Arakawa Chemical Industries, Ltd.) as a flux activator (C). and 250 parts by mass of slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) as an inorganic filler (D) (125 parts by mass in terms of non-volatile content), and an organic peroxide as a curing catalyst (E) α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) 1.12 parts by mass, 2-ethyl which is an imidazole compound as a curing catalyst (E) -1 part by mass of 4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) is mixed, stirred in a hot water bath at 60 ° C. for 40 minutes using a high-speed stirrer, and then MEK is added. A varnish with a solid content concentration of 60% by mass was obtained. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative Example 7)
41 parts by mass of a maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by formula (3) as compound (B), and bis(3-ethyl-5- 41 parts by mass of methyl-4-maleimidophenyl)methane (BMI-70 (trade name), K.I Kasei Co., Ltd.) and a maleimide compound represented by formula (6) (MIR-3000-70MT (trade name) , Nippon Kayaku Co., Ltd., non-volatile content 70% by mass) 26 parts by mass (18 parts by mass in terms of non-volatile content), and hydrogenated rosin ester (Pine Crystal (registered trademark) KR-140 ( (trade name), Arakawa Chemical Industries, Ltd.) 25 parts by mass, and slurry silica (YA050C-MJE (trade name), Admatechs Co., Ltd.) 250 parts by mass as an inorganic filler (D) (125 parts by mass in terms of non-volatile content part) and 1.12 parts by mass of α,α'-di(t-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, NOF Corporation) which is an organic peroxide as a curing catalyst (E) , 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., Ltd.) which is an imidazole compound as a curing catalyst (E), and mixed in a hot water bath at 60 ° C. using a high-speed stirring device. The mixture was stirred for 40 minutes, and then MEK was added to obtain a varnish having a solid content concentration of 60% by mass. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

(Comparative Example 8)
LA-1356 (trade name, DIC Corporation) as aminotriazine novolak resin (A) from 66.7 parts by mass (40 parts by mass in terms of non-volatile content) to 108.3 parts by mass (65 parts by mass in terms of non-volatile content) and changed the maleimide compound (BMI-1000P (trade name), K-I Kasei Co., Ltd.) represented by the formula (3) as the compound (B) from 60 parts by mass to 25 parts by mass. A varnish was prepared in the same manner as in Example 1. Using this varnish, a laminate having a resin composition layer with a thickness of 30 μm was obtained in the same manner as in Example 1.

[Evaluation of laminate]

Using the laminates obtained in Examples 1 to 12 and Comparative Examples 1 to 8, the following evaluations were performed. The results are shown in Tables 1 and 2.

(1) Evaluation of Voids after Semiconductor Chip Mounting The obtained laminate was cut into squares of 8 mm×8 mm. The cut laminate was applied to the 15 μm copper circuit surface in the pad portion of the semiconductor chip mounting board (WALTS-KIT CC80 (W)-0105JY (trade name) manufactured by Waltz Co., Ltd.). It was laminated so that the resin composition layer in was in contact with. After that, the polyethylene terephthalate film in the laminate was peeled off. Then, using a flip-chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.), under the conditions of a stage temperature of 85 ° C., a bond head temperature of 120 ° C., a load of 100 N, and a time of 1 second, it is composed of copper and solder. On a semiconductor chip having a Cu pillar as an electrode, placed so that the peeled surface of the resin composition layer is in contact and thermocompression bonded, then further heated under the conditions of a bond head temperature of 260 ° C., a load of 50 N, and a time of 4 seconds. Mounted by crimping. Image data of the mounted sample (semiconductor chip/resin composition layer/substrate for mounting semiconductor chip) was acquired using an ultrasonic precision flaw detection image processing device (μ-SDS (trade name), manufactured by KJTD Co., Ltd.). , the presence or absence of voids in the resin composition layer in the range of the semiconductor chip mounting portion was confirmed from the image data. If the ratio of the area occupied by the portion where voids can be confirmed is less than 10% with respect to the entire area occupied by the resin composition layer in the range of the semiconductor chip mounting portion, A is the case, and 10% or more and less than 20%. was rated as B, the case of 20% or more and less than 30% was rated as C, and the case of 30% or more was rated as D. In addition, it is evaluated that the smaller the ratio of the area occupied by the portion where voids can be confirmed, the higher the insulation reliability can be obtained. , it is evaluated that a laminate with very high insulation reliability can be obtained. In addition, in Table 1, E was evaluated when the resin composition layer was too sticky and the polyethylene terephthalate film in the laminate could not be peeled off and mounting was impossible.

(2) Evaluation of Voids after Thermal Curing The obtained laminate was cut into squares of 8 mm×8 mm. The cut laminate was applied to the 15 μm copper circuit surface in the pad portion of the semiconductor chip mounting board (WALTS-KIT CC80 (W)-0105JY (trade name) manufactured by Waltz Co., Ltd.). It was laminated so that the resin composition layer in was in contact with. After that, the polyethylene terephthalate film in the laminate was peeled off. Then, using a flip-chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.), under the conditions of a stage temperature of 85 ° C., a bond head temperature of 120 ° C., a load of 100 N, and a time of 1 second, it is composed of copper and solder. On a semiconductor chip having a Cu pillar as an electrode, placed so that the peeled surface of the resin composition layer is in contact and thermocompression bonded, then further heated under the conditions of a bond head temperature of 260 ° C., a load of 50 N, and a time of 4 seconds. Mounted by crimping. After mounting, it was cured by heat treatment at a temperature of 180° C. for 2 hours using a dryer (ESPEC SPHH-201 (trade name)). Image data of the cured sample (semiconductor chip/resin composition layer/substrate for mounting semiconductor chip) was acquired using an ultrasonic precision flaw detection image processing device (μ-SDS (trade name), manufactured by KJTD Co., Ltd.). , the presence or absence of voids in the resin composition layer in the range of the semiconductor chip mounting portion was confirmed from the image data. If the ratio of the area occupied by the portion where voids can be confirmed is less than 10% with respect to the entire area occupied by the resin composition layer in the range of the semiconductor chip mounting portion, A is the case, and 10% or more and less than 20%. was rated as B, the case of 20% or more and less than 30% was rated as C, and the case of 30% or more was rated as D. In addition, it is evaluated that the smaller the ratio of the area occupied by the portion where voids can be confirmed, the higher the insulation reliability can be obtained. , it is evaluated that a laminate with very high insulation reliability can be obtained. In addition, in Table 1, E was evaluated when the resin composition layer was too sticky and the polyethylene terephthalate film in the laminate could not be peeled off and mounting was impossible.

(3) Evaluation of Chip Adhesiveness The obtained laminate was cut into a square of 8 mm×8 mm. The cut laminate was applied to the 15 μm copper circuit surface in the pad portion of the semiconductor chip mounting board (WALTS-KIT CC80 (W)-0105JY (trade name) manufactured by Waltz Co., Ltd.). It was laminated so that the resin composition layer in was in contact with. After that, the polyethylene terephthalate film in the laminate was peeled off. Then, using a flip-chip bonder (LFB-2301 (trade name), Shinkawa Co., Ltd.), under the conditions of a stage temperature of 85 ° C., a bond head temperature of 120 ° C., a load of 100 N, and a time of 1 second, it is composed of copper and solder. On a semiconductor chip having a Cu pillar as an electrode, placed so that the peeled surface of the resin composition layer is in contact and thermocompression bonded, then further heated under the conditions of a bond head temperature of 260 ° C., a load of 50 N, and a time of 4 seconds. Mounted by crimping. After mounting, it was cured by heat treatment at a temperature of 180° C. for 2 hours using a dryer (ESPEC SPHH-201 (trade name)). The cured sample (semiconductor chip/resin composition layer/semiconductor chip mounting substrate) was polished using a rotary polishing device (device name: MetaServ (registered trademark) 3000 (trade name), manufactured by Buehler) to remove only the semiconductor chip. It was removed to obtain a laminate (A) of the resin composition layer and the substrate for mounting a semiconductor chip. In the laminate (A), the surface of the resin composition layer was visually observed to check whether the wiring layer derived from the semiconductor chip was adhered to the surface of the resin composition layer or not. When the wiring layer was adhered to the entire surface of the resin composition layer, it was evaluated as A because no peeling occurred. When the wiring layer is attached only to a part of the resin composition layer (that is, when there is a portion where the wiring layer is not attached to the resin composition layer), it is assumed that slight peeling occurs, and B evaluated. When the semiconductor chip was removed from the resin composition layer during the removal operation of the semiconductor chip, it was evaluated as C because peeling occurred. When the evaluation is A, the semiconductor chip does not fall off from the resin composition layer, and the chip adhesion is very excellent, so the laminate is evaluated as having very high insulation reliability. If the evaluation is B, the chip adhesion evaluation indicates that some peeling has occurred, but since the semiconductor device operates without problems, the chip adhesion is good and the insulation reliability is high. is evaluated. In addition, in Table 1, after the semiconductor chip is mounted, there are many voids between the semiconductor chip and the resin composition layer, and there are many parts where the semiconductor chip and the resin composition layer are not bonded. If it cannot be measured, it is written as "E".

This application is based on a Japanese patent application (Japanese Patent Application No. 2021-169268) filed on October 15, 2021 and a Japanese patent application (Japanese Patent Application No. 2022-26829) filed on February 24, 2022. The contents are incorporated herein by reference.

Since the resin composition of the present embodiment has low void properties and excellent chip adhesiveness, it can be used as a material for laminates, semiconductor chips with resin composition layers, substrates for mounting semiconductor chips with resin composition layers, and semiconductor devices. It is preferably used. The resin composition is suitable as an underfill material, and more suitable as a pre-applied underfill material.

Claims

an aminotriazine novolac resin (A);
and one or more compounds (B) selected from the group consisting of maleimide compounds (BA) and citraconimide compounds (BB),
The content of the aminotriazine novolak resin (A) is 15 to 60 parts by mass with respect to a total of 100 parts by mass of the aminotriazine novolak resin (A) and the compound (B).
Resin composition.
2. The aminotriazine novolac resin (A) according to claim 1, wherein the aminotriazine novolac resin (A) contains one or more selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2). Resin composition.

(In formula (1), R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group; l, m, and n each independently represent an integer of 0 to 10; (l + m + n) indicates an integer from 1 to 20.)

(In formula (2), each R 2 independently represents a hydrogen atom, a methyl group, or an ethyl group; o, p, q, r, and s each independently represents an integer of 0 to 10; , (o+p+q+r+s) represents an integer from 1 to 20).
The compound (B) comprises a compound (B1) and a compound (B2),
The compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less and a citraconimide compound (BB-1) having a weight average molecular weight of 3,000 or more and 9,500 or less. One or more selected from the group consisting of
The compound (B2) is selected from the group consisting of a maleimide compound (BA-2) having a weight average molecular weight of 300 or more and less than 3,000 and a citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000. is one or more of the
Each weight average molecular weight is a value converted to standard polystyrene obtained by GPC (gel permeation chromatography) method,
The resin composition according to claim 1.
The content of the compound (B1) is 45 to 90 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2),
The content of the compound (B2) is 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2).
The resin composition according to claim 3.
The resin composition according to claim 1, further comprising a flux activator (C).
The resin composition according to claim 5, wherein the flux activator (C) contains a rosin-based resin.
The resin composition according to claim 1, further comprising an inorganic filler (D).
8. The inorganic filler (D) according to claim 7, comprising one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide. of the resin composition.
The resin composition according to claim 7, wherein the inorganic filler (D) has an average particle size of 3 µm or less.
8. The content of the inorganic filler (D) is 20 to 500 parts by mass with respect to a total of 100 parts by mass of the aminotriazine novolac resin (A) and the compound (B). Resin composition.
The resin composition according to claim 1, further comprising a curing catalyst (E).
The resin composition according to claim 11, wherein the curing catalyst (E) contains one or more selected from the group consisting of organic peroxides and imidazole compounds.
The aminotriazine novolak resin (A) contains one or more selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2),

(In formula (1), R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group; l, m, and n each independently represent an integer of 0 to 10; (l + m + n) indicates an integer from 1 to 20.)

(In formula (2), each R 2 independently represents a hydrogen atom, a methyl group, or an ethyl group; o, p, q, r, and s each independently represents an integer of 0 to 10; , (o + p + q + r + s) represents an integer from 1 to 20.)
The compound (B) comprises a compound (B1) and a compound (B2),
The compound (B1) is a maleimide compound (BA-1) having a weight average molecular weight of 3,000 or more and 9,500 or less and a citraconimide compound (BB-1) having a weight average molecular weight of 3,000 or more and 9,500 or less. One or more selected from the group consisting of
The compound (B2) is selected from the group consisting of a maleimide compound (BA-2) having a weight average molecular weight of 300 or more and less than 3,000 and a citraconimide compound (BB-2) having a weight average molecular weight of 300 or more and less than 3,000. is one or more of the
Each weight average molecular weight is a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography) method,
The content of the compound (B1) is 45 to 90 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2),
The content of the compound (B2) is 10 to 55 parts by mass with respect to a total of 100 parts by mass of the compound (B1) and the compound (B2),
Including an inorganic filler (D),
The inorganic filler (D) contains one or more selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide,
The inorganic filler (D) has an average particle size of 3 μm or less,
2. The content of the inorganic filler (D) according to claim 1, which is 20 to 500 parts by mass with respect to a total of 100 parts by mass of the aminotriazine novolac resin (A) and the compound (B). Resin composition.
The resin composition according to claim 13, further comprising a flux activator (C).
The resin composition according to claim 14, wherein the flux activator (C) contains a rosin-based resin.
The resin composition according to claim 13, further comprising a curing catalyst (E).
The resin composition according to claim 16, wherein the curing catalyst (E) contains one or more selected from the group consisting of organic peroxides and imidazole compounds.
The resin composition according to any one of claims 1 to 17, which is used as an underfill material.
a supporting substrate;
A layer containing the resin composition according to any one of claims 1 to 17, which is laminated on the supporting substrate;
A laminate.
The laminate according to claim 19, wherein the layer containing the resin composition has a thickness of 5 to 500 µm.
a semiconductor chip;
A layer formed using the resin composition according to any one of claims 1 to 17, which is laminated on the semiconductor chip;
A semiconductor chip with a resin composition layer.
a substrate for mounting a semiconductor chip;
A layer formed using the resin composition according to any one of claims 1 to 17, which is laminated on the semiconductor chip mounting substrate;
A substrate for mounting a semiconductor chip with a resin composition layer.
A semiconductor device comprising the semiconductor chip with the resin composition layer according to claim 21.
A semiconductor device comprising the substrate for mounting a semiconductor chip with the resin composition layer according to claim 22 .