Thin film, laminate, semiconductor wafer with thin film layer, semiconductor mounting substrate with thin film layer, and semiconductor device

Abstract

The present invention provides a film comprising: a compound (A) containing at least one selected from the group consisting of maleimide compounds and citraconimide compounds; an organic peroxide (B) containing at least one selected from the group consisting of organic peroxides represented by a specific formula; and a hydroperoxide (C).

Description

Technical Field

[0001] The present invention relates to a thin film, a laminate using the thin film, a semiconductor wafer with a thin film layer, a semiconductor mounting substrate with a thin film layer, and a thin film. Specifically, the present invention relates to a thin film useful as a pre-underfill material. Background Art

[0002] In recent years, as semiconductor devices have become smaller and more performant, flip-chip mounting has attracted attention as a method of mounting a semiconductor chip (hereinafter sometimes referred to as a "chip") on a semiconductor mounting substrate (hereinafter sometimes referred to as a "substrate"). Flip-chip mounting generally involves the following process: after bonding the chip to the substrate, the gap between the chip and the substrate is filled with an underfill material and cured. However, as semiconductor devices have become smaller and more performant, the pitch of electrodes arranged on the chip and the gap between electrodes have become narrower, and the prolonged filling of the underfill material has led to deterioration in operability and the occurrence of filling defects such as non-filling, which has become a problem. In response to this, the following process is being studied: after pre-applying the underfill material to the chip or substrate, the chip and substrate are bonded and the underfill material is filled simultaneously.

[0003] The underfill material is a component that is in direct contact with the chip and the substrate. Therefore, important properties required of the underfill material include: ensuring optimal melt viscosity during the process of manufacturing semiconductor devices, and suppressing the unfilled portion of the underfill between the chip and the substrate (hereinafter sometimes referred to as "gaps") in the environment of manufacturing and using semiconductor devices.

[0004] Patent Document 1 describes a pre-underfill material using a radical polymerizable monomer as a main resin. Patent Document 1 also describes the blending of a silane coupling agent for the purpose of improving adhesion to a chip.

[0005] Patent Document 2 describes an underfill material containing an epoxy resin, an imidazole compound, and a maleimide compound.

[0006] Patent Document 3 describes a pre-underfill material using an epoxy compound and a carboxyl group-containing flux component, and mentions bonding.

[0007] Patent Document 4 describes a resin composition comprising a maleimide compound, an epoxy resin, and an epoxy resin curing agent as essential components, and states that the resin composition can obtain high adhesion after being thermally cured.

[0008] Patent Document 5 describes a resin composition for a printed circuit board. The composition is a thermosetting resin composition used to form an insulating layer in a printed circuit board and contains a maleimide compound having a specific structure, a benzoxazine compound, and an inorganic filler (C).

[0009] Patent Document 6 describes an adhesive for electronic components containing an aliphatic epoxy compound and a benzoxazine compound as a main curing agent, and also containing a phenolic curing agent.

[0010] Patent Document 7 describes an adhesive composition comprising a thermosetting compound, a polymer having a functional group reactive with the thermosetting compound, and a thermosetting agent. The adhesive composition has a melt viscosity at the bonding temperature of 10 Pa·s to 15,000 Pa·s, a gel time at the bonding temperature of 10 seconds to 10 seconds, and a gel time at 240°C of 1 second to 10 seconds.

[0011] Patent Document 8 describes a method for producing a semiconductor device using a sheet-shaped thermosetting resin composition.

[0012] In addition, when the chip and the substrate are joined by means of easily oxidized metals such as solder and copper, a flux component derived from carboxylic acid or the like is sometimes added to the pre-underfill material in order to remove the metal oxide film that will hinder the joining from the joining portion and obtain a good metal joint.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Application No. 2015-503220

[0016] Patent Document 2: Japanese Patent Application No. 2014-521754

[0017] Patent Document 3: Japanese Patent Application Laid-Open No. 2013-112730

[0018] Patent Document 4: Japanese Patent Application Laid-Open No. 2003-221443

[0019] Patent Document 5: Japanese Patent Application Laid-Open No. 2016-196548

[0020] Patent Document 6: Japanese Patent Application Laid-Open No. 2013-008800

[0021] Patent Document 7: Japanese Patent Application Laid-Open No. 2011-157529

[0022] Patent Document 8: Japanese Patent Application Laid-Open No. 2006-245242 Summary of the Invention

[0023] Problems to be solved by the invention

[0024] However, free radical polymerizable monomers typically cure quickly, and the mobility of the bonding site of the blended silane coupling agent is controlled by the silanol groups on the chip surface and the main resin, which polymerizes before a sufficient number of bonds are formed. As a result, the pre-underfill material described in Patent Document 1 fails to maintain optimal melt viscosity, failing to achieve sufficient adhesion and bonding to chips and substrates such as printed circuit boards. Consequently, voids tend to form. Furthermore, because free radical polymerizable monomers cure quickly, the resin composition cures before filling the unevenness on the chip surface. Therefore, the pre-underfill material described in Patent Document 1 suffers from the problem of not achieving a sufficient anchoring effect, which is useful for improving adhesion.

[0025] The material described in Patent Document 2 has a problem of having a narrow application range because it acts only on a polyimide passivation film.

[0026] With the technology described in Patent Document 3, even at room temperature, the carboxyl-containing compound reacts minutely with the epoxy compound, causing flux activity to decrease over time during storage. Consequently, the pre-underfill material described in Patent Document 3 suffers from low bonding stability and insufficient mass production capabilities.

[0027] The technology described in Patent Document 4 suffers from a problem of significantly reduced chip adhesion after moisture absorption treatment due to the high water absorption of maleimide resin. Insufficient adhesion allows water to penetrate through the peeling interface, significantly reducing insulation reliability. It should be noted that using only maleimide resin makes it difficult to achieve both good adhesion to the chip and to the printed circuit board.

[0028] Patent Document 5 does not describe flux activity or flux components, so the resin composition described in Patent Document 5 has a problem in that good metal bonding cannot be achieved.

[0029] In Patent Document 6, although the epoxy compound has high adhesiveness, there is a problem in that the epoxy compound also reacts with the flux component, and sufficient flux activity for achieving good metal bonding cannot be obtained.

[0030] The adhesive composition of Patent Document 7 contains a thermosetting agent having flux activity. However, in the examples, an epoxy compound and an epoxy group-containing polymer are used, and since these react at a temperature lower than the bonding temperature, it is difficult to obtain sufficient flux activity.

[0031] Patent Document 8 also describes that epoxy resin is suitable as a thermosetting resin contained in a thermosetting resin composition. However, as mentioned above, there is also a problem that epoxy compounds also react with flux components, and sufficient flux activity for achieving good metal bonding cannot be obtained.

[0032] The present invention is made in view of such problems, and provides: a film, a laminate, a semiconductor wafer with a thin film layer, a semiconductor mounting substrate with a thin film layer, and a semiconductor device, which have an excellent balance among storage stability, flexibility, flux activity, curability, low voids, and melt viscosity.

[0033] Solutions for solving problems

[0034] The present inventors conducted intensive studies to solve the above-mentioned problems in the conventional art and, as a result, found that the above-mentioned problems can be solved by using specific components in combination, thereby completing the present invention.

[0035] That is, the present invention includes the following contents. [1]

[0037] A film comprising:

[0038] A compound (A) containing at least one selected from the group consisting of maleimide compounds and citraconimide compounds;

[0039] An organic peroxide (B) containing at least one selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2); and

[0040] Hydroperoxide (C).

[0041]

[0042] (In formula (1), R 1 Each independently represents a hydrogen atom, a methyl group, or an ethyl group. ).

[0043]

[0044] (In formula (2), R 2 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 1 represents a group represented by the following formula (3) or (4).

[0045]

[0046] (In formula (3), R 3 represents a hydrogen atom, a methyl group, or an ethyl group, R 4 represents an alkylene group having 1 to 3 carbon atoms, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ).

[0047]

[0048] (In formula (4), R6 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 2 represents a group represented by the following general formulae (a) to (c).

[0049]

[0050] (In formula (c), n 1 represents an integer greater than or equal to 1 and less than or equal to 5. ). [2]

[0052] The film according to [1], wherein the compound (A) contains at least one selected from the group consisting of 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-phenylmaleimide, a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), and a bismaleimide compound containing a structural unit represented by the following formula (9) and maleimide groups located at both ends.

[0053]

[0054] (In formula (5), R 7 Each independently represents a hydrogen atom or a methyl group, n 2 represents an integer greater than 1. ).

[0055]

[0056] (In formula (6), n 3 represents an integer greater than or equal to 1 and less than or equal to 30. ).

[0057]

[0058] (In formula (7), R 8 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, R 9 Each independently represents a hydrogen atom or a methyl group. ).

[0059]

[0060] (In formula (8), R 10 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 represents an integer greater than or equal to 1 and less than or equal to 10. ).

[0061]

[0062] (In formula (9), 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, R 13 Each 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, n 5 represents an integer greater than or equal to 1 and less than or equal to 10.) [3]

[0064] The film according to [2], wherein the compound (A) contains at least one selected from the group consisting of 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, a maleimide compound represented by the above formula (5), a maleimide compound represented by the above formula (6), a maleimide compound represented by the above formula (7), a maleimide compound represented by the above formula (8), and a bismaleimide compound containing a structural unit represented by the above formula (9) and maleimide groups located at both ends. [4]

[0066] The film according to any one of [1] to [3], wherein the hydroperoxide (C) contains at least one selected from the group consisting of a hydroperoxide represented by the following formula (10), a hydroperoxide represented by the following formula (11), and a hydroperoxide represented by the following formula (12).

[0067]

[0068] (In formula (10), R 14 Each independently represents a hydrogen atom or a methyl group, R 15 represents a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group. ).

[0069]

[0070] (In formula (11), R 16 Each independently represents a hydrogen atom or a methyl group, R 17 represents a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group. ).

[0071]

[0072] (In formula (12), R 18Each independently represents a hydrogen atom or a methyl group, R 19 Each independently represents a hydrogen atom or a methyl group, R 20 Each independently represents a hydrogen atom or a methyl group. ). [5]

[0074] The film according to any one of [1] to [4], wherein the molecular weight of the hydroperoxide (C) is 100 or more. [6]

[0076] The film according to any one of [1] to [5], wherein the hydroperoxide (C) contains at least one selected from the group consisting of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and tert-amyl hydroperoxide. [7]

[0078] The film according to any one of [1] to [6], wherein the organic peroxide (B) contains at least one selected from the group consisting of diisopropyl benzene peroxide, n-butyl-4,4-di-(tert-butylperoxy)valerate, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3-ol, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane. [8]

[0080] The film according to any one of [1] to [7], further comprising a benzoxazine compound (D) represented by the following formula (13), the following formula (14), the following formula (15), and the following formula (16).

[0081]

[0082] (In formula (13), R 21 Each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 22 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulae (d) to (w), n 6 represents an integer from 1 to 4. ).

[0083]

[0084] (In formula (14), R 23 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 24 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulas (d) to (r), n 7 represents an integer from 1 to 4. ).

[0085]

[0086] (In formula (15), R 25 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent. )

[0087]

[0088] (In formula (16), R 26 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent. )

[0089]

[0090]

[0091] (In formulas (d) to (w), R a represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, R b represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.) [9]

[0093] The film according to [8], wherein the benzoxazine compound (D) contains at least one selected from the group consisting of compounds represented by the following formula (17) and the following formula (18).

[0094]

[0095] (In formula (17), R 27 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 28 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, X 3 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO2-", a group represented by the formula "-CO-", an oxygen atom, or a single bond.).

[0096]

[0097] (In formula (18), R 29 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 30 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, X 4 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO2-", a group represented by the formula "-CO-", an oxygen atom, or a single bond.).

[0098]

[0099] (In formula (19), Y is an alkylene group or a hydrocarbon group having 6 or more and 30 or less carbon atoms and an aromatic ring, n 8 represents an integer greater than 0. ).

[10]

[0101] The film according to [8] or [9], wherein the benzoxazine compound (D) contains at least one selected from the group consisting of a compound represented by the following formula (20), a compound represented by the following formula (21), a compound represented by the following formula (22), a compound represented by the following formula (23), a compound represented by the following formula (24), and a compound represented by the following formula (25).

[0102]

[0103]

[0104] (In formula (22), R 31 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. )

[0105]

[11]

[0107] The film according to any one of [8] to

[10] , wherein the content of the benzoxazine compound (D) is 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A).

[12]

[0109] The film according to any one of [1] to

[11] , further comprising an acrylic compound (E).

[13]

[0111] The film according to

[12] , wherein the content of the acrylic compound (E) is 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A).

[14]

[0113] The film according to any one of [1] to

[13] , further comprising a flux component (F).

[15]

[0115] The film according to

[14] , wherein the content of the flux component (F) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total amount of the compound (A).

[16]

[0117] The film according to any one of [1] to

[15] , further comprising an inorganic filler (G).

[17]

[0119] The film according to

[16] , wherein the average particle size of the inorganic filler (G) is 3 μm or less.

[18]

[0121] The thin film according to

[16] or

[17] , wherein the inorganic filler (G) contains at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide.

[19]

[0123] The film according to any one of

[16] to

[18] , wherein the content of the inorganic filler (G) is 300 parts by mass or less relative to 100 parts by mass of the compound (A).

[20]

[0125] The film according to any one of [1] to

[19] , further comprising an imidazole compound (H). [twenty one]

[0127] The film according to

[20] , wherein the content of the imidazole compound (H) is 10 parts by mass or less relative to 100 parts by mass of the compound (A). [twenty two]

[0129] The film according to any one of [1] to

[21] , wherein the film has a thickness of 10 μm or more and 100 μm or less. [twenty three]

[0131] The film according to any one of [1] to

[22] , which is used for pre-application of an underfill material. [twenty four]

[0133] A laminate comprising:

[0134] a supporting substrate; and,

[0135] A layer comprising the thin film according to any one of [1] to

[23] , laminated on the supporting substrate.

[25]

[0137] A semiconductor wafer with a thin film layer, comprising:

[0138] semiconductor wafers; and,

[0139] The laminated body described in

[24] stacked on the aforementioned semiconductor wafer,

[0140] A layer including the thin film is stacked on the semiconductor wafer.

[26]

[0142] A semiconductor mounting substrate with a thin film layer, comprising:

[0143] a semiconductor mounting substrate; and

[0144] The laminated body described in

[24] laminated on the aforementioned semiconductor mounting substrate,

[0145] The layer including the thin film is laminated on the semiconductor mounting substrate.

[27]

[0147] A semiconductor device comprising: the semiconductor wafer with a thin film layer described in

[25] and / or the semiconductor mounting substrate with a thin film layer described in

[26] .

[0148] Effects of the Invention

[0149] According to the present invention, a film, a laminate, a semiconductor wafer with a thin film layer, a semiconductor mounting substrate with a thin film layer, and a semiconductor device can be provided, which have an excellent balance among storage stability, flexibility, flux activity, curability, low voids, and melt viscosity. DETAILED DESCRIPTION

[0150] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described. Note that the following this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

[0151] [film]

[0152] The film of this embodiment comprises: a compound (A) containing at least one selected from the group consisting of maleimide compounds and citraconimide compounds (hereinafter, also referred to as "compound (A)"); an organic peroxide (B) containing at least one selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2) (hereinafter, also referred to as "organic peroxide (B)"); and a hydroperoxide (C). Due to this composition, the film of this embodiment exhibits an excellent balance of storage stability, flexibility, flux activity, curability, low voiding properties, and melt viscosity. Due to these properties, the film of this embodiment is suitable for use as a pre-underfill material used in flip-chip chip mounting.

[0153]

[0154] (In formula (1), R 1 Each independently represents a hydrogen atom, a methyl group, or an ethyl group. ).

[0155]

[0156] (In formula (2), R 2 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 1 represents a group represented by the following formula (3) or (4).

[0157]

[0158] (In formula (3), R 3 represents a hydrogen atom, a methyl group, or an ethyl group, R 4 represents an alkylene group having 1 to 3 carbon atoms, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ).

[0159]

[0160] (In formula (4), R 6 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 2 represents a group represented by the following general formulae (a) to (c).

[0161]

[0162] (In formula (c), n 1 represents an integer greater than or equal to 1 and less than or equal to 5. ).

[0163] [Compound (A)]

[0164] The film of this embodiment includes a compound (A) containing at least one selected from the group consisting of maleimide compounds and citraconimide compounds from the perspective of insulation reliability and heat resistance. Compound (A) is not particularly limited as long as it contains at least one selected from the group consisting of a maleimide group and a citraconimide group in its molecule. Compound (A) preferably does not react with the flux component (F) described below. Compound (A) may be used alone or as a mixture of two or more.

[0165] The compound (A) of the present embodiment preferably contains a maleimide compound from the viewpoint of obtaining excellent reactivity with the acrylic compound (E) described later, insulation reliability, and heat resistance.

[0166] The maleimide compound is not particularly limited as long as it is a resin or compound having one or more maleimide groups in its molecule. The maleimide compound may be used alone or in combination of two or more.

[0167] Specific examples of maleimide compounds include, but are not limited to, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 4,4-diphenylmethanebismaleimide, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethanemaleimide, Imine, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4-diphenyl ether bismaleimide, 4,4-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, polyphenylmethane maleimide, novolac type maleimide compound, biphenyl aralkyl type maleimide compound, 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N , N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-phenylmaleimide, a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), and a maleimide compound containing a structural unit represented by the following formula (9) and maleimide groups at both ends. As compound (A), it can be included in the film of this embodiment in the form of a prepolymer obtained by polymerizing a maleimide compound, a prepolymer obtained by polymerizing a maleimide compound and other compounds such as an amine compound, etc.

[0168]

[0169] (In formula (5), R 7 Each independently represents a hydrogen atom or a methyl group, n 2 represents an integer greater than or equal to 1, preferably an integer greater than or equal to 1 and less than or equal to 10. ).

[0170]

[0171] (In formula (6), n 3 represents an integer greater than or equal to 1 and less than or equal to 30. ).

[0172]

[0173] (In formula (7), R 8 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, R 9 Each independently represents a hydrogen atom or a methyl group. ).

[0174]

[0175] (In formula (8), R 10 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 represents an integer greater than or equal to 1 and less than or equal to 10. ).

[0176]

[0177] (In formula (9), 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, R 13 Each 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, n 5 represents an integer greater than or equal to 1 and less than or equal to 10. ).

[0178] Among the above, the compound (A) preferably contains, from the viewpoint of solubility in an organic solvent, a compound selected from the group consisting of 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-phenylmaleimide, the maleimide compound represented by the above formula (5), the maleimide compound represented by the above formula (6), the maleimide compound represented by the above formula (7), and the above formula (8) The present invention further comprises at least one selected from the group consisting of a maleimide compound represented by the above formula (9) and a bismaleimide compound containing a structural unit represented by the above formula (9) and a maleimide group located at both ends, and more preferably comprises at least one selected from the group consisting of 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, a maleimide compound represented by the above formula (5), a maleimide compound represented by the above formula (6), a maleimide compound represented by the above formula (7), a maleimide compound represented by the above formula (8), and a bismaleimide compound containing a structural unit represented by the above formula (9) and a maleimide group located at both ends. Furthermore, from the viewpoint of maintaining good storage stability, flexibility, flux activity, curability and low voiding properties, and in particular improving melt viscosity, the maleimide compound preferably contains the maleimide compound represented by the above formula (8), and further preferably contains 2,2-bis{4-(4-maleimidephenoxy)phenyl}propane, the maleimide compound represented by the above formula (6), the maleimide compound represented by the above formula (7), and the maleimide compound represented by the above formula (8).

[0179] As the maleimide compound, a commercially available product can be used. As 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, for example, BMI-80 (trade name) manufactured by Yamato Chemical Industry Co., Ltd. As the maleimide compound represented by formula (5), for example, BMI-2300 (trade name) manufactured by Yamato Chemical Industry Co., Ltd. can be mentioned. Examples of the maleimide compound represented by formula (6) include BMI-1000P (trade name, n3 in formula (6) = 14 (average)) manufactured by KI Chemical Industry Co., Ltd., BMI-650P (trade name, n3 in formula (6) = 9 (average)) manufactured by KI Chemical Industry Co., Ltd., BMI-250P (trade name, n3 in formula (6) = 3 to 8 (average)), and CUA-4 (trade name, n3 in formula (6) = 1) manufactured by KI Chemical Industry Co., Ltd. Examples of the maleimide compound represented by formula (7) include BMI-70 (trade name; bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane) manufactured by KI Chemical Industry Co., Ltd. Examples of the maleimide compound represented by formula (8) include MIR-3000-70MT (trade name, R in formula (8)) manufactured by Nippon Kayaku Co., Ltd. 10 All are hydrogen atoms, and n 4 (wherein the formula (9) is a mixture of 1 to 10). Examples of the maleimide compound containing the structural unit represented by formula (9) and maleimide groups at both terminals include MIZ-001 (trade name) manufactured by Nippon Kayaku Co., Ltd.

[0180] The citraconimide compound is not particularly limited, and examples thereof include o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 4,4-diphenylmethanebiscitraconimide, 2,2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis(3,5-diethyl-4-citraconimidephenyl)methane, Citraconimide includes 1,3-dimethylsilyl)amino-1-propyl]citraconimide, ...

[0181] In the film of this embodiment, the content of compound (A) is not particularly limited. From the viewpoint of ensuring the insulation reliability and heat resistance of the package after installation, the content of compound (A) in the film is preferably 10 mass % or more and 60 mass % or less, more preferably 15 mass % or more and 50 mass % or less, and further preferably 20 mass % or more and 40 mass % or less.

[0182] [Organic peroxide (B)]

[0183] The film of this embodiment includes, from the viewpoint of imparting curability during installation, an organic peroxide (B) containing at least one selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2). The organic peroxide (B) can be used alone or as a mixture of two or more.

[0184]

[0185] (In formula (1), R 1 Each independently represents a hydrogen atom, a methyl group, or an ethyl group. ).

[0186]

[0187] (In formula (2), R 2 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 1 represents a group represented by the following formula (3) or (4).

[0188]

[0189] (In formula (3), R 3represents a hydrogen atom, a methyl group, or an ethyl group, R 4 represents an alkylene group having 1 to 3 carbon atoms, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ).

[0190]

[0191] (In formula (4), R 6 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 2 represents a group represented by the following general formulae (a) to (c).

[0192]

[0193] (In formula (c), n 1 represents an integer greater than or equal to 1 and less than or equal to 5. ).

[0194] In this embodiment, from the viewpoint of solubility in organic solvents and suppression of volatilization or thermal decomposition during film formation, the organic peroxide (B) preferably contains at least one selected from the group consisting of diisopropyl benzene peroxide, n-butyl-4,4-di-(tert-butylperoxy)valerate, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0195] In the film of this embodiment, the content of the organic peroxide (B) is not particularly limited. From the viewpoint of reducing volatile components during installation, the content is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the compound (A).

[0196] 〔Hydroperoxide (C)〕

[0197] The film of this embodiment may also contain a hydroperoxide (C) from the viewpoint of imparting curability during installation. The hydroperoxide (C) is not particularly limited as long as the hydrogen atom of hydrogen peroxide is substituted with an organic group. In this embodiment, the hydroperoxide (C) may be used alone or as a mixture of two or more.

[0198] Examples of the hydroperoxide (C) include a hydroperoxide represented by the following formula (10), a hydroperoxide represented by the following formula (11), and a hydroperoxide represented by the following formula (12).

[0199]

[0200] (In formula (10), R 14 Each independently represents a hydrogen atom or a methyl group, R 15 represents a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group. ).

[0201]

[0202] (In formula (11), R 16 Each independently represents a hydrogen atom or a methyl group, R 17 represents a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group. ).

[0203]

[0204] (In formula (12), R 18 Each independently represents a hydrogen atom or a methyl group, R 19 Each independently represents a hydrogen atom or a methyl group, R 20 Each independently represents a hydrogen atom or a methyl group. ).

[0205] The molecular weight of the hydroperoxide (C) is not particularly limited, but is preferably 100 or greater, more preferably 130 or greater, from the viewpoint of reducing volatile components during installation. From the same viewpoint, the hydroperoxide (C) preferably contains at least one selected from the group consisting of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and tert-amyl hydroperoxide.

[0206] In the film of the present embodiment, the content of the hydroperoxide (C) is not particularly limited. However, from the viewpoint of achieving both curability during mounting and reduction of volatile components, the content is preferably 10 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.1 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the compound (A).

[0207] [Benzoxazine compound (D)]

[0208] In the film of the present embodiment, from the viewpoint of imparting adhesion, a benzoxazine compound (D) may also be contained. As a benzoxazine compound, there is no particular limitation as long as it has an oxazine ring as a basic skeleton. In the present embodiment, the benzoxazine compound also includes compounds having a polycyclic oxazine skeleton such as naphthoxazine compounds. In the present embodiment, the benzoxazine compound (D) can be used alone or as a mixture of two or more. In the present embodiment, the benzoxazine compound (D) is preferably represented by the following formula (13), the following formula (14), the following formula (15), and the following formula (16).

[0209]

[0210] (In formula (13), R 23 Each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 24 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulae (d) to (w), n 5 represents an integer from 1 to 4. ).

[0211]

[0212] (In formula (14), R 25 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 26 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulas (d) to (r), n 6 represents an integer from 1 to 4. ).

[0213]

[0214] (In formula (15), R 27 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent. )

[0215]

[0216] (In formula (16), R 28 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent. )

[0217]

[0218]

[0219] (In formulas (d) to (w), R a represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, R b represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group. ).

[0220] In the present embodiment, from the viewpoint of flame retardancy and heat resistance, the benzoxazine compound (D) preferably contains at least one selected from the group consisting of compounds represented by the following formula (17) and the following formula (18).

[0221]

[0222] (In formula (17), R 29 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 30Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, X 3 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO2-", a group represented by the formula "-CO-", an oxygen atom, or a single bond.).

[0223]

[0224] (In formula (18), R 31 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 32 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, X 4 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO2-", a group represented by the formula "-CO-", an oxygen atom, or a single bond.).

[0225]

[0226] (In formula (19), Y is an alkylene group or a hydrocarbon group having 6 or more and 30 or less carbon atoms and an aromatic ring, n 7 represents an integer greater than or equal to 0, preferably an integer greater than or equal to 0 and less than or equal to 5. ).

[0227] In this embodiment, from the viewpoint of solubility in an organic solvent, the benzoxazine compound (D) preferably contains at least one selected from the group consisting of a compound represented by the following formula (20), a compound represented by the following formula (21), a compound represented by the following formula (22), a compound represented by the following formula (23), a compound represented by the following formula (24), and a compound represented by the following formula (25).

[0228]

[0229] (In formula (22), R 33 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0230]

[0231]

[0232] In addition, in this embodiment, the benzoxazine compound (D) may contain oligomers etc. produced by polymerization of monomers.

[0233] In the film of this embodiment, the content of the benzoxazine compound (D) is not particularly limited. From the viewpoint of achieving both the adhesiveness and flexibility of the film, the content is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 55 parts by mass or less, and even more preferably 15 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the compound (A).

[0234] [Propylene compound (E)]

[0235] In the film of the present embodiment, from the viewpoint of imparting adhesion and curing properties during installation, an acryl compound (E) may be included. As the acryl compound (E), there is no particular limitation as long as it contains an acryl group. In the present embodiment, the acryl compound (E) may be used alone or as a mixture of two or more. In the present embodiment, the acryl compound (E) preferably contains a structural unit represented by the following formula (26) at the end of the molecule.

[0236]

[0237] In formula (26), -* represents an atomic bond, which is bonded to the main chain of the polymer.

[0238] Since the acryl compound (E) has highly reactive acryl groups at the ends, reactions between acryl groups and reactions between maleimide and citraconimide groups and acryl groups readily occur during the curing process. Consequently, the resulting cured product has an increased crosslink density, resulting in low porosity and improved heat resistance (glass transition temperature). Furthermore, the presence of polar groups improves chip adhesion to adherends such as chips and substrates and the underfill material.

[0239] The polymer serving as the main chain of the acrylic compound (E) is not particularly limited as long as it contains an alkenyl group and a hydroxyl group.

[0240] The alkenyl group is not particularly limited, and examples thereof include vinyl, (meth)allyl, propenyl, butenyl, and hexenyl. Among these, propenyl is preferred.

[0241] The polymer is not particularly limited, and examples thereof include bisphenol A, tetramethylbisphenol A, diallylbisphenol A, biphenol, bisphenol F, diallylbisphenol F, triphenylmethane-type phenol, tetraphenol, novolac-type phenol, cresol novolac resin, and polymers having an alkenyl group on the phenol ring of phenol having a biphenyl aralkyl skeleton (biphenyl-type phenol). These polymers may optionally have substituents. These polymers may be one type or a suitable combination of two or more types.

[0242] Examples of such substituents include halogen atoms and linear, branched, or cyclic hydrocarbon groups. Preferably, the linear, branched, or cyclic hydrocarbon group has an alkenyl group as a substituent. The alkenyl group is as described above.

[0243] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0244] The linear or branched hydrocarbon group is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, and tert-hexyl.

[0245] The cyclic hydrocarbon group is not particularly limited, and examples thereof include aliphatic cyclic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the aliphatic cyclic hydrocarbon group include monocyclic aliphatic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic hydrocarbon groups such as bicyclo[2.2.2]octyl, tricyclo[5.2.1.02,6]decyl, tricyclo[3.3.1.13,7]decyl, tetracyclo[6.2.1.13,6.02,7]dodecyl, and adamantyl. Examples of the aromatic hydrocarbon group include groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0246] The acrylic compound (E) is not particularly limited. However, from the viewpoint of preventing voids caused by volatilization of the acrylic compound (E) during flip-chip mounting, the mass average molecular weight of the acrylic compound (E) is preferably 300 or more and 10,000 or less, more preferably 400 or more and 7,000 or less, and even more preferably 1,000 or more and 3,000 or less, as measured by polystyrene conversion by gel permeation chromatography (GPC).

[0247] The acrylic compound (E) preferably includes a resin represented by the following formula (26-1) in which 20% or more of the alkenyl groups in the molecule are acrylic groups. If the film of this embodiment includes such an acrylic compound (E), excellent heat resistance can be obtained.

[0248]

[0249] (In formula (26-1), W each independently represents a hydrocarbon group having 6 to 15 carbon atoms which may have a substituent. U each independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. 1 represents the number of repetitions, whose average value is a real number between 1 and 20.

[0250] In formula (26-1), W each independently represents a hydrocarbon group having 6 to 15 carbon atoms, which may have a substituent. The substituent in W preferably contains an aromatic ring. In this case, the propenyl compound (E) is preferably a resin represented by formula (26-2) described below, in which 20% or more of the alkenyl groups in the molecule are propenyl groups.

[0251] In formula (26-1), W is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 10 to 15 carbon atoms. W is not particularly limited, and examples thereof include the following structures. These structures may be used alone or in combination of two or more.

[0252]

[0253] Among these, W preferably has an alkyl-type biphenyl skeleton from the viewpoint of heat resistance.

[0254] In formula (26-1), "20% or more of the alkenyl groups in the molecule are propenyl groups" means that 20% or more of the total of U and terminal propenyl groups are propenyl groups. In formula (26-1), preferably 40% or more of the alkenyl groups in the molecule are propenyl groups, and more preferably 60% or more. The upper limit is not particularly limited but is 100%. When the alkenyl group content in the molecule is within the above range, excellent curability can be achieved.

[0255] In formula (26-1), U other than the propenyl group independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl, (meth)allyl, butenyl, and hexenyl. As U other than the propenyl group, a hydrogen atom is preferred from the perspective of being able to appropriately control the curability.

[0256] In formula (26-1), n 1 represents the number of repetitions, and its average value is a real number ranging from 1 to 20. From the perspective of being able to appropriately control the curing properties, n 1 The average value is preferably a real number of 1 to 10, and more preferably a real number of 1 to 6.

[0257] When W in formula (26-1) contains an aromatic ring as a substituent, the acrylic compound (E) is preferably a resin represented by the following formula (26-2) in which 20% or more of the alkenyl groups in the molecule are acrylic groups.

[0258]

[0259] In formula (26-2), Y each independently represents a hydrocarbon group having 1 to 6 carbon atoms. X each independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. 2 Represents the number of repetitions, whose average value is a real number from 1 to 20.

[0260] In formula (26-2), Y each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms. Y is a structure in which one hydrogen atom of the divalent hydrocarbon group having 1 to 6 carbon atoms is replaced by a phenol ring having an alkenyl group. Y is not particularly limited, but is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms and being linear, branched, or cyclic.

[0261] The linear hydrocarbon group is not particularly limited, and examples thereof include methylene, ethylene, propylene, butylene, pentylene, and hexylene. Examples of branched hydrocarbon groups include alkylmethylene groups such as -C(CH3)2-, -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; and alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-.

[0262] The cyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

[0263] These hydrocarbon groups may be used alone or in combination of two or more.

[0264] Among these, Y is preferably a methylene group from the viewpoint of obtaining good compatibility with other resins such as the radically polymerizable resin described later or the compound (B).

[0265] In formula (26-2), "20% or more of the alkenyl groups in the molecule are propenyl groups" means that 20% or more of the total of X and the terminal propenyl groups are propenyl groups. In formula (26-2), preferably 40% or more of the alkenyl groups in the molecule are propenyl groups, and more preferably 60% or more. The upper limit is not particularly limited and is 100%. When the alkenyl group content in the molecule is within the above range, excellent curability can be achieved.

[0266] In formula (26-2), X other than the propenyl group independently represents a hydrogen atom or an alkenyl group having 2 to 6 carbon atoms. The alkenyl group having 2 to 6 carbon atoms is as described above. As U other than the propenyl group, a hydrogen atom is preferred from the viewpoint of being able to suitably control the curability.

[0267] In formula (26-2), n 2 represents the number of repetitions, whose average value is a real number from 1 to 20. 2 From the viewpoint of being able to appropriately control curability, the average value is preferably a real number of 1 to 10, and more preferably a real number of 1 to 6.

[0268] The method for producing the propenyl compound (E) represented by the formula (26-1) or (26-2) according to the present embodiment is not particularly limited, and the compound can be produced by a known method.

[0269] As a production method, for example, a method using a phenolic resin as a raw material can be mentioned. The phenolic resin is not particularly limited, and can be mentioned: bisphenol A, tetramethylbisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane-type phenol, tetraphenol, novolac-type phenol, cresol novolac resin, phenol having a biphenyl aralkyl skeleton (biphenyl-type phenol), and phenol having a triphenylmethane skeleton (triphenylmethane-type phenol).

[0270] In the production method, the hydroxyl groups in these phenolic resins are allylated to synthesize an allyl ether, and the resulting allyl ether groups are then rearranged to form propenyl ether groups. Alternatively, the resulting allyl ether groups are subjected to a Claisen rearrangement reaction to form an allylated phenol, and the allyl groups are then rearranged to form propenyl groups according to a known method.

[0271] Preferred examples of the acrylic compound (E) include an acrylic resin having a structure represented by the following formula (26-3) and an acrylic resin having a structure represented by the following formula (26-4). Commercially available products can be used as such acrylic compounds (E). For example, the acrylic resin having a structure represented by the following formula (26-3) includes BPN01-S (trade name, mass average molecular weight: 1830) manufactured by Gunei Chemical Industry Co., Ltd., and the acrylic resin having a structure represented by the following formula (26-4) includes TPMP01 (trade name, mass average molecular weight: 2371) manufactured by Gunei Chemical Industry Co., Ltd.

[0272]

[0273] (The above formula (26-3) is n 11 A mixture of 1 to 10.

[0274]

[0275] (Formula (26-4) is n 12 A mixture of 1 to 10.

[0276] In the film of this embodiment, the content of the acrylic compound (E) is not particularly limited, but is preferably 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A) from the viewpoint of achieving both film flexibility and adhesiveness.

[0277] 〔Flux ingredients (F)〕

[0278] In order to demonstrate flux activity in flip-chip mounting, the film of this embodiment preferably further comprises a flux component (F). The flux component (F) is not particularly limited as long as it is an organic compound having one or more acidic sites in the molecule. As acidic sites, for example, phosphate groups, phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups are preferred. In a semiconductor device using the film of this embodiment as a pre-underfill material, phenolic hydroxyl groups or carboxyl groups are more preferred from the viewpoint of more effectively preventing the migration and corrosion of metals such as solder and copper constituting the joint. The flux component (F) can be used alone or as a mixture of two or more.

[0279] The flux component (F) is not particularly limited. However, in order to sufficiently remove the oxide film at the joint, the acid dissociation constant pKa is preferably 3.8 or more and 15.0 or less. From the viewpoint of achieving a balance between the storage stability of the varnish and the resin laminate and the flux activity, it is more preferably 4.0 or more and 14.0 or less.

[0280] The flux component (F) in the film of this embodiment is not particularly limited. However, from the perspective of preventing volatilization before flux activity is exhibited during flip-chip mounting, that is, from the perspective of preventing volatilization of the flux component (F) before the oxide film at the joint is removed, the molecular weight is preferably 200 or greater, more preferably 250 or greater. In order to have acidic mobility and obtain sufficient flux activity, the molecular weight is preferably 8000 or less, more preferably 1000 or less, and even more preferably 500 or less.

[0281] The flux component (F) is not particularly limited, and examples thereof include abietic acid, neoabietic acid, dehydroabietic acid, pimaric acid, isopimaric acid, palustric acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, abietic acid-modified resins such as rosin-modified maleic acid resin, N,N'-bis(salicylidene)-1,2-propanediamine, N,N'-bis(salicylidene)-1,3-propanediamine, and phenolphthalein. These flux components (F) are preferred due to their excellent solvent solubility and storage stability.

[0282] Among these, dehydroabietic acid, diphenolic acid, dihydroabietic acid, tetrahydroabietic acid, rosin-modified maleic acid resins and other rosin-modified resins, N,N'-bis(salicylidene)-1,2-propanediamine, and N,N'-bis(salicylidene)-1,3-propanediamine are more preferred from the viewpoint of preventing deactivation by compound (A). Dehydroabietic acid, dihydroabietic acid, rosin-modified maleic acid resins and other rosin-modified resins, N,N'-bis(salicylidene)-1,2-propanediamine, and N,N'-bis(salicylidene)-1,3-propanediamine are relatively low in reactivity. Therefore, they are more preferred from the viewpoint of maintaining sufficient flux activity required for oxide film removal without substantially causing reaction with the acrylic group-containing resin (A) of this embodiment and the radically polymerizable resin or compound (B) of this embodiment.

[0283] As the flux component (F), a commercially available product can be used. Examples of rosin-modified maleic acid resins include, but are not limited to, Marquide No. 32 (manufactured by Arakawa Chemical Industries, Ltd.).

[0284] In the film of this embodiment, the content of the flux component (F) is not particularly limited. From the viewpoint of insulation reliability and ensuring sufficient flux activity during mounting, the content is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 65 parts by mass or less, and even more preferably 15 parts by mass or more and 60 parts by mass or less, relative to 100 parts by mass of the compound (A).

[0285] [Inorganic filler (G)]

[0286] The film of this embodiment preferably further comprises an inorganic filler (G) to improve flame resistance, improve thermal conductivity, and reduce thermal expansion. The use of an inorganic filler can improve the flame resistance and thermal conductivity of the film and reduce thermal expansion.

[0287] The average particle size of the inorganic filler (G) is not particularly limited. When the film of this embodiment is used as a pre-bottom-filling material, it is preferably 3 μm or less, and more preferably 1 μm or less, from the viewpoint of narrowing the spacing of the electrodes arranged on the chip and the narrowing of the gap between the electrodes. The lower limit of its average particle size is not particularly limited, for example, it is 10 nm. It should be noted that, in this embodiment, the "average particle size" of the inorganic filler (G) refers to the median particle size of the inorganic filler (G). The median particle size here refers to the particle size in which the volume of the particles on the larger particle size side and the volume of the particles on the smaller particle size side each occupy 50% of the total powder when the particle size distribution of the powder is divided into two parts based on a certain particle size. The average particle size (median particle size) of the inorganic filler (G) is measured by a wet laser diffraction / scattering method.

[0288] The inorganic filler (G) is not particularly limited, and examples thereof include: silica such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum compounds such as boehmite, aluminum hydroxide, aluminum oxide, and aluminum nitride; magnesium compounds such as magnesium oxide and magnesium hydroxide; 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; mica; and glass such as short fiber glass, spherical glass, and fine powder glass (e.g., E-glass, T-glass, and D-glass). Furthermore, when it is desired to impart electrical conductivity or anisotropic conductivity to the thin film of this embodiment, metal particles of gold, silver, nickel, copper, a tin alloy, and palladium may be used as the inorganic filler (G).

[0289] Among these, from the viewpoint of improving the flame retardancy and reducing the thermal expansion coefficient of the film of this embodiment, the inorganic filler (G) preferably contains at least one selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide, more preferably silica, alumina, and boron nitride, and among them, silica is further preferred. Examples of silica include SFP-120MC (trade name) and SFP-130MC (trade name) manufactured by Denka Co., Ltd., 0.3 μm SX-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-MJF (trade name), and YA050C-MJA (trade name) manufactured by ADMATECHS CO., LTD.

[0290] These inorganic fillers (G) can be used alone or in combination of two or more.

[0291] The inorganic filler (G) may be one surface-treated with a silane coupling agent.

[0292] The silane coupling agent is not particularly limited as long as it is a silane coupling agent commonly used for surface treatment of inorganic substances. Examples include vinylsilane-based silane coupling agents such as vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane; phenylaminosilane-based silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane; phenylsilane-based silane coupling agents such as trimethoxyphenylsilane; and imidazolesilane-based silane coupling agents. These silane coupling agents can be used alone or in combination of two or more.

[0293] In the film of this embodiment, the content of the inorganic filler (G) is not particularly limited. From the viewpoint of both improving the flame retardancy of the film and reducing the thermal expansion coefficient, it is preferably contained in an amount of 300 parts by mass or less, more preferably in an amount of 20 parts by mass or more and 300 parts by mass or less, and further preferably in an amount of 50 parts by mass or more and 250 parts by mass or less, relative to 100 parts by mass of the compound (A).

[0294] [Imidazole compound (H)]

[0295] The film of this embodiment may also contain an imidazole compound (H) from the viewpoint of imparting curability during installation. The imidazole compound (H) is not particularly limited as long as it has an imidazole group. The imidazole compound (H) may be used alone or in combination of two or more.

[0296] In the present embodiment, the imidazole compound (H) preferably includes one represented by the following formula (h1).

[0297]

[0298] (In formula (h1), R 7 Represents methyl or ethyl, R 8 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and R 9 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group.)

[0299] In the present embodiment, from the viewpoint of solubility in an organic solvent and reduction of volatile components during installation, the imidazole compound (H) is preferably an imidazole compound represented by the following formula (h2).

[0300]

[0301] (In formula (h2), R 17 Represents methyl or ethyl, R 18 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group, and R 19 represents a hydrogen atom or a methyl group.)

[0302] In the present embodiment, from the viewpoint of ensuring molecular mobility during mounting, the imidazole compound (H) is preferably an imidazole compound represented by the following formula (h3).

[0303]

[0304] (In formula (h3), R 20 Represents methyl or ethyl, R 21 represents a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, R 22 represents a hydrogen atom or a methyl group.)

[0305] In this embodiment, from the viewpoint of achieving both excellent flux activity and solubility in organic solvents, the imidazole compound (H) preferably contains at least one selected from the group consisting of 1-benzyl-2-methylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole.

[0306] In the film of this embodiment, the content of the imidazole compound (H) is not particularly limited. From the viewpoint of achieving both storage stability of the varnish and curability during installation, the content is preferably 10 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the compound (A).

[0307] [Other ingredients]

[0308] The film of this embodiment may contain one or more other components in addition to the compound (A), organic peroxide (B), hydroperoxide (C), benzoxazine compound (D), acrylic compound (E), flux component (F), inorganic filler (G) and imidazole compound (H).

[0309] As other components, there are no particular limitations, and for example, flexibility imparting components can be cited. Flexibility imparting components are not particularly limited as long as they can impart flexibility to the layer comprising a film. For example, thermoplastic polymers such as polyimide, polyamide-imide, polystyrene, polyolefin, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), (meth) acrylonitrile-butadiene rubber (NBR), polyurethane, polypropylene, (meth) acrylic oligomers, (meth) acrylic polymers, and silicone resins can be cited. These flexibility imparting components can be used alone or in combination of two or more.

[0310] The film of this embodiment may also contain a silane coupling agent as an additional component to improve the adhesion between the resin and the inorganic filler interface and to improve moisture absorption and heat resistance. Examples of silane coupling agents include vinylsilane-based silane coupling agents such as vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane; phenylaminosilane-based silane coupling agents such as N-phenyl-3-aminopropyltrimethoxysilane; phenylsilane-based silane coupling agents such as trimethoxyphenylsilane; and imidazolesilane-based silane coupling agents. These silane coupling agents may be used alone or in combination of two or more.

[0311] When a silane coupling agent is used, its content is not particularly limited, but is preferably 0.05 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the compound (A) from the viewpoint of improving moisture absorption heat resistance and reducing the amount of volatilization during flip-chip mounting.

[0312] In the film of the present embodiment, as other components, for the purposes such as the manufacturability improvement of laminate and the dispersibility of filler, a wetting dispersant can also be included. As a wetting dispersant, as long as it is the wetting dispersant usually used in coatings etc., it is not particularly limited. For example, can be enumerated: Disperbyk (registered trademark) -110 (trade name), Disperbyk (registered trademark) -111 (trade name), Disperbyk (registered trademark) -180 (trade name), Disperbyk (registered trademark) -161 (trade name), BYK-W996 (trade name), BYK-W9010 (trade name) and BYK-W903 (trade name) made by BYK Japan KK. These wetting dispersants can be used alone as one or suitably mixed as two or more and used.

[0313] When a wetting dispersant is used, its content is not particularly limited. However, from the perspective of improving the manufacturability of the laminate, it is preferably from 0.1 parts by mass to 5 parts by mass, and more preferably from 0.5 parts by mass to 3 parts by mass, relative to 100 parts by mass of the inorganic filler (G). It should be noted that when two or more wetting dispersants are used in combination, their total amount preferably satisfies the aforementioned ratio.

[0314] As other components, the film of this embodiment may contain various additives according to various purposes, within a range that does not impair the desired properties. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, leveling agents, glossing agents, flame retardants, and ion scavengers. These additives may be used alone or in combination of two or more.

[0315] In the film of the present embodiment, the content of other additives is not particularly limited, but is usually 0.01 to 10 parts by mass of each additive relative to 100 parts by mass of the compound (A).

[0316] The film of this embodiment is suitable as a pre-priming material, and therefore, is preferably in a semi-cured state (B stage). The film is in a semi-cured state, so that excellent, low voids and chip adhesion can be obtained. In this embodiment, the semi-cured state (B stage) means that the components contained in the film do not actively start to react (curing), but the film is heated to a dry state, that is, to a degree of non-adhesion, and the solvent is volatilized. It also includes a state in which the solvent is only volatilized without curing even without heating. In this embodiment, the minimum melt viscosity of the semi-cured state (B stage) is generally 50,000 Pa·s or less. It should be noted that the minimum melt viscosity can be measured by the method described in the examples described later.

[0317] The thickness of the film of this embodiment is not particularly limited, but is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm, from the viewpoint of ensuring underfill filling between connection terminals during mounting.

[0318] [Thin film manufacturing method]

[0319] The film of the present embodiment is not particularly limited to the manufacturing method as long as it can obtain the above-mentioned composition. As the manufacturing method of the film of the present embodiment, for example, compound (A), organic peroxide (B) and hydroperoxide (C) are suitably mixed with benzoxazine compound (D), propenyl compound (E), flux component (F), inorganic filler (G), imidazole compound (H) and other components as needed, and then a varnish in which these components are dissolved or dispersed in an organic solvent is formed, and the varnish is applied to a support and dried, thereby obtaining. For a specific manufacturing method, the manufacturing method and examples of the laminate described later can be used as reference. After drying, the film of the present embodiment can be peeled off from the support and used, or it can be used together with the support.

[0320] The organic solvent is not particularly limited as long as it can appropriately dissolve or disperse the aforementioned components and does not impair the desired effects of the film of this 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; amides such as dimethylacetamide and dimethylformamide; and aromatic hydrocarbons such as toluene and xylene. These organic solvents can be used alone or in combination of two or more.

[0321] The support may be any known material without particular limitation, but is preferably a resin film. Examples of the resin film include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate film, polyvinyl alcohol film, and triacetyl acetate film. Among these, PET film is preferred.

[0322] [Laminated body]

[0323] The laminate of the present embodiment comprises: a supporting substrate; and a layer containing the film of the present embodiment stacked on the supporting substrate. For such a laminate, the film of the present embodiment is supported on a supporting substrate. As the supporting substrate, there is no particular limitation, and a polymer film can be used. As the material of the polymer film, for example, there can be mentioned: a film containing at least one resin selected from the group consisting of polyesters such as polyvinyl chloride, polyvinylidene chloride, polybutene, polybutadiene, polyurethane, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, polyimide, and polyamide, and a release film having a release agent coated on the surface of these films. Among these, polyesters, polyimides, and polyamides are preferred, and polyethylene terephthalate, which is a type of polyester, is more preferred.

[0324] The thickness of the support substrate is not particularly limited. From the perspective of the manufacturability of the laminate, for example, the stability of the coating thickness when a thin film is coated on the support substrate, and the transportability of the laminate, it is preferably 10 to 100 μm. As the lower limit of the thickness of the support substrate, from the perspective of ensuring the yield when manufacturing the laminate, it is more preferably 12 μm or more, further preferably 25 μm or more, and further more preferably 30 μm or more. As the upper limit of the thickness of the support substrate, from the perspective of preventing the support substrate from ultimately existing as a component of the semiconductor device and being peeled off in the middle of the process, and from the perspective of the manufacturing cost of the laminate, it is more preferably 80 μm or less, and further preferably 50 μm or less.

[0325] There is no particular limitation on the method for manufacturing the laminate of the present embodiment by forming a layer (hereinafter also referred to as "film layer") comprising the film of the present embodiment on a supporting substrate. As such a manufacturing method, for example, the following method can be cited: a varnish in which the film of the present embodiment is dissolved or dispersed in an organic solvent is applied to the surface of the supporting substrate, dried under heating and / or reduced pressure, the solvent is removed, and the film of the present embodiment is cured to form a film layer. The drying conditions are not particularly limited. Regarding the ratio of the organic solvent to the film layer, the drying is generally performed in a manner of 10 parts by mass or less, preferably 5 parts by mass or less, relative to the total amount of the film layer (100 parts by mass). The conditions for achieving the above drying can be appropriately adjusted according to the type and compounding amount of the organic solvent in the varnish. For example, in the case of a varnish containing 10 to 120 parts by mass of methyl ethyl ketone relative to 100 parts by mass of compound (A), the goal is to dry for about 3 to 10 minutes at 1 atmosphere and under heating conditions of 90 to 160°C. It should be noted that the above film layer can function as an insulating layer.

[0326] [Semiconductor wafer with thin film layer, and semiconductor mounting substrate with thin film layer]

[0327] The semiconductor wafer with a thin film layer according to this embodiment comprises: a semiconductor wafer; and a laminate according to this embodiment laminated on the semiconductor wafer, wherein the layer including the thin film is laminated on the semiconductor wafer. Furthermore, the semiconductor mounting substrate with a thin film layer according to this embodiment comprises: a semiconductor mounting substrate; and a laminate according to this embodiment laminated on the semiconductor mounting substrate, wherein the layer including the thin film is laminated on the semiconductor mounting substrate.

[0328] The method for producing the semiconductor wafer with a thin film layer according to this embodiment is not particularly limited. For example, the thin film layers of the laminate according to this embodiment are bonded to the surface of the semiconductor wafer on which the electrodes are formed, i.e., the surface to be bonded to the substrate, so that the thin film layers of the laminate according to this embodiment face each other. Furthermore, the method for producing the semiconductor mounting substrate with a thin film layer according to this embodiment is not particularly limited. For example, the thin film layers of the laminate according to this embodiment are bonded to the chip mounting side of the semiconductor mounting substrate, so that the thin film layers of the laminate according to this embodiment face each other.

[0329] There is no particular limitation on the method for laminating the laminate of this embodiment to a semiconductor wafer or a semiconductor mounting substrate, and a vacuum pressurized laminator can be used as appropriate. In this case, it is preferred to pressurize and laminate the laminate of this embodiment with the aid of an elastic body such as rubber. There is no particular limitation on the lamination conditions as long as they are the conditions commonly used in this field. For example, at a temperature of 50 to 140°C and a pressure of 1 to 11 kgf / cm 2The lamination process is carried out under a contact pressure in the range of 20 hPa and an atmospheric pressure reduction of 20 hPa or less. After the lamination process, the laminated body can be smoothed by hot pressing using metal plates. The lamination process and smoothing process can be carried out continuously using a commercially available vacuum pressure laminator. For the laminate attached to the semiconductor wafer or the semiconductor mounting substrate, the support substrate is removed before the flip-chip mounting of the chip in any case.

[0330] [Semiconductor devices]

[0331] The semiconductor device of the present embodiment comprises: a semiconductor wafer with a thin film layer of the present embodiment and / or a semiconductor mounting substrate with a thin film layer of the present embodiment. The method for manufacturing the semiconductor device of the present embodiment is not particularly limited. For example, the following method can be cited: thinning the semiconductor wafer with a thin film layer of the present embodiment by means of grinding or the like, and singulating it by a dicing machine or the like to make a chip with a thin film layer, which is then mounted on a semiconductor mounting substrate. In addition, the chip can be mounted on the semiconductor mounting substrate with a thin film layer of the present embodiment. In the method of mounting the chip with a thin film layer on the semiconductor mounting substrate and the method of mounting the semiconductor chip on the semiconductor mounting substrate with a thin film layer, a flip chip bonder corresponding to a thermal compression bonding process can be suitably used. In addition, although the present embodiment simply describes the case where the chip is flip-chip mounted on the semiconductor mounting substrate, the object to which the thin film of the present embodiment is applied can also be set to be other than the semiconductor mounting substrate while the chip is flip-chip mounted. For example, the film of this embodiment can also be used for the joint between the semiconductor wafer and the chip when the chip is mounted on the semiconductor wafer, or the joint between each chip in the chip stack in which the chips are connected to each other via TSV (Through Silicon Via) technology, etc. In any case, the excellence based on the present invention can be obtained.

[0332] Example

[0333] Hereinafter, this embodiment will be described in more detail using examples and comparative examples. This embodiment is not limited in any way to the following examples.

[0334] [Production of Films and Laminates]

[0335] (Example 1)

[0336] As compound (A), the following four compounds were used in combination. That is, n represented by the above formula (6) was prepared. 358.44 parts by mass of a maleimide compound (BMI-1000P (trade name), manufactured by KI Chemical Industry Co., Ltd.) having an average value of 14, 10.02 parts by mass (5.01 parts by mass as non-volatile matter) of a MEK solution of bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70 (trade name), manufactured by KI Chemical Industry Co., Ltd.), 20.04 parts by mass (10.02 parts by mass as non-volatile matter) of a MEK solution of 2,2-bis{4-(4-maleimidophenoxy)phenyl}propane (BMI-80 (trade name), manufactured by KI Chemical Industry Co., Ltd.), and a mixture containing R in the above formula (8) 10 37.90 parts by mass (26.53 parts by mass as nonvolatile content) of a MEK solution of a maleimide compound containing only hydrogen atoms (MIR-3000-70MT (trade name), manufactured by Nippon Kayaku Co., Ltd., nonvolatile content 70% by mass)

[0337] In addition, 83.48 parts by mass (41.74 parts by mass as non-volatile matter) of a MEK solution (50% by mass of non-volatile matter) of Pd-type benzoxazine (manufactured by Shikoku Chemicals Co., Ltd.) as a benzoxazine compound (D), 50.46 parts by mass (25.23 parts by mass as non-volatile matter) of a MEK solution (50% by mass of non-volatile matter) of an acrylic group-containing resin having a structure represented by the following formula (26-3) as an acrylic compound (E), and rosin-modified maleic acid resin (Marquide No. 32 (trade name)) as a flux component (F) were mixed. 100.18 parts by mass (50.09 parts by mass as non-volatile matter) of a MEK solution (non-volatile matter 50% by mass, manufactured by Arakawa Chemical Industries, Ltd.), 417.44 parts by mass (208.72 parts by mass as non-volatile matter) of a slurry silica (YA050C-MJE (trade name), solid content 50%, average particle size: 50 nm, manufactured by ADMATECH CO., LTD.) as an inorganic filler (G), and a hydroperoxide (PERMENTA) represented by the following formula (11-1) as a hydroperoxide (C) H (trade name), manufactured by NOF Corporation, 50% non-volatile matter) 3.74 parts by mass (1.87 parts by mass as non-volatile matter), 1.87 parts by mass of an organic peroxide represented by the following formula (1-1) as an organic peroxide (B) (dicumyl peroxide, manufactured by Kishida Chemical Co., Ltd.), and 5.01 parts by mass of an imidazole compound represented by the following formula (h4) as an imidazole compound (H) (2E4MZ (trade name), manufactured by Shikoku Chemicals Co., Ltd.) were mixed with the above four compounds (A) and stirred for 40 minutes using a high-speed stirring device to obtain a varnish.

[0338] The resulting varnish was applied to a 38 μm thick polyethylene terephthalate film (TR1-38 (trade name), manufactured by Unitika Ltd.) coated with a release agent, and then dried by heating at 100°C for 5 minutes to obtain a laminate having a film layer (insulating layer) with a thickness of 30 μm. The content of compound (A) in the film, calculated from the mass of the film, was 23.1% by mass.

[0339]

[0340] (The above formula (26-3) is n 11 A mixture of 1 to 10.

[0341]

[0342] (Example 2)

[0343] A varnish was prepared in the same manner as in Example 1 except that the amount of PERMENTA H as the hydroperoxide (C) was changed to 0.47 parts by mass, to obtain a laminate having a film layer having a thickness of 30 μm.

[0344] (Example 3)

[0345] A varnish was prepared in the same manner as in Example 1 except that 1.87 parts by mass of a hydroperoxide represented by the following formula (10-1) (PERCUMY P (trade name), manufactured by NOF Corporation) was used instead of PERMENTA H as the hydroperoxide (C). A laminate having a thin film layer thickness of 30 μm was obtained.

[0346]

[0347] (Example 4)

[0348] A varnish was prepared in the same manner as in Example 3 except that the amount of PERCUMY P as the hydroperoxide (C) was changed to 0.47 parts by mass, to obtain a laminate having a thin film layer with a thickness of 30 μm.

[0349] (Example 5)

[0350] A varnish was prepared in the same manner as in Example 1 except that 1.87 parts by mass of a hydroperoxide represented by the following formula (10-2) (PERCUMY H-80 (trade name), manufactured by NOF Corporation) was used instead of PERMENTA H as the hydroperoxide (C). A laminate having a thin film layer having a thickness of 30 μm was obtained.

[0351]

[0352] (Example 6)

[0353] A varnish was prepared in the same manner as in Example 5 except that the amount of PERCUMY H-80 as the hydroperoxide (C) was changed to 0.47 parts by mass, to obtain a laminate having a film layer having a thickness of 30 μm.

[0354] (Example 7)

[0355] A varnish was prepared in the same manner as in Example 1, except that 1.17 parts by mass of an organic peroxide represented by the following formula (2-1) (PERBUTYL P (trade name), manufactured by NOF Corporation) was used instead of dicumyl peroxide as the organic peroxide (B), and the amount of PERMENTAH blended as the hydroperoxide (C) was changed to 1.17 parts by mass, to obtain a laminate having a thin film layer having a thickness of 30 μm.

[0356]

[0357] (Example 8)

[0358] A varnish was prepared in the same manner as in Example 7 except that the amount of PERBUTYL P as the organic peroxide (B) was changed to 2.50 parts by mass and the amount of PERMENTA H as the hydroperoxide (C) was changed to 0.87 parts by mass to obtain a laminate having a film layer thickness of 30 μm.

[0359] (Example 9)

[0360] A varnish was prepared in the same manner as in Example 1, except that 1.87 parts by mass of an organic peroxide represented by the following formula (2-2) (PERHEXA V (trade name), manufactured by NOF Corporation) was used instead of dicumyl peroxide as the organic peroxide (B), and the amount of PERMENTAH blended as the hydroperoxide (C) was changed to 0.62 parts by mass. A laminate having a thin film layer thickness of 30 μm was obtained.

[0361]

[0362] (Example 10)

[0363] A varnish was prepared in the same manner as in Example 1 except that 2.97 parts by mass of PERHEXA V was used as the organic peroxide (B) instead of dicumyl peroxide, and 1.10 parts by mass of PERCUMY H-80 was used as the hydroperoxide (C) instead of PERMENTA H, to obtain a laminate having a thin film layer thickness of 30 μm.

[0364] (Example 11)

[0365] A varnish was prepared in the same manner as in Example 1 except that 2E4MZ was not used as the imidazole compound (H), the amount of dicumyl peroxide as the organic peroxide (B) was changed to 5.56 parts by mass, and the amount of PERMENTA H as the hydroperoxide (C) was changed to 3.74 parts by mass. A laminate having a thin film layer thickness of 30 μm was obtained.

[0366] (Example 12)

[0367] A varnish was prepared in the same manner as in Example 1 except that 1.87 parts by mass of a hydroperoxide represented by the following formula (12-1) (PEROCTA H (trade name), manufactured by NOF Corporation) was used instead of PERMENTA H as the hydroperoxide (C). A laminate having a thin film layer thickness of 30 μm was obtained.

[0368]

[0369] (Example 13)

[0370] A varnish was prepared in the same manner as in Example 11 except that 3.74 parts by mass of PEROCTA H was used instead of PERMENTA H as the hydroperoxide (C), thereby obtaining a laminate having a film layer having a thickness of 30 μm.

[0371] (Example 14)

[0372] A varnish was prepared in the same manner as in Example 1 except that 1.87 parts by mass of a hydroperoxide represented by the following formula (12-2) (Luperox TAH (trade name), manufactured by ARKEMA Yoshitomi, Ltd.) was used instead of PERMENTA H as the hydroperoxide (C). A laminate having a thin film layer thickness of 30 μm was obtained.

[0373]

[0374] (Example 15)

[0375] A varnish was prepared in the same manner as in Example 11 except that 3.74 parts by mass of Luperox TAH was used instead of PERMENTA H as the hydroperoxide (C), thereby obtaining a laminate having a film layer having a thickness of 30 μm.

[0376] (Example 16)

[0377] Using the n shown in the above formula (5) 2 In addition, 10.32 parts by mass of a maleimide compound (BMI-2300 (trade name), manufactured by Yamato Chemical Industry Co., Ltd.) containing 1 to 3 components was used instead of MIR-3000-70MT among the four types used as compound (A), the blending amount of BMI-70 was changed to 15.62 parts by mass (converted as non-volatile components), and the blending amount of BMI-80 was changed to 15.62 parts by mass (converted as non-volatile components). A varnish was prepared in the same manner as in Example 11 to obtain a laminate having a thin film layer with a thickness of 30 μm.

[0378] (Comparative Example 1)

[0379] A varnish was prepared in the same manner as in Example 1 except that PERMENTA H as the hydroperoxide (C) was not used, thereby obtaining a laminate having a thin film layer having a thickness of 30 μm.

[0380] (Comparative Example 2)

[0381] A varnish was prepared in the same manner as in Comparative Example 1 except that the blending amount of dicumyl peroxide as the organic peroxide (B) was changed to 10.85 parts by mass, to obtain a laminate having a thin film layer with a thickness of 30 μm.

[0382] (Comparative Example 3)

[0383] A varnish was prepared in the same manner as in Example 1 except that dicumyl peroxide as the organic peroxide (B) was not used, thereby obtaining a laminate having a thin film layer having a thickness of 30 μm.

[0384] (Comparative Example 4)

[0385] A varnish was prepared in the same manner as in Comparative Example 3 except that the amount of PERMENTA H as the hydroperoxide (C) was changed to 10.85 parts by mass, to obtain a laminate having a film layer having a thickness of 30 μm.

[0386] (Comparative Example 5)

[0387] A varnish was prepared in the same manner as in Example 3 except that dicumyl peroxide as the organic peroxide (B) was not used, thereby obtaining a laminate having a thin film layer with a thickness of 30 μm.

[0388] (Comparative Example 6)

[0389] A varnish was prepared in the same manner as in Comparative Example 5 except that the amount of PERCUMY P as the hydroperoxide (C) was changed to 10.85 parts by mass, to obtain a laminate having a thin film layer with a thickness of 30 μm.

[0390] (Comparative Example 7)

[0391] A varnish was prepared in the same manner as in Example 5 except that dicumyl peroxide as the organic peroxide (B) was not used, thereby obtaining a laminate having a thin film layer having a thickness of 30 μm.

[0392] (Comparative Example 8)

[0393] A varnish was prepared in the same manner as in Comparative Example 7 except that the amount of PERCUMY H-80 as the hydroperoxide (C) was changed to 10.85 parts by mass, to obtain a laminate having a thin film layer with a thickness of 30 μm.

[0394] (Comparative Example 9)

[0395] A varnish was prepared in the same manner as in Example 1 except that 1.87 parts by mass of an organic peroxide represented by the following formula (1′) (PERBUTYL D (trade name), manufactured by NOF Corporation) was used instead of dicumyl peroxide as the organic peroxide (B). A laminate having a thin film layer thickness of 30 μm was obtained.

[0396]

[0397] (Comparative Example 10)

[0398] A varnish was prepared in the same manner as in Comparative Example 9 except that 2E4MZ was not used as the imidazole compound (H), the amount of PERMENTA H as the hydroperoxide (C) was changed to 3.74 parts by mass, and the amount of PERBUTYL D as the organic peroxide (B) was changed to 5.56 parts by mass. A laminate having a thin film layer thickness of 30 μm was obtained.

[0399] (Comparative Example 11)

[0400] A varnish was prepared in the same manner as in Comparative Example 3 except that 1.87 parts by mass of a hydroperoxide represented by the following formula (12-3) (Luperox TBH (trade name), manufactured by ARKEMA Yoshitomi, Ltd.) was used instead of PERMENTA H as the hydroperoxide (C). A laminate having a thin film layer thickness of 30 μm was obtained.

[0401]

[0402] (Comparative Example 12)

[0403] A varnish was prepared in the same manner as in Comparative Example 11 except that the blending amount of Luperox TBH as the hydroperoxide (C) was changed to 3.74 parts by mass, to obtain a laminate having a thin film layer with a thickness of 30 μm.

[0404] [Evaluation of Laminated Body]

[0405] (1) Storage stability of varnish

[0406] The viscosity (a) of the varnishes obtained in Examples 1 to 15 and Comparative Examples 1 to 11 was measured at 25°C using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The viscosity (b) was measured again using the B-type viscometer after standing in a sealed container at 25°C for one week. The viscosity change rate after one week was calculated using the following formula: AA indicates a viscosity change rate of less than 10%, A indicates a viscosity change rate of 10% or more but less than 20%, B indicates a viscosity change rate of 20% or more but less than 40%, C indicates a viscosity change rate of 40% or more, and D indicates a viscosity change rate of less than 10%. The viscosity change rate after one week was calculated using the following formula: AA indicates a viscosity change rate of less than 10%, A indicates a viscosity change rate of 10% or more but less than 20%, B indicates a viscosity change rate of 20% or more but less than 40%, C indicates a viscosity change rate of 40% or more, and D indicates a viscosity change rate of less than 40% but less than 40%.

[0407] Viscosity change rate = {|viscosity (b) - viscosity (a)| / viscosity (a)} × 100

[0408] (2) Bendability

[0409] After cutting the laminates obtained in Examples 1 to 15 and Comparative Examples 1 to 11 into strips of 5 cm × 10 cm, they were wound around a metal tube with a specified outer diameter at room temperature so that the polyethylene terephthalate film supporting the substrate became the inner side, and the film was unwound after being held for 5 seconds. After repeating this operation 10 times, the flexibility was evaluated by visually confirming the presence or absence of cracks in the resin composition layer. The case where the outer diameter of the smallest metal tube in which no cracks in the resin composition layer were confirmed was 10 mm or less was recorded as AA, the case where it was 10 mm or more and 20 mm or less was recorded as A, the case where it was 20 mm or more and 60 mm or less was recorded as B, and the case where it was 60 mm or more was recorded as C. The results are shown in Tables 1 to 2.

[0410] (3) Flux activity

[0411] Resin powder obtained by pulverizing the thin film layers obtained in Examples 1 to 15 and Comparative Examples 1 to 11 was spread on the shiny surface of a 12 μm thick electrolytic copper foil (3EC-III (trade name), manufactured by Mitsui Mining & Smelting Co., Ltd.), and a 0.5 mm diameter solder ball (ECO SOLDER (registered trademark) Ball M705 (trade name), Sn-3.0Ag-0.5Cu alloy, manufactured by Senju Metal Industries, Ltd.) was placed. This was heated on a hot plate maintained at 235°C for 1 minute to melt the solder on the copper foil, and then cooled to room temperature. The contact angle of the solder ball was measured as it spread on the copper foil to evaluate the flux activity. The contact angle of the solder ball was determined using a digital microscope (KH-7700 (trade name), manufactured by Hirox Co., Ltd.) to determine the radius (c) and height (d) of the solder ball that melted and spread on the copper foil, and the contact angle was calculated using the following formula.

[0412] Contact angle of solder ball = 2arctan{(d) / (c)}

[0413] The contact angle of the solder ball was AA when it was less than 1.60 rad, A when it was 1.60 rad or more and less than 2.00 rad, B when it was 2.00 rad or more and less than 2.20 rad, and C when it was 2.20 rad or more. The results are shown in Tables 1 and 2.

[0414] (4) Curing

[0415] The resin powders obtained by pulverizing the thin film layers obtained in Examples 1 to 15 and Comparative Examples 1 to 11 were measured for heat release in the range of 30°C to 350°C using a differential scanning calorimeter (Q100 (trade name), manufactured by TA Instruments Co., Ltd.) at a heating rate of 10°C / min. Heat release (W / g) at 145°C was measured as AA for a value of 0.05 W / g or greater, A for a value of 0.04 W / g or greater and less than 0.05 W / g, B for a value of 0.03 W / g or greater and less than 0.04 W / g, and C for a value less than 0.03 W / g. The results are shown in Tables 1 and 2.

[0416] (5) Gap

[0417] The laminates obtained in Examples 1 to 15 and Comparative Examples 1 to 11 were cut into 8 mm × 8 mm squares and laminated onto an evaluation substrate. A semiconductor chip having a Cu column composed of copper and solder on an electrode was thermally compressed and mounted using a flip-chip bonder (LFB-2301 (trade name), manufactured by Shinkawa Co., Ltd.) at a table temperature of 70°C, a bonding head temperature of 260°C, a load of 50 N, and a time of 6 seconds. For the mounted samples, an ultrasonic defect detection visualization device (μ-SDS (trade name), manufactured by Japan Clout Claimer Co., Ltd.) was used to confirm the presence or absence of voids in the thin film layer within the semiconductor chip mounting area. The void ratio was recorded as AA when it was less than 5%, A when it was 5% or more and less than 10%, B when it was 10% or more and less than 30%, and C when it was 30% or more. The results are shown in Tables 1 and 2.

[0418] (6) Minimum melt viscosity

[0419] 1 g of the resin powder obtained by crushing the film layers obtained in Examples 1 to 15 and Comparative Examples 1 to 11 was weighed and formed into a sheet having a diameter of 25 mm and a thickness of 1.5 mm using a tablet forming machine (SSP-10A (trade name), manufactured by Shimadzu Corporation) under a pressure of 20 kN and a time of 5 minutes. The viscosity was measured in the range of 40°C to 260°C using a rheometer (ARES-G2 (trade name), manufactured by TA Instruments Co., Ltd.) at a heating rate of 10°C / min. The case where the minimum melt viscosity was 10,000 Pa·s or more and less than 50,000 Pa·s was designated as AA, the case where the minimum melt viscosity was 50,000 Pa·s or more and less than 70,000 Pa·s, or 1,000 Pa·s or more and less than 10,000 Pa·s was designated as A, the case where the minimum melt viscosity was 70,000 Pa·s or more and less than 100,000 Pa·s, or 100 Pa·s or more and less than 1,000 Pa·s was designated as B, and the case where the minimum melt viscosity was 100,000 Pa·s or less than 100 Pa·s was designated as C. The results are shown in Tables 1 and 2.

[0420] [Table 1]

[0421]

[0422] [Table 2]

[0423]

[0424] This application is based on Japanese patent application (Japanese Patent Application No. 2019-122335) filed on June 28, 2019, the contents of which are incorporated herein by reference.

[0425] Industrial applicability

[0426] The film of this embodiment exhibits an excellent balance of physical properties, including storage stability, flexibility, flux activity, curability, low voiding, and melt viscosity, making it suitable as a pre-underfill material. Furthermore, the film of this embodiment exhibits excellent flux activity, enabling the laminated bodies formed by bonding chips to substrates, chips to semiconductor wafers, or chips to chips to achieve high reliability that can withstand long-term use.

Claims

1. A film comprising: A compound (A) containing at least one selected from the group consisting of maleimide compounds and citraconimide compounds; An organic peroxide (B) containing at least one selected from the group consisting of organic peroxides represented by the following formula (1) and the following formula (2); and Hydroperoxide (C), In formula (1), R 1 each independently represents a hydrogen atom, a methyl group, or an ethyl group, In formula (2), R 2 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 1 represents a group represented by the following formula (3) or (4), In formula (3), R 3 represents a hydrogen atom, a methyl group, or an ethyl group, R 4 represents an alkylene group having 1 to 3 carbon atoms, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, In formula (4), R 6 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, X 2 represents a group represented by the following general formulae (a) to (c), In formula (c), n 1 represents an integer greater than or equal to 1 and less than or equal to 5, The film is used for pre-applying the underfill material.

2. The film according to claim 1, wherein The compound (A) contains at least one selected from the group consisting of 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, 1,2-bis(maleimide)ethane, 1,4-bis(maleimide)butane, 1,6-bis(maleimide)hexane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-phenylmaleimide, a maleimide compound represented by the following formula (5), a maleimide compound represented by the following formula (6), a maleimide compound represented by the following formula (7), a maleimide compound represented by the following formula (8), and a bismaleimide compound containing a structural unit represented by the following formula (9) and maleimide groups at both ends. In formula (5), R 7 Each independently represents a hydrogen atom or a methyl group, n 2 represents an integer greater than 1, In formula (6), n 3 represents an integer greater than or equal to 1 and less than or equal to 30, In formula (7), R 8 Each independently represents a hydrogen atom, a methyl group, or an ethyl group, R 9 each independently represents a hydrogen atom or a methyl group, In formula (8), R 10 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 represents an integer greater than or equal to 1 and less than or equal to 10, In formula (9), 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, R 13 Each 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, n 5 It represents an integer greater than or equal to 1 and less than or equal to 10.

3. The film according to claim 2, wherein The compound (A) contains: at least one selected from the group consisting of 2,2'-bis{4-(4-maleimidephenoxy)phenyl}propane, the maleimide compound represented by the formula (5), the maleimide compound represented by the formula (6), the maleimide compound represented by the formula (7), the maleimide compound represented by the formula (8), and a bismaleimide compound containing a structural unit represented by the formula (9) and maleimide groups located at both ends.

4. The film according to any one of claims 1 to 3, wherein The hydroperoxide (C) contains at least one selected from the group consisting of a hydroperoxide represented by the following formula (10), a hydroperoxide represented by the following formula (11), and a hydroperoxide represented by the following formula (12). In formula (10), R 14 Each independently represents a hydrogen atom or a methyl group, R 15 represents a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group, In formula (11), R 16 Each independently represents a hydrogen atom or a methyl group, R 17 represents a hydrogen atom, a methyl group, an isopropyl group, or a tert-butyl group, In formula (12), R 18 Each independently represents a hydrogen atom or a methyl group, R 19 Each independently represents a hydrogen atom or a methyl group, R 20 Each independently represents a hydrogen atom or a methyl group.

5. The film according to any one of claims 1 to 3, wherein The molecular weight of the hydroperoxide (C) is 100 or more.

6. The film according to any one of claims 1 to 3, wherein The hydroperoxide (C) contains at least one selected from the group consisting of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and tert-amyl hydroperoxide.

7. The film according to any one of claims 1 to 3, wherein The organic peroxide (B) contains at least one selected from the group consisting of diisopropyl benzene peroxide, n-butyl-4,4-di-(tert-butylperoxy)valerate, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3-ol, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

8. The film according to any one of claims 1 to 3, further comprising a benzoxazine compound (D) represented by the following formula (13), the following formula (14), the following formula (15), and the following formula (16), In formula (13), R 21 Each independently represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 22 represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulae (d) to (w), n 6 represents an integer from 1 to 4, In formula (14), R 23 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 24 represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, a cycloalkyl group, or a monovalent to tetravalent organic group represented by the following general formulas (d) to (r), n 7 represents an integer from 1 to 4, In formula (15), R 25 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent, In formula (16), R 26 represents an alkyl group, a cycloalkyl group, or a phenyl group which may have a substituent, In formulas (d) to (w), R a represents an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, R b represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group.

9. The film according to claim 8, wherein The benzoxazine compound (D) contains at least one selected from the group consisting of compounds represented by the following formula (17) and the following formula (18), In formula (17), R 27 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 28 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, X 3 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO2-", a group represented by the formula "-CO-", an oxygen atom, or a single bond, In formula (18), R 29 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, and R 30 Each independently represents a hydrogen atom, an aryl group, an aralkyl group, an alkenyl group, an alkyl group, or a cycloalkyl group, X 4 represents an alkylene group, a group represented by the following formula (19), a group represented by the formula "-SO2-", a group represented by the formula "-CO-", an oxygen atom, or a single bond, In formula (19), Y is an alkylene group or a hydrocarbon group having 6 or more and 30 or less carbon atoms and an aromatic ring, and n 8 Indicates an integer greater than 0.

10. The film according to claim 8, wherein The benzoxazine compound (D) contains at least one selected from the group consisting of a compound represented by the following formula (20), a compound represented by the following formula (21), a compound represented by the following formula (22), a compound represented by the following formula (23), a compound represented by the following formula (24), and a compound represented by the following formula (25), In formula (22), R 31 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, 11. The film according to claim 8, wherein The content of the benzoxazine compound (D) is 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A). 12 . The film according to claim 1 , further comprising an acrylic compound (E).

13. The film according to claim 12, wherein The content of the acrylic compound (E) is 5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the compound (A). 14 . The film according to claim 1 , further comprising a flux component (F).

15. The film according to claim 14, wherein The content of the flux component (F) is 5 parts by mass or more and 60 parts by mass or less relative to 100 parts by mass of the total amount of the compound (A). 16 . The film according to claim 1 , further comprising an inorganic filler (G).

17. The film according to claim 16, wherein The average particle size of the inorganic filler (G) is 3 μm or less.

18. The film according to claim 16, wherein The inorganic filler (G) contains at least one selected from the group consisting of silica, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, magnesium oxide, and magnesium hydroxide.

19. The film according to claim 16, wherein The content of the inorganic filler (G) is 300 parts by mass or less relative to 100 parts by mass of the compound (A). 20 . The film according to claim 1 , further comprising an imidazole compound (H).

21. The film according to claim 20, wherein The content of the imidazole compound (H) is 10 parts by mass or less relative to 100 parts by mass of the compound (A). 22 . The film according to claim 1 , having a thickness of 10 μm to 100 μm.

23. A laminate comprising: a supporting substrate; and, A layer comprising the thin film according to any one of claims 1 to 22, laminated on the supporting substrate.

24. A semiconductor wafer with a thin film layer, comprising: semiconductor wafers; and, The laminate according to claim 23, which is laminated on the semiconductor wafer, A layer including the thin film is stacked on the semiconductor wafer.

25. A semiconductor mounting substrate with a thin film layer, comprising: a semiconductor mounting substrate; and The laminate according to claim 23, which is laminated on the semiconductor mounting substrate, A layer including the thin film is stacked on the semiconductor mounting substrate. 26 . A semiconductor device comprising: the semiconductor wafer with a thin film layer according to claim 24 and / or the semiconductor mounting substrate with a thin film layer according to claim 25 .

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